Method for organic compound degradation and method for producing hydrogen

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention generally relates to a catalyst, a manufacturing method of the catalyst, a method of carbon dioxide (CO₂) reduction using the catalyst, a method of heavy metal reduction using the catalyst, a method of hydrogenation of organic compounds, a method of organic compound degradation, and a method of hydrogen production. In particular, the present invention relates to an oxysulfide catalyst including copper.

2. Description of Related Art

Recently, global warming and climate change has become a huge threat to the environment. Therefore, CO₂emission is an important issue awaiting to be solved worldwide. In particular, a method of converting CO₂into ethanol (C₂H₅OH) using ruthenium (Ru) metal complex has been proposed. However, such mechanism requires external energy, such as external high power light sources, to trigger the reaction. Therefore, it is difficult to conduct the conversion at room temperature and atmosphere pressure. High power light sources not only impose a burden on the cost of the conversion, but also raise safety issues on a scale-up production system. Therefore, providing catalyst which enables elimination of CO₂while being cost effective has become a topic to be researched in the field.

One of the heavy metal ions with highly toxic property is hexavalent chromium (Cr(VI)) which is widely used in industrial activities such as plastic, leather, textile, metal, electroplating processing, etc. The existence of Cr(VI) in drinking water has engrossed the attention of many scientists to remediate it due to its poisonous property and adverse effect on drinking water. The highly mobile nature and non biodegradability of Cr(VI) are not only harmful to aqueous environment but also to human life. Therefore, the reduction of Cr(VI) is highly required for environmental remediation.

Hydrogenation of organic compounds involves in many chemical reactions to facilitate the formation of second compound. The hydrogenation reaction has been popular to undergo with the hydrogen gas flow and catalyst of Pt, Pd, Ni, etc. High temperature is needed for the H₂-involving reaction. The reduction reaction at mild condition for a green and safe synthesis is encouraging.

SUMMARY OF THE INVENTION

The invention provides a catalyst and a manufacturing thereof, which effectively aids the conversion of CO₂gas into ethanol, effectively aids the reduction of heavy metal, or effectively aids the hydrogenation of organic compounds at atmospheric condition.

The invention provides a bimetal oxysulfide solid-solution catalyst. The catalyst is represented by formula (1):

M⁽¹⁾_xM⁽²⁾_yO_zS_γ (1),

wherein in formula (1), M⁽¹⁾includes a multivalent metal and M⁽²⁾includes a mono-, di-, tri-, tetra-, or penta-valent metal; 0<y<0.3; 0.7<x<1.0; 0<z<0.5; 0.5<γ<1.0.

In an embodiment of the invention, M⁽¹⁾includes Copper (Cu) and the bimetal oxysulfide solid-solution catalyst is represented by formula (2):

Cu_xM⁽²⁾_yO_zS_γ (2),

wherein in formula (2), M⁽²⁾comprises the mono-, di-, tri-, tetra-, or penta-valent metal; 0<y<0.3; 0.7<x<1.0; 0<z<0.5; 0.5<γ<1.0.

In an embodiment of the invention, in formula (2), M⁽²⁾includes monovalent Silver (Ag), divalent Zinc (Zn), Manganese (Mn), Nickel (Ni), Cobalt (Co), and Tin (Sn^II), trivalent Indium (In), Cerium (Ce), Antimony (Sb), and Gallium (Ga), tetravalent Tin (Sn^IV), or pentavalent Molybdenum (Mo).

The invention provides a manufacturing method of the bimetal oxysulfide solid-solution catalyst. First, a copper-containing salt is dissolved in distilled water to obtain a first solution. Meanwhile, an M⁽²⁾-containing compound is dissolved in distilled water to obtain a second solution. The first solution and the second solution are mixed to obtain a mixture solution. An organosulfur compound is added into the mixture solution, and the mixture solution is heated to a temperature range of 50-100° C. A precipitate is centrifuged from the mixture solution and is dried to obtain the bimetal oxysulfide solid-solution catalyst.

In an embodiment of the invention, the method further includes a step of adding hydrazine to the mixture solution in a dropwise manner.

The invention provides a method for CO₂reduction. First, the bimetal oxysulfide solid-solution catalyst and a reactant solution are provided in the reactor. Subsequently, CO₂gas is passed into the reactor to react with the reactant solution.

The invention provides a method for heavy metal reduction. First, the bimetal oxysulfide solid-solution catalyst is provided in a reactor. Then, a heavy metal aqueous solution is added to the reactor. Subsequently, the bimetal oxysulfide solid-solution catalyst and the heavy metal aqueous solution are reacted.

In an embodiment of the invention, the heavy metal includes hexavalent chromium (Cr(VI)).

The invention provides a method for the hydrogenation of organic compounds at an atmospheric condition. First, the bimetal oxysulfide solid-solution catalyst, an aqueous solution of organic compounds, and a reducing agent are added to a reactor. Subsequently, the bimetal oxysulfide solid-solution catalyst and the organic aqueous solution are reacted.

In an embodiment of the invention, the compounds includes rhodamine B, methyl orange, or methylene blue.

In an embodiment of the invention, the reducing agent includes sodium boron hydride or oxalic acid.

The invention provides a method for organic compound degradation. First, a bimetal oxysulfide solid-solution catalyst is provided. An aqueous solution of the organic compound and the bimetal oxysulfide solid-solution catalyst are added into a reactor. The bimetal oxysulfide solid-solution catalyst and the aqueous solution of the organic compound are reacted.

In an embodiment of the invention, the organic compound includes methylene blue.

In an embodiment of the invention, the bimetal oxysulfide solid-solution catalyst includes monovalent Silver (Ag), divalent Zinc (Zn), Manganese (Mn), Nickel (Ni), Cobalt (Co), and Tin (Sn^II), trivalent Indium (In), Cerium (Ce), Antimony (Sb), and Gallium (Ga), tetravalent Tin (Sn^IV), or pentavalent Molybdenum (Mo).

In an embodiment of the invention, the reactor is shielded from an ambient light.

The invention provides a method for producing hydrogen. First, a bimetal oxysulfide solid-solution catalyst dispersed in an aqueous solution is provided. Alcohol or organic acid is added into a catalytic reactor. After adding alcohol or organic acid into the catalytic reactor, the bimetal oxysulfide solid-solution catalyst starts to react.

In an embodiment of the invention, the alcohol includes methanol or ethanol.

In an embodiment of the invention, the organic acid includes acetic acid.

In an embodiment of the invention, the catalytic reactor is shielded from an ambient light.

Based on the above, the bimetal oxysulfide solid-solution catalyst of the invention includes copper element and may be manufactured at a low temperature. Due to the specific structure of the catalyst of the invention, CO₂gas may be converted to ethanol and reduction of heavy metal and the hydrogenation/degradation of organic chemicals may be performed at atmospheric condition. Moreover, hydrogen may also be produced under atmospheric condition with the aid of the bimetal oxysulfide solid-solution catalyst of the invention. As such, the power requirement for external energy may be eliminated. In addition, the bimetal oxysulfide solid-solution catalyst of the invention may be recycled. Therefore, the cost for the reduction processes may be significantly lowered.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings are included to provide a further understanding of the disclosure, and are incorporated in and constitute a part of this specification. The drawings illustrate embodiments of the disclosure and, together with the description, serve to explain the principles of the disclosure.

FIG. 1A is a diagram illustrating the ability of ethylene blue degradation in the dark for powders 13-17.

FIG. 1B is a diagram illustrating the ability of methylene blue degradation in the dark for powders 13, 17, 18-21.

FIG. 1C is a diagram illustrating the ability of methylene blue degradation in the dark for powders 22-29.

FIG. 1D is a diagram illustrating the ability of methylene blue degradation in the dark for powders 17, 30-31.

FIG. 2A is a diagram illustrating the ability of hydrogen production in the dark for powders 32-37.

FIG. 2B is a diagram illustrating the ability of hydrogen production in the dark for powders 32, 38-41.

FIG. 2C is a diagram illustrating the hydrogen production in the solutions with different amount of methanol using powder 32.

