Patent Grant
9073037
The present invention relates to a photocatalyst and preparation method and use thereof, especially, to a semiconductor photocatalyst for photocatalytically reforming biomass derivatives to generate hydrogen, and preparation method and use thereof.
Energy resource is the basis for the development of the current society, and is also an index for restricting the development of national economy and evaluating the national comprehensive strength. It is therefore important for the national safety and is always the first strategic field developed by the countries in the world. Up to date, the traditional fossil fuels, such as coal, oil and natural gas, suffer from low utilization rate, serious environmental pollution and shortage, and thus will not satisfy the requirement in future for an energy system that needs highly efficient, clean, economy and safe. The development of sustainable energy source is a huge challenge and under great pressure in both scientific and industry community. Meanwhile, people's concerns on the global environmental problems such as climate change and environmental pollution make the future energy production and utilization focus on the environmental and ecologic effect. The development of renewable energy solutions must be one of the important issues in the century.
Hydrogen energy is considered as an important secondary energy in the 21st century. It is a superior new energy source with main advantages as follows. Hydrogen has a high combustion heat value, and the combustion heat of every kilogram of hydrogen is about 3 times to that of petroleum, 3.9 times to that of alcohol and 4.5 times to that of char. The burning product of hydrogen is water, and thus it is indeed a clean energy. Hydrogen has abundant resources, and it could be obtained from water or biomass, both of them are the most abundant resource on earth, which is well evidenced by a classic procedure of nature in a recycling and sustainable way. The application of hydrogen energy is quickly growing with the progress of various techniques, and thus it is of great interest to develop hydrogen energy.
Nowadays, the production of hydrogen from fossil fuels is the main approach to obtain hydrogen in industry. As an alternative, the production of hydrogen by electrolysis is the other one. Although the current techniques for producing hydrogen from fossil fuels is mature with low production cost, the resources is limited and is non-renewable. In the long run, it does not meet the requirements for sustainable development. It is of great interest to produce hydrogen by solar energy, which converts the inexhaustible and dispersed solar energy into highly concentrated clean hydrogen energy. Currently, the methods for producing hydrogen by water-splitting with solar energy include a method for producing hydrogen by pyrolysing water with solar energy, a method for producing hydrogen by electrolysing water with solar powered electricity, a method for producing hydrogen by splitting water with solar energy, a method for producing hydrogen by photocatalytically reforming biomass with solar energy, and so on. It is of great significance in reality to produce hydrogen with solar energy, which, however, is a challengable research project with a large amount of theoretical and technical problems to be solved. It has drawn a great attention in the world, and many labor, funds and material resources have been invested. Particularly, the production of hydrogen with biomass, as an effective approach for solving energy problem, has recently appeared at a forefront.
Biomass is the most abundant material on earth, and includes all animals, plants and microorganisms as well as many organics derived, excreted and metabolised from the living materials. All the biomass has energy. Biomass energy is the energy produced from biomass using biomass as the carrier. The biomass energy is an energy form of solar energy that is stored in organism in the form of chemical energy, and comes from photosynthesis of plants, either directly or indirectly. Although the overall energy consumed by photosynthesis of plants only accounts for 0.2% of the total solar energy reaching on earth, the absolute value is surprisingly huge and the energy generated by photosynthesis is about 40 times to the total energy that human have consumed. Thus, biomass refers to a huge energy source. Yet, the biomass energy has clear disadvantages of low energy density and random distribution, although biomass is distributed all over the world with great reserves. As mentioned above, hydrogen is an excellent clean energy with high energy density and high efficiency. Hydrogen could be transported, or stored in long term, and liquified hydrogen has a density higher than natural gas. Thus, it would be easier to convert the large amount of dispersed biomass into hydrogen to transport and store, which is an important approach to store and concentrate biomass energy. More importantly, the technique of photocatalytically reforming biomass to generate hydrogen can be carried out under ambient temperature and pressure powered by solar energy. The fact for this energy conversion converts the inexhaustible solar energy into human desired energy is not only sustainable, but also environmental-friendly.