FIG. 2D is a diagram illustrating the hydrogen production at different reaction temperatures using powder 32.

FIG. 3A is a diagram illustrating the reusability of powder 32 for hydrogen production.

FIG. 3B is a diagram illustrating the high resolution Cu2p XPS spectrum of powder 32 after 5 runs.

DESCRIPTION OF THE EMBODIMENTS

Reference will now be made in detail to the present preferred embodiments of the invention, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numbers are used in the drawings and the description to refer to the same or like parts.

A bimetal oxysulfide solid-solution catalyst is prepared at a low temperature condition. Specifically, 4.6 grams of a M⁽¹⁾-containing salt is dissolved in distilled water to obtain a first solution. Meanwhile, 2 grams to 6 grams of an M⁽²⁾-containing compound is dissolved in 250 mL of distilled water to obtain a second solution. M⁽¹⁾is a multivalent metal. For example, M⁽¹⁾may be copper and the M⁽¹⁾-containing salt may be copper nitrate. However, it construes no limitation in the invention. Other suitable copper-containing salt may be used as well. On the other hand, M⁽²⁾is, for example, mono-, di-, tri-, tetra-, or penta-valent metal. Specific examples of M⁽²⁾includes, but not limited to, monovalent Silver (Ag), divalent Zinc (Zn), Manganese (Mn), Nickel (Ni), Cobalt (Co), and Tin (Sn^II), trivalent Indium (In), Cerium (Ce), Antimony (Sb), and Gallium (Ga), tetravalent Tin (Sn^IV), pentavalent Molybdenum (Mo), or other similar metal elements. In other words, examples of the M⁽²⁾-containing compound may include zinc acetate dihydrate, manganese (II) chloride, cobalt (II) chloride, nickel (II) chloride, indium (III) chloride, tin (II) chloride, cerium (III) nitrate hexahydrate, antimony (III) chloride, gallium (III) acetate, tin (IV) chloride hydrate, molybdenum (V) chloride, silver (I) nitrate, or other metal salts. However, they construe no limitation in the disclosure. Other compounds including suitable metal compounds may also be adapted. Subsequently, the first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. An organosulfur compound having a concentration of 15 g/L is added into the mixture solution and the mixture solution is allowed to react with the organosulfur compound for 30 minutes. The organosulfur compound is, for example, thioacetamide or other suitable compound. Subsequently, the mixture solution is heated to a temperature range of 50° C. to 100° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. Thereafter, the precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain a bimetal oxysulfide solid-solution catalyst.

The bimetal oxysulfide solid-solution catalyst obtained is represented by formula (1):

M⁽¹⁾_xM⁽²⁾_yO_zS_1-z (1),

in formula (1), M⁽¹⁾includes Copper (Cu) and M⁽²⁾includes monovalent Silver (Ag), divalent Zinc (Zn), Manganese (Mn), Nickel (Ni), Cobalt (Co), and Tin (Sn^II), trivalent Indium (In), Cerium (Ce), Antimony (Sb), and Gallium (Ga), tetravalent Tin (Sn^IV), or pentavalent Molybdenum (Mo), 0<y<0.3, 0.7<x<1.0, 0<z<0.5, and 0.5<γ<1.0.

The bimetal oxysulfide solid-solution catalyst obtained may have various applications. For example, the bimetal oxysulfide solid-solution catalyst may be used for CO₂reduction, heavy metal reduction, or hydrogenation of organic compounds.

Specifically, when the bimetal oxysulfide solid-solution catalyst is used for CO₂reduction, 0.1 gram of catalyst is provided in a reactor. Subsequently, 100 mL of reactant solution is added to the reactor. The reactant solution is, for example, a solution includes water. The reactant solution and the bimetal oxysulfide solid-solution catalyst are being stirred with a magnet with a stirring speed of 280 rpm (revolutions per minute). Thereafter, CO₂gas is passed into the reactor to react with the reactant solution. In the present embodiment, the CO₂gas may be generated by decomposing sodium bicarbonate (NaHCO₃) with the droplet addition of diluted nitric acid (HNO₃) aqueous solution to control the CO₂generation. However, it construes no limitation in the invention. Other alternative CO₂gas source may be adapted. The CO₂gas is allowed to react with the reactant solution for 16-24 hours to generate ethanol. In other words, the bimetal oxysulfide solid-solution catalyst of the present embodiment aids the conversion of CO₂gas into ethanol. It should be noted that the foregoing process is conducted at atmospheric condition. In other words, the process is performed at room temperature under atmosphere pressure. Alternatively speaking, only ambient light is present and no additional energy source is required. However, the invention is not limited thereto. In some other alternative embodiments, the reaction may be conducted in a dark room. That is, the reaction may be performed without the presence of any external energy.

In some alternative embodiments, the bimetal oxysulfide solid-solution catalyst of the invention may be used for heavy metal reduction. Specifically, when the bimetal oxysulfide solid-solution catalyst is used for heavy metal reduction, 0.1 grams of the bimetal oxysulfide solid-solution catalyst is provided in a reactor. Subsequently, 100 mL of a heavy metal aqueous solution with a concentration of 50 ppm is added into the reactor. The heavy metal is, for example, metallic element having an atomic number of 20 or greater. In the present embodiment, the heavy metal may include environment harmful hexavalent chromium (Cr(VI)). However, it construes no limitation in the invention. Other heavy metals may also be the subject for reduction. Thereafter, shake the reactor to render a uniform distribution of the bimetal oxysulfide solid-solution catalyst in the heavy metal aqueous solution. The bimetal oxysulfide solid-solution catalyst and the heavy metal aqueous solution are allowed to react for 2 minutes, so as to perform heavy metal reduction.

In some alternative embodiments, the bimetal oxysulfide solid-solution catalyst may be recycled. For example, after the foregoing heavy metal reduction process, the bimetal oxysulfide solid-solution catalyst may be centrifuged to separate from the solution. Without rinsing the bimetal oxysulfide solid-solution catalyst, the foregoing step of heavy metal reduction may be repeated again.

In some alternative embodiments, the bimetal oxysulfide solid-solution catalyst of the invention may be used for the hydrogenation of organic compounds. Specifically, when the bimetal oxysulfide solid-solution catalyst is used for hydrogenation reaction, 100 mL of aqueous solution of organic compounds (a dye aqueous solution) with a concentration of 100 ppm is add into in a 250 mL conical flask. Subsequently, 5 mL of reducing agent aqueous solution with a concentration of 0.1 mole is added into the conical flask. The organic compound is, for example, hydrocarbon having double or triple bonds. In the present embodiment, the organic compound may include methylene blue, methylene orange, or rhodamine B. However, it construes no limitation in the invention. Other organic compounds may also be the subject for hydrogenation reaction. On the other hand, the reducing agent is, for example, sodium boron hydride or oxalic acid. Under the stirring condition, 0.01 grams of the bimetal oxysulfide solid-solution catalyst is provided in the conical flask. Thereafter, shake the conical flask to render a uniform distribution of the bimetal oxysulfide solid-solution catalyst in the dye aqueous solution. The bimetal oxysulfide solid-solution catalyst and the dye aqueous solution are allowed to react for hydrogenation reaction.

In some alternative embodiments, the bimetal oxysulfide solid-solution catalyst of the invention may be used for degradation of organic compounds. Specifically, when the bimetal oxysulfide solid-solution catalyst is used for degradation, 100 mL of aqueous solution of organic compounds (a dye aqueous solution) and the bimetal oxysulfide solid-solution catalyst are added into a reactor for reaction. The organic compound is, for example, methylene blue. However, it construes no limitation in the invention. Other organic compounds may also be the subject for degradation. The degradation reaction may occur in a dark room condition. In other words, the reactor is shielded from an ambient light. The reactant mixture is under magnetic stirring with 280 r/m. 3 mL sample is taken every 5 minutes from the reactor. Thereafter, the degradation ratio of the organic compound is calculated.

In some alternative embodiments, the bimetal oxysulfide solid-solution catalyst of the invention may be used for producing hydrogen. Specifically, when the bimetal oxysulfide solid-solution catalyst is used for hydrogen production, alcohol or organic acid was added into a catalyst dispersion solution containing 225 mg of catalyst to from a total 450 mL batch solution. The alcohol is, for example, methanol or ethanol. On the other hand, the organic acid may be acetic acid. However, it construes no limitation in the invention. Other alcohols and organic acids may also be used for hydrogen production. The hydrogen production reaction may occur in a dark room condition. In other words, the reactor is shielded from an ambient light. The gas sampling is taken in the time interval of 20 minutes. A hydrogen calibration line may be built to quantitatively measure the H₂generation rate.

The examples of the invention will be described in detail below.

Synthesis Example 1: Copper Zinc Oxysulfide (Cu_xZn_yO_zS_γ) Powder 1

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 6.0 grams of zinc acetate dihydrate (Zn(CH₃COO)₂.2H₂O) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 90° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 1.

Synthesis Example 2: Copper Manganese Oxysulfide (Cu_xMn_yO_zS_γ) Powder 2

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 2.0 grams of manganese (II) chloride (MnCl₂) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 90° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 2.

Synthesis Example 3: Copper Cobalt Oxysulfide (Cu_xCo_yO_zS_γ) Powder 3

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 3.0 grams of cobalt (II) chloride (CoCl₂) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 90° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 3.

Synthesis Example 4: Copper Nickel Oxysulfide (Cu_xNi_yO_zS_γ) Powder 4

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 3.0 grams of nickel (II) chloride (NiCl₂) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 90° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 4.

Synthesis Example 5: Copper Indium Oxysulfide (Cu_xIn_yO_zS_γ) Powder 5

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 3.0 grams of indium (III) chloride (InCl₃) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 90° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 5.

Synthesis Example 6: Copper Tin (II) Oxysulfide (Cu_xSn^II_yO_zS_γ) Powder 6

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 3.0 grams of anhydrous tin (II) chloride (SnCl₂) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 90° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 6.

Synthesis Example 7: Copper Cerium Oxysulfide (Cu_xCe_yO_zS_γ) Powder 7

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 4.64 grams of cerium (III) nitrate hexahydrate (Ce(NO₂)₃.6H₂O) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 85° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 7.

Synthesis Example 8: Copper Antimony Oxysulfide (Cu_xSb_yO_zS_γ) Powder 8

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 3.0 grams of antimony (III) chloride (SbCl₃) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 90° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 8.

Synthesis Example 9: Copper Gallium Oxysulfide (Cu_xGa_yO_zS_γ) Powder 9

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 3.0 grams of gallium (III) acetate (Ga(CH₃COO)₃) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 95° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 9.

Synthesis Example 10: Copper Tin (IV) Oxysulfide (Cu_xSn^IV_yO_zS_γ) Powder 10

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 4.0 grams of tin (IV) chloride hydrate (SnCl₄.xH₂O) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 90° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 10.

Synthesis Example 11: Copper Molybdenum Oxysulfide (Cu_xMo_yO_zS_γ) Powder 11

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 3.0 grams of molybdenum (V) chloride (MoCl₅) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 95° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 11.

Synthesis Example 12: Copper Silver Oxysulfide (Cu_xAg_yO_zS_γ) Powder 12

4.6 grams of copper nitrate (Cu(NO₃)₂.2.5H₂O) is dissolved in 250 mL of distilled water to obtain a first solution. 3.0 grams of silver (I) nitrate (AgNO₃) is dissolved in 250 mL of distilled water to obtain a second solution. The first solution and the second solution are mixed while being stirred by a magnet for 30 minutes to obtain a mixture solution. Thereafter, 100 mL of thioacetamide (CH₃CSNH₂) solution having a concentration of 15 g/L is added to the mixture solution and the mixture solution is allowed to react with the thioacetamide solution for 30 minutes. Subsequently, the mixture solution is heated to 80° C. and 0.15 mL of hydrazine is added to the mixture solution in a dropwise manner to react for 2 hours. The precipitate is centrifuged. After rinsing the precipitate with distilled water until the precipitate is neutral, the precipitate is further rinsed twice with absolute ethanol. The precipitate is dried by an evaporator to obtain powder 12.

CO₂Reduction Reaction

Example 1: CO₂Reduction Reaction for Ethanol Using Catalyst Powder 1

The catalytic reduction of CO₂is conducted in a quartz glass reactor. 0.1 grams of the catalyst powder 1 and 100 mL of distilled water are added to the reactor and are being stirred with a magnet with a stirring speed of 280 rpm (revolutions per minute). Subsequently, CO₂gas is passed into the reactor. The CO₂gas is generated by decomposing sodium bicarbonate (NaHCO₃) with the addition of diluted nitric acid (HNO₃) aqueous solution (V:V) in a dropwise manner. The CO₂gas is allowed to react with the distilled water for 16-24 or t hours, depending upon the rate of NaHCO₃consumption. The volume V₁(unit:mL) of excessive amount of the non-reacted CO₂passed into the reactor is measured by collecting gas over water displacement method. In other words, the volume of non-reacted CO₂in the reactor during the duration of the reaction time of t hours is denoted by V₁. After the reaction time of t hours, the remaining NaHCO₃is continued to be decomposed by the addition of HNO₃, and the volume V₂(unit:mL) of CO₂gas generated herein is measured by collecting gas over water displacement method. Another trial of decomposing NaHCO₃without the presence of the catalyst is performed, and the volume of CO₂generated is denoted by V₀. Specifically, in the present embodiment, 5.0 grams of NaHCO₃has been decomposed and 1295 mL of CO₂is obtained. In other words, V₀is a constant value of 1295 mL in the present embodiment.

The volume V₃of CO₂gas being converted with the aid of the catalyst may be calculated by the following formula:

V₃=V₀−V₁−V₂.

The volume V₃of CO₂converting into ethanol can be calculated in terms of reaction rate with the unit of mmol/g·h by the following formula:

$R (mmol / g \cdot h) = \frac{(V_{3} / 1000)}{22.4 \times m \times t}$

R is the ethanol generation rate, t is the reaction time (unit:hour), m is the amount of catalyst used (unit:g), and 22.4 L/mole is the molar volume of ideal gas at STP condition.

It should be noted that no other organic compounds except for ethanol is detected in the solution. Moreover, the procedure of Example 1 has been conducted thrice. The first trial and the second trial are conducted with the presence of ambient light. The third trial is conducted in a dark room. In other words, no external energy is present in the third trial. The amount of ethanol obtained in Example 1 is illustrated in Table 1 below.

Examples 2-8: CO₂Reduction Reaction for Ethanol Using Catalyst Powders 2-8

Similar procedures as that of Example 1 have been conducted except the catalyst powder 1 is replaced by catalyst powders 2-8 respectively in Examples 2-8 and the procedures of some Examples have not been conducted for the second/third trials. It should be noted that Example 2-8 are only performed at a condition in which ambient light is present. The amount of ethanol obtained in Examples 2-8 are summarized in Table 1 below.

Example 9: CO₂Reduction Reaction for Ethanol Using the Recycled Catalyst Powder 1 after the First Trial

Similar procedure as that of Example 1 for powder 1 under the ambient light has been conducted for the recycled powder 1 after the first trial. The amount of ethanol obtained in Example 9 are summarized in Table 1 below.

Comparative Example 1: CO₂Reduction Reaction for Ethanol Using Catalyst Powder Having a Chemical Formula of CuO_zS_γ

Similar procedure as that of Example 1 has been conducted except the catalyst powder 1 is replaced by catalyst powder having a chemical formula of CuO_zS_γwithout the second metal M⁽²⁾from its precursor. The amount of ethanol obtained in Comparative Example 1 is summarized in Table 1 below.

TABLE 1

C₂H₅OH rate
C₂H₅OH rate

C₂H₅OH rate

for first trial
for second trial
C₂H₅OH rate
for the used

in ambient
in ambient
for third trial
catalyst

light
light
in dark room
in ambient light

Catalyst
(mmol/g · h)
(mmol/g · h)
(mmol/g · h)
(mmol/g · h)

Example 1
Cu_xZn_yO_zS_γ
14.98
12.00
6.6
—

(12.79)*

(6.5)*

Example 2
Cu_xMn_yO_zS_γ
9.34
7.83
—
—

(9.45)*

Example 3
Cu_xCo_yO_zS_γ
8.37
7.96
—
—

(8.39)*

Example 4
Cu_xNi_yO_zS_γ
7.28
7.58
—
—

(7.13)*

Example 5
Cu_xIn_yO_zS_γ
6.49
6.14
—
—

(6.64)*

Example 6
Cu_xSn^II_yO_zS_γ
14.51
14.61
—
—

(14.66)*

Example 7
Cu_xCe_yO_zS_γ
6.30
—
—
—

(6.24)*

Example 8
Cu_xSb_yO_zS_γ
5.76
—
—
—

(5.90)*

Example 9
Cu_xZn_yO_zS_γ
—
—
—
11.48

Comparative
CuO_zS_γ
0
—
—
—

Example 1

*The values in brackets are the ethanol generation rate obtained by GC-FID.

The numerical value of ethanol obtained in Table 1 is the amount of ethanol obtained per hour per gram of catalyst powder used. As clearly illustrated in Table 1, the bimetal oxysulfide solid-solution catalyst of the invention is able to aid the conversion of CO₂gas to ethanol under atmospheric condition or in a dark room. As such, the power requirement for external energy may be eliminated. In addition, as the reduction duration lasting for 16-24 hours, the second trials with the new catalyst has the similar ethanol generation rate to the first one. Moreover, as clearly illustrated in Example 9, the ethanol generation rate obtained by recycling used bimetal oxysulfide solid-solution catalyst is still decent, thereby proving the reusability of the bimetal oxysulfide solid-solution catalyst of the invention. Therefore, the cost of the reduction process may be significantly lowered.

In order to verify the volume V₃of CO₂gas is converted to ethanol, the following verification procedure is performed on the mixture solution.

Verification Method: Gas Chromatography-Flame Ionization Detector (GC-FID)

A GC-FID detector is being used to measure the ethanol concentration in the mixture solution for the ethanol generation rate. The testing condition is as follows:

- HP-INNDWAX capillary column: 30 m×0.25 mm
- Device: FID detector
- Inlet temperature: 200° C.
- Split ratio: 100:1
- Sample volume: 2 μL
- Column oven temperature: 180° C.
- Detector temperature: 200° C.
- Flow rate of hydrogen gas: 35 mL/min
- Flow rate of air: 400 mL/min
- Flow rate of high purity N₂assist gas: 30 mL/min

The ethanol generation rates were confirmed by GC-FID detector for Examples 1-8 in the ambient light and for Example 1 in the dark room. The data were shown in the brackets in Table 1 and matches with the results obtained from the CO₂volume conversion.

Based on the verification method above, it is apparent that the bimetal oxysulfide solid-solution catalyst of the invention is able to aid the conversion of CO₂to ethanol. In other words, by using the bimetal oxysulfide solid-solution catalyst of the invention, undesired CO₂gas can be easily converted to useful fuel sources without the presence of external energy. Therefore, the reduction of CO₂gas may be achieved at a lower cost.

Heavy Metal Reduction Reaction

Example 1: Hexavalent Chromium (Cr(VI)) Reduction Reaction Using Catalyst Powder 1

0.1 grams of the catalyst powder 1 is placed in a 250 mL conical flask. Subsequently, 100 mL of hexavalent chromium (Cr(VI)) aqueous solution with a concentration of 50 ppm is added into the conical flask. Thereafter, shake the conical flask to render a uniform distribution of the catalyst powder 1 in the hexavalent chromium aqueous solution. The catalyst powder 1 and the hexavalent chromium aqueous solution are allowed to react for 2 minutes. Subsequently, a sample of 2 mL of the solution is filter by a syringe filter. The absorbance of the sample is measured by UV-VIS spectrophotometer and the concentration of the hexavalent chromium in the sample is calculated according to Lambert-Beer Law.

The foregoing process may be repeated with the catalyst powder 1 being recycled. In detail, the catalyst powder 1 may be centrifuged to separate from the solution. Without rinsing the catalyst powder 1, the foregoing process is repeated for 6 times.

The removal rate of hexavalent chromium in the solution is illustrated in Table 2 below. It should be noted that the removal rate of the hexavalent chromium may be calculated by comparing the original hexavalent chromium concentration and the remaining hexavalent chromium concentration after the heavy metal reduction reaction.

Examples 2-7: Hexavalent Chromium (Cr(VI)) Reduction Reaction Using Catalyst Powders 2-6, 11

Similar procedure as that of Example 1 has been conducted except the catalyst powder 1 is replaced by catalyst powders 2-6 respectively in Examples 2-6, and by catalyst powder 11 in Example 7. The removal rates of hexavalent chromium in the solution are summarized in Table 2 below.

TABLE 2

First
Second
Third
Fourth
Fifth
Sixth

Trial
Trial
Trial
Trial
Trial
Trial

Catalyst
(%)
(%)
(%)
(%)
(%)
(%)

Exam-
Cu_xZn_yO_zS_γ
100
100
100
97.8
94.1
82.9

ple 1

Exam-
Cu_xMn_yO_zS_γ
100
100
100
100
97.2
94.6

ple 2

Exam-

ple 3
Cu_xCo_yO_zS_γ
100
100
100
100
97.2
93.8

Exam-

ple 4
Cu_xNi_yO_zS_γ
100
100
100
97.7
96.9
95.0

Exam-
Cu_xIn_yO_zS_γ
100
100
97.6
96.0
93.3
90.5

ple 5

Exam-
Cu_xSn^II_yO_zS_γ
100
100
96.9
95.1
94.1
84.4

ple 6

Exam-
Cu_xMo_yO_zS_γ
100
99.3
98.7
95.6
91.1
—

ple 7

Examples 8-12: Hexavalent Chromium (Cr(VI)) Reduction Reaction Using Catalyst Powders 7-10 and 12

Similar procedure as that of Example 1 has been conducted except the catalyst powder 1 is replaced by catalyst powders 7-10 respectively in Examples 8-11, and by catalyst powder 12 in Example 12 and the hexavalent chromium aqueous solutions are allowed to react for 60 minutes. The removal rates of hexavalent chromium in the solution are 18% for Example 8 (Cu_xCe_yO_zS_γ), 38.5% for Example 9 (Cu_xSb_yO_zS_γ), 32.2% for Example 10 (Cu_xGa_yO_zS_γ), 85.7% for Example 11 (Cu_xSn^IV_yO_zS_γ), and 5.3% for Example 12 (Cu_xAg_yO_zS_γ).

It is commonly known that hexavalent chromium is highly toxic. As clearly illustrated in Table 2, the catalyst of the invention is able to aid the elimination of hexavalent chromium under atmospheric condition in a fast rate. 0.1 g of the catalyst is able to remove 0.03 g Cr(VI) in a short period and is still available. The resulting solution may be recycled for other use without causing damage to human body. In addition, as illustrated in Table 2, when the catalyst is recycled, the ability of aiding the conversion is not compromised. Therefore, the cost for the reduction processes may be significantly lowered.

Hydrogenation Reaction of Organic Compounds

Example 1 (RhB): Rhodamine B Hydrogenation Reaction Using Catalyst Powder 1

50 mL of Rhodamine B aqueous solution (a dye solution) with a concentration of 20 ppm is add into a 100 mL conical flask. Subsequently, 5 mL of sodium boron hydride aqueous solution with a concentration of 0.1 mole is added into the conical flask. Under the stirring condition, 0.01 grams of catalyst powder 1 is provided in the conical flask. The catalyst powder 1 and the Rhodamine B aqueous solution are allowed to react. Subsequently, a sample of 2 mL of the solution is taken out after the dye colour change into colourless and filter by a syringe filter. The absorbance of the filtered solution is measured by UV-VIS spectrophotometer and the dye concentration in the sample is calculated according to Lambert-Beer Law.

The time required for the complete hydrogenation reaction of Rhodamine B in the solution is illustrated in Table 3 below. It should be noted that the complete reduction of the Rhodamine B may be calculated by comparing the original Rhodamine B concentration without the addition of sodium boron hydride and the remaining dye concentration after the hydrogenation reduction reaction.

Examples 2-12 (RhB): Rhodamine B Hydrogenation Reactions Using Catalyst Powders 2-12

Similar procedure as that of Example 1 (RhB) has been conducted except the catalyst powder 1 is replaced by catalyst powders 2-12 respectively in Examples 2-12 (RhB). The times required for the complete hydrogenation reaction of Rhodamine B in the solution are summarized in Table 3 below.

Examples 1-12 (MO): Methyl Orange Hydrogenation Reactions Using Catalyst Powders 1-12

Similar procedure as that of Example 1 (RhB) has been conducted for catalyst powders 1-12 respectively in Examples 1-12 (MO) except for Rhodamine B changed to methyl orange. The times required for the complete hydrogenation reaction of methyl orange in the solution are summarized in Table 3 below.

Examples 1-12 (MB): Methylene Blue Hydrogenation Reactions Using Catalyst Powders 1-12

Similar procedure as that of Example 1 (RhB) has been conducted for catalyst powders 1-12 respectively in Examples 1-12 (MB) except for Rhodamine B changed to methylene blue and its dye solution changed to 100 mL of methylene blue aqueous solution with a concentration of 100 ppm in a 250 mL conical flask. The times required for the complete hydrogenation reaction of methylene blue in the solution are summarized in Table 3 below.

Comparative Example 1 (RhB): Rhodamine B Hydrogenation Reactions Using Catalyst CuO_zS_γ

Similar procedure as that of Example 1 (RhB) has been conducted. The times required for the complete hydrogenation reaction of Rhodamine B in the solution are summarized in Table 3 below.

Comparative Example 1 (MO): Methyl Orange Hydrogenation Reactions Using Catalyst CuO_zS_γ

Similar procedure as that of Example 1 (MO) has been conducted. The times required for the complete hydrogenation reaction of methyl orange in the solution are summarized in Table 3 below.

Comparative Example 1 (MB): Methylene Blue Hydrogenation Reactions Using Catalyst CuO_zS_γ

Similar procedure as that of Example 1 (MB) has been conducted. The times required for the complete hydrogenation reaction of methylene blue in the solution are summarized in Table 3 below.

TABLE 3

Time for
Time for
Time for

completing
completing
completing

hydrogenation of
hydrogenation of
hydrogenation of

Rhodamine B
Methyl orange
Methylene blue

(RhB)
(MO)
(MB)

Catalyst
(minute)
(minute)
(minute)

Example 1
Cu_xZn_yO_zS_γ
1
slow
3

Example 2
Cu_xMn_yO_zS_γ
2
3
5

Example 3
Cu_xCo_yO_zS_γ
2
1
3

Example 4
Cu_xNi_yO_zS_γ
1
1
4

Example 5
Cu_xIn_yO_zS_γ
2
slow
4

Example 6
Cu_xSn^II_yO_zS_γ
1
2
3

Example 7
Cu_xCe_yO_zS_γ
2
slow
2

Example 8
Cu_xSb_yO_zS_γ
slow
4
6

Example 9
Cu_xGa_yO_zS_γ
2
slow
8

Example 10
Cu_xSn^IV_yO_zS_γ
2
slow
13

Example 11
Cu_xMo_yO_zS_γ
slow
1
3

Example 12
CuAg_yO_zS_γ
No reaction
No reaction
No reaction

Comparative
CuO_zS_γ
2
3
3

Example 1

The hydrogenation reactions of rhodamine B, methyl orange, and methylene blue under catalyst involve the C—N═C bonding in molecules changed to C—NH—C. Cu_xSn^II_yO_zS_γ performs the best in all three different organic molecules. These hydrogenation reactions at the ambient condition involve the green chemical processes, which can be beneficial for the industry, biology, and pharmacy.

Organic Compound Degradation

Synthesis Example 13: Copper Nickel Oxysulfide (Cu_xNi_yO_zS_γ) Powder 13

Under magnetic stirring, 1.5 grams of thioacetamide (CH₃CSNH₂) is added into a 500 ml solution containing cupric nitrate (Cu(NO₃)₂.2.5H₂O) and nickel (II) chloride (NiCl₂.6H₂O) with the molar ratio of n(Ni):n(Cu)=1/3. After 30 minutes of stirring, the mixture solution is heated to 95° C. with a heating rate of 2° C./min. The mixture solution is further stirred for 2 hours. The precipitate solid is collected by centrifugation and is washed with deionized water until pH=7. The precipitate solid is further washed with absolute ethanol for two times. Finally, the solid is vacuum dried at 80° C. for 24 hours. The obtained powder 13 is labelled as CuNiOS-0 (1/3).

Synthesis Examples 14-16: Copper Nickel Oxysulfide (Cu_xNi_yO_zS_γ) Powders 14-16

Similar procedures as that of Synthesis Example 13 is conducted except the cupric nitrate (Cu(NO₃)₂.2.5H₂O) and nickel (II) chloride (NiCl₂.6H₂O) molar ratio (n(Ni):n(Cu)) are substituted with 2/3, 3/3, 4/3. The obtained powders 14-16 are respectively labelled as CuNiOS-0 (2/3), CuNiOS-0 (3/3), CuNiOS-0 (4/3).

Synthesis Example 17: Copper Oxysulfide (CuOS) Powder 17

For comparison, the Ni-free CuOS powder 17 is synthesized with the same procedure as that of Synthesis Example 13 except for the elimination of Ni precursor.

Synthesis Examples 18-21: Copper Nickel Oxysulfide (Cu_xNi_yO_zS_γ) Powders 18-21

Similar procedures as that of Synthesis Example 15 is conducted except 0.1, 0.2, 0.3, or 0.4 mL of hydrazine (N₂H₄) is added to the mixture solution after the mixture solution was heated to 95° C. The obtained powders 18-21 are respectively labelled as CuNiOS-1, CuNiOS-2, CuNiOS-3, and CuNiOS-4.

The manufacturing parameters of powders 13-21 are summarized in Table 4 below.

TABLE 4

Ni/Cu
Amount of

Powder

precursor
hydrazine added

Number
Labelling
weight ratio
(mL)

13
CuNiOS-0 (1/3)
1/3
0

14
CuNiOS-0 (2/3)
2/3
0

15
CuNiOS-0 (3/3)
3/3
0

16
CuNiOS-0 (4/3)
4/3
0

17
CuOS-0
N/A
0

18
CuNiOS-1
3/3
0.1

19
CuNiOS-2
3/3
0.2

20
CuNiOS-3
3/3
0.3

21
CuNiOS-4
3/3
0.4

Synthesis Example 22: Copper Cobalt Oxysulfide (Cu_xCo_yO_zS_γ) Powder 22

Under magnetic stirring, 1.5 grams of thioacetamide (CH₃CSNH₂) is added into a 500 ml solution containing cupric nitrate (Cu(NO₃)₂.2.5H₂O) and cobalt (II) chloride (CoCl₂) with the molar ratio of n(Co):n(Cu)=3/3. After 30 minutes of stirring, the mixture solution is heated to 95° C. with a heating rate of 2° C./min. The mixture solution is further stirred for 2 hours. The precipitate solid is collected by centrifugation and is washed with deionized water until pH=7. The precipitate solid is further washed with absolute ethanol for two times. Finally, the solid is vacuum dried at 80° C. for 24 hours. The obtained powder 22 is labelled as CuCoOS-0.

Synthesis Examples 23-29: Copper Cobalt Oxysulfide (Cu_xCo_yO_zS_γ) Powders 23-29

Similar procedures as that of Synthesis Example 22 is conducted except 0.1 or 0.3 mL of hydrazine (N₂H₄) is added to the mixture solution after the mixture solution was heated to 95° C. The obtained powders 23-24 are respectively labelled as CuCoOS—N1 and CuCoOS—N2. Similar procedures as that of Synthesis Example 22 is conducted except 0.25, 0.5, 0.75, 1.0, or 2.0 mL of hydrogen peroxide (H₂O2) is added to the mixture solution after the mixture solution was heated to 95° C. The obtained powders 25-29 are respectively labelled as CuCoOS—O1, CuCoOS—O2, CuCoOS—O3, CuCoOS—O4, and CuCoOS—O5.

Synthesis Example 30: Copper Indium Oxysulfide (Cu_xIn_yO_zS_γ) Powder 30

Under magnetic stirring, 1.5 grams of thioacetamide (CH₃CSNH₂) is added into a 500 ml solution containing cupric nitrate (Cu(NO₃)₂.2.5H₂O) and indium (III) chloride (InCl₃) with the molar ratio of n(In):n(Cu)=3/3. After 30 minutes of stirring, the mixture solution is heated to 95° C. with a heating rate of 2° C./min. The mixture solution is further stirred for 2 hours. The precipitate solid is collected by centrifugation and is washed with deionized water until pH=7. The precipitate solid is further washed with absolute ethanol for two times. Finally, the solid is vacuum dried at 80° C. for 24 hours. The obtained powder 30 is labelled as CuInOS-0.

Synthesis Example 31: Copper Indium Oxysulfide (Cu_xIn_yO_zS_γ) Powder 31

Similar procedures as that of Synthesis Example 30 is conducted except 0.5 mL of hydrogen peroxide (H₂O₂) is added to the mixture solution after the mixture solution was heated to 95° C. The obtained powder 31 labelled as CuInOS-0.5H₂O₂.

The manufacturing parameters of powders 22-31 are summarized in Table 5 below.

TABLE 5

Amount of
Amount of

Powder

hydrazine added
hydrogen peroxide

Number
Labelling
(mL)
added (mL)

22
CuCoOS-0
0
0

23
CuCoOS—N1
0.1
0

24
CuCoOS—N2
0.3
0

25
CuCoOS—O1
0
0.25

26
CuCoOS—O2
0
0.50

27
CuCoOS—O3
0
0.75

28
CuCoOS—O4
0
1.0

29
CuCoOS—O5
0
2.0

30
CuInOS-0
0
0

31
CuInOS—0.5H₂O₂
0
0.5

Methylene Blue (MB) Degradation Measurements

CuNiOS catalytic degradation activity on methylene blue (MB) is tested in a home-made and jacketed quartz reactor. The reactor is shielded from an ambient light such that the catalytic reactions is conducted in a dark condition. For example, the reactor may be wrapped by an aluminium foil in order to avoid additional interference in interpreting the dye degradation mechanism. The catalytic degradation is tested with 100 mL MB solution of 10 mg/L while the catalyst concentration is kept at 0.25 g/L. The reactant mixture is under magnetic stirring with 280 r/min. A sample of 3 mL is taken every 5 minutes from the reactor, followed by instant centrifugation in 1 minute. Absorbance of the supernatant is measured with JASCD V-670 UV-Vis spectrophotometer at 663 nm. The concentration of the samples is calculated based on the Lambert-Beer law. The degradation ratio of MB is calculated using the following expression:

Degradation ratio of MB=(C₀−C_t)/C₀×100%,

where C₀is the initial concentration at t=0 minute and C_tis the concentration after reaction for t minutes. To evaluate the reusability of CuNiOS, the catalysts after the first run without being washed is reused for the next trial at the same condition after re-filling with a fresh MB dye solution.

The experimental results are demonstrated in FIG. 1A to FIG. 1D.

FIG. 1A illustrated the ability of MB degradation in the dark for powders 13-17. It should be noted that the degradation activity of CuNiOS (powders 13-16) is much higher than CuOS (powder 17). Powder 15 (CuNiOS-0 (3/3)) is able to completely degrade MB in 5 minutes. On the contrary, powder 17 (CuOS-0) only removed 9.9% MB in 30 minutes. The degradation of MB with the efficiency is in the following order: Powder 15 (CuNiOS-0 (3/3))>Powder 14 (CuNiOS-0 (2/3)) Powder 16 (CuNiOS-0 (4/3))>Powder 13 (CuNiOS-0 (1/3))>Powder 17 (CuOS-0).

FIG. 1B illustrated the ability of MB degradation in the dark for powders 13, 17, 18-21. As demonstrated in FIG. 1B, the hydrazine (N₂H₄) added during the synthesis step of the bimetal oxysulfide solid-solution catalyst has an important effect on the degradation of MB. The efficiency is in the following order: Powder 13 (CuNiOS-0)>Powder 18 (CuNiOS-1)>Powder 19 (CuNiOS-2)>Powder 20 (CuNiOS-3)>Powder 21 (CuNiOS-4)>Powder 17 (CuOS-0). N₂H₄-free CuNiOS-0 is able to completely degrade MB in 5 minutes. On the contrary, the CuNiOS-4 catalyst (Powder 21) only removed 28.3% MB in 30 minutes. The data indicate that the addition of N₂H₄for preparing CuNiOS has degraded its oxidation capability.

In order to test the catalyst reusability, the supernatant of the best CuNiOS-0 catalyst for MB degradation after the first test is decanted. Then, a fresh 100 mL MB solution of 10 ppm is added for the reuse tests in the dark. The second run is also completed in 5 minutes. After the third run, the CuNiOS-0 remained effective to degrade 93% MB in 5 minutes. To differentiate the dye degradation from adsorption, the wash-out ethanol solution of CuNiOS-0 powder after the runs is analyzed with UV-Vis spectrophotometer at 663 nm. The disappearance of the characteristic peak confirmed there is no MB residues adsorbed on CuNiOS. A comparative experiment on activated carbon (AC) with S_BETabove 1000 m²/g did show the characteristic peak at 663 nm for MB on AC after the activated carbon (AC) powder was washed. The bimetal oxysulfide solid-solution catalyst of the invention has a S_BETvalue of ˜22 m²·g⁻¹, which is too low for adsorption to proceed. Therefore, the MB dye is confirmed to be degraded by the catalytic reaction in the dark.

FIG. 1C is a diagram illustrating the ability of methylene blue degradation in the dark for powders 22-29. As demonstrated in FIG. 1C, the hydrazine (N₂H₄) and the hydrogen peroxide (H₂O₂) added during the synthesis step of the bimetal oxysulfide solid-solution catalyst have an important effect on the degradation of MB. By adding sufficient amount of hydrogen peroxide, the degradation of MB is enhanced. However, adding too much hydrogen peroxide slows down the degradation of MB. The efficiency is in the following order: Powder 27 (CuCoOS—O3)>Powder 26 (CuCoOS—O2)>Powder 25 (CuCoOS—O1)>Powder 22 (CuCoOS-0)>Powder 28 (CuCoOS—O4)>Powder 29 (CuCoOS—O5)≈Powder 24 (CuCoOS—N2) Powder 23 (CuCoOS—N1).

FIG. 1D is a diagram illustrating the ability of methylene blue degradation in the dark for powders 17, 30-31. As demonstrated in FIG. 1D, the hydrogen peroxide (H₂O₂) added during the synthesis step of the bimetal oxysulfide solid-solution catalyst has an important effect on the degradation of MB. By adding sufficient amount of hydrogen peroxide, the degradation of MB may be enhanced. The efficiency is in the following order: Powder 31 (CuInOS-0.5H₂O₂)>Powder 30 (CuInOS-0)>Powder 17 (CuOS-0).

The comparison of MB degradation with various catalysts is summarized in Table 6 below.

TABLE 6

Testing condition

Total
MB
total
Reaction

Catalyst
solution
solution
time

MB/Catal.
Removal

Catalyst
(mg)
(ppm)
(ml)
(min)
Light type
(mg/mg)
(%)

CuS + H₂O₂
10 mg
10 ppm
10 ml
15 min
dark
0.01
100

Ag—In—Ni—S
20 mg
3.16 ppm
14 ml
12 min
dark
0.002212
98

NiS
5 mg
3.16 ppm
14 ml
15 min
dark
0.008848
100

MoS₂+
N/A
10 ppm
N/A
5 min
dark
N/A
100

Ultrasonic wave

CeGeO₄
150 mg
6 ppm
100 ml
24 h
dark
0.004
100

ZnO:Eu
100 mg
10 ppm
100 ml
150 min
Xe-lamp
0.01
88

300 W

Ag/Ag₃PO₄
50 mg
20 ppm
50 ml
120 min
Xe-lamp
0.02
100

500 W

Au/SiO₂/WO₃
10 mg
4.9 ppm
50 ml
60 min
Xe-lamp
0.0245
100

72 W

Mn₃O₄—MnO₂
50 mg
10 ppm
100 ml
60 min
Xe-lamp
0.02
93.5

300 W

TiO₂—GO
20 mg
~5 ppm
50 ml
25 min
UV-light
0.0125
100

100 W

CuNiOS-0
25 mg
10 ppm
100 ml
5 min
Dark
0.04
100

(Powder 13)

As seen in Table 6, with the bimetal oxysulfide solid-solution catalyst of the invention, the MB degradation takes the shortest time period. Moreover, no extra external energy is required when using the bimetal oxysulfide solid-solution catalyst of the invention.

Hydrogen Generation

Synthesis Example 32: Copper Cobalt Oxysulfide (Cu_xCo_yO_zS_γ) Powder 32

Under magnetic stirring, 1.5 grams of thioacetamide (CH₃CSNH₂) is added into a 500 ml solution containing cupric nitrate (Cu(NO₃)₂.2.5H₂O) and precursor (cobalt (II) chloride (CoCl₂)) with the molar ratio of n(Co):n(Cu)=1:1. After 30 minutes of stirring, the mixture solution is heated to 95° C. with a heating rate of 2° C./min. The mixture solution is further stirred for 2 hours. The precipitate solid is washed, dried, and collected. The obtained powder 32 is labelled as CuCoOs-0.

Synthesis Examples 33-36: Copper Nickel Oxysulfide (Cu_xNi_yO_zS_γ) Powder 33, Copper Indium Oxysulfide (Cu_xIn_yO_zS_γ) Powder 34, Copper Cerium Oxysulfide (Cu_xCe_yO_zS_γ) Powder 35, and Copper Zinc Oxysulfide (Cu_xZn_yO_zS_γ) Powder 36

Similar procedures as that of Synthesis Example 32 is conducted except the precursor is replaced by nickel (II) chloride (NiCl₂.6H₂O), indium (III) chloride (InCl₃.4H₂O), cerium (III) nitrate hexahydrate (Ce(NO₂)₃.6H₂O), and zinc (II) acetate dihydrate (Zn(CH₃COO)₂.2H₂O). The obtained powders 33-36 are respectively labelled as CuNiOS-0, CuInOS-0, CuCeOS-0, and CuZnOS-0.

Synthesis Example 37: Copper Oxysulfide (CuOS) Powder 37

For comparison, the CuOS powder 37 is synthesized with the same procedure as that of Synthesis Example 32 except for the elimination of precursor.

Synthesis Examples 38-41: Copper Cobalt Oxysulfide (Cu_xCo_yO_zS_γ) Powders 38-41

Similar procedures as that of Synthesis Example 32 is conducted except 0.1, 0.2, 0.3, or 0.4 mL of hydrazine (N₂H₄) is added to the mixture solution after the mixture solution was heated to 95° C. The obtained powders 38-41 are respectively labelled as CuCoOS-1, CuCoOS-2, CuCoOS-3, and CuCoOS-4.

Synthesis Examples 42-47: Copper Manganese Oxysulfide (Cu_xMn_yO_zS_γ) Powders 42-47

Similar procedures as that of Synthesis Example 32 is conducted except the precursor is replaced by manganese (II) chloride (MnCl₂). Moreover, 0, 0.1, 0.2, 0.3, or 0.4 mL of hydrazine (N₂H₄) is added to the mixture solution after the mixture solution was heated to 95° C. The obtained powders 42-46 are respectively labelled as CuMnOS-0, CuMnOS-1, CuMnOS-2, CuMnOS-3, and CuMnOS-4. Powder 42 further undergoes an annealing process at 200° C. and is labelled as CuMnOS-0-200 or Powder 47.

The manufacturing parameters of powders 32-47 are summarized in Table 7 below.

TABLE 7

Amount of

Powder

hydrazine added

Number
Labelling
Precursor
(mL)

32
CuCoOS-0
Cobalt
0

33
CuNiOS-0
Nickel
0

34
CuInOS-0
Indium
0

35
CuCeOS-0
Cerium
0

36
CuZnOS-0
Zinc
0

37
CuOS
N/A
0

38
CuCoOS-1
Cobalt
0.1

39
CuCoOS-2
Cobalt
0.2

40
CuCoOS-3
Cobalt
0.3

41
CuCoOS-4
Cobalt
0.4

42
CuMnOS-0
Manganese
0

43
CuMnOS-1
Manganese
0.1

44
CuMnOS-2
Manganese
0.2

45
CuMnOS-3
Manganese
0.3

46
CuMnOS-4
Manganese
0.4

47
CuMnOS-0-200
Manganese
0

Catalytic Hydrogen Generation

Hydrogen generation is conducted in a home-made and jacketed quartz reactor equipped with the input and output valves to control the gas flow. The reactor is shielded from an ambient light such that the catalytic reactions is conducted in a dark condition. In other words, to exclude the UV and visible light irradiations for the purpose of understanding the intrinsic nature for H₂generation, the reactor may be wrapped by an aluminium foil. The input valve is connected to a gas tank of 99.99% Argon (Ar) and the output valve is connected to a well-callibrated gas chromatography (GC) with thermal conduction detector (TCD) system. The hydrogen generation reaction is carried out by well dispersing 225 mg of catalyst in an aqueous solution to react with methanol (CH₃OH), ethanol (C₂H₅OH), or acetic acid in a 450 ml reactor. The gas sampling is taken in the time interval of 20 min. Gas sampling is conducted by flowing the Ar gas through the reactor to GC-TCD system for several minutes. A hydrogen calibration line may be built to quantitatively measure the H₂generation rate.

The experimental results are demonstrated in FIG. 2A to FIG. 2D, FIG. 3A to FIG. 3B, and Table 8.

FIG. 2A illustrated the hydrogen production rate in dark condition for powders 32-37. It should be noted that the aqueous solution for this set of experiment is by adding methanol into H₂O to form 10% methanol solution. The hydrogen production efficiency is in the following order: Powder 32 (CuCoOS-0)>Powder 36 (CuZnOS-0)>Powder 35 (CuCeOS-0)>Powder 33 (CuNiOS-0)>Powder 34 (CuInOS-0)>Powder 37 (CuOS). Powder 32 (CuCoOS-0) has the highest hydrogen production rate at 748 μmol·g⁻¹·h⁻¹, while the hydrogen production rate is 27 μmol·g⁻¹·h⁻¹for Powder 37 (CuOS). For comparative purpose, the trial using Pt-coated P25-TiO₂as the catalyst (instead of the bimetal oxysulfide solid-solution catalyst of the invention) is also performed. However, Pt/P25-TiO₂under the same condition did not have any hydrogen generation in the dark. The trial using Pt-coated P25-TiO₂as the catalyst yields a H₂generation rate of 129.3 μmol·g⁻¹·h⁻¹under 350 W Xe lamp. Using the bimetal oxysulfide solid-solution catalyst of the invention as the catalyst indeed yields a higher hydrogen generation rate. Moreover, it is also confirmed that H₂production from the liquid fuel at natural environment does happen with the aid of the bimetal oxysulfide solid-solution catalyst of the invention.

FIG. 2B illustrated the hydrogen production in dark condition for powders 32, 38-41. As demonstrated in FIG. 1B, the hydrazine (N₂H₄) added during the synthesis step of the bimetal oxysulfide solid-solution catalyst has an important effect on the hydrogen production rate. There is a trend of lowering the H₂yield for CuCoOS prepared with a higher N₂H₄amount, where CuCoOS shows a higher S⁶⁺/S²⁻ or Cu⁺/Cu²⁺ content. The Powder 32 (CuCoOS-0) without adding N₂H₄had the highest H₂yield.

FIG. 2C illustrated the H₂production in the solutions with different amount of methanol using powder 32. It should be noted that the catalysts in pure H₂O and methanol did not generate hydrogen, but the aqueous solutions of methanol produced H₂at normal temperature and pressure (NTP) in the dark. Referring to FIG. 2A and FIG. 2C simultaneously, the highest H₂yield of 748 μmol·g⁻¹·h⁻¹in the 20% methanol solution (FIG. 2C) is much higher than that of CuOS at 27 μmol·g⁻¹·h⁻¹(FIG. 2A). Moreover, the H₂generation also occurred for Powder 32 (CuCoOS-0) in ethanol (231 μmol·g⁻¹·h⁻¹) solution and acetic acid (459 μmol·g⁻¹·h⁻¹) solution. For pure ethanol, pure acetic acid, and acid mixture solution of alcohol and acetic acid without water, no H₂generation is observed. These results indicated that hydrogen generation process involves the reactions of catalysts with water and alcohol, or water and acetic acid. The reaction between catalyst and water, therefore, becomes critical.

FIG. 2D illustrated the H₂production at different reaction temperatures range from 15° C. to 60° C. using powder 32. As illustrated in FIG. 2D, powder 32 (CuCoOS-0) showed the highest H₂yield of 748 μmol·g⁻¹·h⁻¹at 25° C. and became lower at higher temperatures. The increased yield at 60° C. and the decreased yield at 15° C. may be related to the thermal activation of other kinetic steps. As the major reaction at 25-50° C. (around room temperature) is not a thermal activation process, the occurrence of hydrogen generation involves a totally different reaction mechanism.

TABLE 8

Condition

20%

20%
20%
ethanoic

Dark/
methanol +
ethanol +
acid +

Catalyst
Light
H₂O
H₂O
H₂O
H₂O
ethanol

CuOS
Dark
27
23
—
0
0

CuMnOS-0
Dark
154
854
217
0
0

CuMnOS-1
Dark
765
945
—
0
0

CuMnOS-2
Dark
105
213
—
—
—

CuMnOS-3
Dark
224
203
—
—
—

CuMnOS-4
Dark
165
226
—
—
—

CuMnOS-0
Visible
204
245
—
—
—

CuMnOS-
Dark
120
—
—
—
—

0-200

Note: Unit for the yield: μmol · g⁻¹catal. · h⁻¹

As seen from Table 8, the highest H₂yield is 765 μmol·g⁻¹catal.·h⁻¹in the methanol solution and 945 μmol·g⁻¹catal.·h⁻¹in the ethanol solution. These yields are higher than the trial using Powder 37 (CuOS) at 27 μmol·g⁻¹catal.·h⁻¹. The H₂generation also occurred for powder 42 (CuMnOS-0) with the yield of 217 μmol·g^−lcatal.·h⁻¹in an ethanoic acid solution. Under the visible illumination of 150 W Halogen lamp, the H₂yield degraded to 204 μmol·g⁻¹catal.·h⁻¹in methanol solution. The ineffectiveness of photo-induced electron-hole pairs under light illumination for H₂production at NTP indicates dehydrogenation of CH₃OH by aqueous CuMnOS-0 dispersion solution is not initiated by the electron/hole charges. After CuMnOS-0 nanoflower catalyst is annealed at 200° C. (Powder 47), its H₂yield further degraded to 120 μmol·g⁻¹catal.·h⁻¹due to the deactivation of the catalyst activity. There is a trend of lowering the H₂yield at the higher Cu⁺ content for preparing CuMnOS with higher N₂H₄amount. To test catalyst reusability, after immersing the CuMnOS-1 catalyst in alcohol solution for 24 hours, the step of drying and re-filling is performed and the catalyst is tested again. A H₂yield of 663 μmol·g⁻¹catal.·h⁻¹is obtained.

For the photocatalytic reactions in the water/methanol solution, conventional Ni₂P/CdS nanorods obtained a record-high H₂production rate of 553 mmol·g⁻¹catal.·h⁻¹under a filtered 300 W Xe lamp. The rate per input light power can be viewed as 1.84 mmol·g⁻¹catal.·h⁻¹·watt⁻¹. The other excellent catalyst was Sr—NaTaO₃with a rate of 48.9 mmol·g⁻¹catal.·h⁻¹or 0.79 mmol·g⁻¹catal.·h⁻¹·watt⁻¹. Ruthenium hydride complex performed the best for the homogeneous catalysis of methanol and water into CO₂and H₂O at 90° C. under the additive of KOH. Without the precious metal, the H₂production rate is low. However, in the invention, the powder 43 (CuMnOS-1) may achieve a hydrogen generation rate of 945 μmol·g⁻¹catal.·h⁻¹even in the dark.

Reusability of the Bimetal Oxysulfide Solid-Solution Catalyst

FIG. 3A illustrated the reusability of Powder 32 (CuCoOS-0) for hydrogen production. The same powder had been used for 5 trials. After the 5th run, the CuCoOS-0 catalyst still maintained the hydrogen generation activity at 621 μmol·g−1·h−1. There is a 17.0% decrease in the H₂production rate after the 5th run, so the catalyst did slightly degrade for each reusability test. If the degradation involved the reactivity of CuCoOS, it is expected that the Cu⁺ and Cu²⁺ in CuCoOS should have a change from their original values of 66.5% and 33.5%, respectively, due to the redox reactions. Therefore, the CuCoOS catalyst after 5 runs needs to be evaluated for its Cu valence state.

FIG. 3B illustrated the high resolution Cu2p XPS spectrum of Powder 32 (CuCoOS-0) after 5 runs. The monovalent Cu⁺ peaks of Cu2p3/2 and Cu2p1/2 located at 933.3 eV and 953.3 eV, respectively. The bivalent Cu²⁺ peaks of 2p3/2 and 2p1/2 located at 934.7 eV and 955.2 eV, respectively. According to the peak area, the molar contents of Cu⁺ and Cu²⁺ are calculated to be 66.7% and 33.2%, respectively. It can been found that the XPS Cu2p peak positions and the Cu⁺ and Cu²⁺ contents are similar to those of the fresh CuCoOS-0 catalyst. The results indicated that the CuCoOS catalyst used 5 runs for the hydrogen generation is stable.

Based on the foregoing, the bimetal oxysulfide solid-solution catalyst in the invention includes several advantages. For example, the bimetal oxysulfide solid-solution catalyst may be manufactured at a low temperature, thereby ensure safety in the manufacturing process. Moreover, due to the specific structure and composition of the bimetal oxysulfide solid-solution catalyst of the invention, reduction of CO₂gas, reduction of heavy metal, hydrogenation/degradation (oxidation) of organic compounds, and production of hydrogen may be performed at atmospheric condition. That is to say, the bimetal oxysulfide catalysts can be adjusted for the different redox reactions. As such, the power requirement for external energy may be eliminated. In addition, the bimetal oxysulfide solid-solution catalyst of the invention may be recycled for repeated uses. Therefore, the cost for the reduction/oxidation processes may be significantly lowered.

It will be apparent to those skilled in the art that various modifications and variations can be made to the structure and composition of the present invention without departing from the scope or spirit of the invention. In view of the foregoing, it is intended that the present invention covers modifications and variations of this invention provided they fall within the scope of the following claims and their equivalents.

Number	Name	Date	Kind
5122357	Bedard et al.	Jun 1992	A
5594263	Bedard et al.	Jan 1997	A
9649622	Kuo	May 2017	B1
20040029726	Domen et al.	Feb 2004	A1

	Number	Date	Country
Parent	15155651	May 2016	US
Child	15476674		US

Method for organic compound degradation and method for producing hydrogen

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CPC

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