Thus, it is of great significance to develop a method for hydrogen production by solar energy with high efficiency and low cost, with respect to the improvement of energy infrastructure, the protection of ecological environment and the promotion of the sustainable development of economy and society.
Early in 1980s, Japanese scientists Kawai et al (Chem. Lett. 1981, 81-84; Nature. 1980, 286, 474-476) reported hydrogen generation by photocatalytically reforming biomass derivatives in water, using Pt/RuO2/TiO2 as the catalyst. Later, many literatures (J. Phys. Chem. 1983, 87, 801-805; J. Am. Chem. Soc. 1985, 107, 1773-1774; Chem. Phys. Lett. 1981, 80, 341-344; Photochem. Reviews 2003, 4, 5-18; Catal. Lett. 2004, 98, 61; Chem. Commun 2004, 2192-2193) reported methods for hydrogen generation from various biomass derivatives, such as methanol, ethanol, lactic acid, glycine, glutamic acid, proline, sugar, soluble starch, gelatin protein, algae, cockroach body, human urine, animal manure, teared filter paper (the major component thereof is cellulose), and so on.
Meanwhile, there are also patents involving photocatalytically reforming biomass derivatives by solar energy to generate hydrogen. Japanese patent application 57,156,302 disclosed a method for photocatalytically reforming methanol using TiO2/CdS/GaP to produce hydrogen, and Japanese patent application 59,203,701 disclosed a method for photocatalyticlly reforming a mixed solution of methanol and water with a ratio of 1:1 to produce hydrogen, which uses TiO2 loaded with one selected from a group consisting of CrB, Ni2B, Co2P, Mo2C and Cr3C2 as a catalyst. The rate of hydrogen generation is about 0.28 to 0.96 mL/h under irradiation of a 500 W UV lamp. Japanese patent application 6,186,943 disclosed a method for photocatalytically reforming a mixed solution of ethanol and water with a ratio of 1:1 to produce hydrogen, which uses amorphous Si loaded with Pt as a catalyst. The rate of hydrogen generation is up to 0.03 mL/h under irradiation of a 100 W halogen lamp. In addition, Can Li et al from DaLian Chemical and Physical institute, Chinese Academy of Sciences reported three different catalysts for photocatalytically reforming biomass derivatives to generate hydrogen. Chinese patent application CN200410031517.3 discloses a novel composite photocatalyst with a formula of A1-xTaO3:Bx, wherein x is 0 or 1, A is an alkaline metal and B is lanthanum or bismuth, for photocatalytically reforming biomass derivatives under UV light to generate hydrogen, and preparation method thereof. Chinese patent application CN200810240366.0 disclosed a photocatalyst based on heterojunction with a formula of m % WOxSy/CdS, wherein x represents the molar fraction of oxygen in the tungsten species with 0≦x≦1, y represents the molar fraction of sulfur in the tungsten species with 0<y≦2, and m is the mass percentage of tungsten element with 0<m≦10. The photocatalyst is based on semiconductor heterojuction, and a heterojunction photocatalyst with high activity for reforming biomass derivatives to generate hydrogen is prepared by using a CdS catalyst as a carrier, supporting a precursor of W on the CdS catalyst by impregnation, and then assembling the sulfide (oxide) of W on the CdS. Chinese patent application 200910136643.8 disclosed a TiO2 photocatalyst for photocataltically reforming biomass derivatives to generate hydrogen, wherein the crystal phase composition of anatase phase and rutile phase can vary in a relatively wide range. The TiO2 photocatalyst may be used in photocataltic reformation of biomass derivatives to generate hydrogen, largely improving the activity for hydrogen generation and effectively restraining the generation of carbon monoxide. The activity of the TiO2 photocatalyst for hydrogen generation is about five times to that of P25 as TiO2 control, and the content of CO in hydrogen is reduced at least two orders of magnitude to less than 5 ppm.
Up to date, however, no literature or patent has reported a high efficient, stable, low cost and easily made photocatalyst for photocatalytically reforming biomass derivatives to generate hydrogen, which can be synthesized in situ by a photochemical method from quantum dots and the salts or complexes of transition metals, particularly cheap transition metals such as nickel, cobalt and iron under mild conditions.
The first technical problem to be solved by the present invention is to provide a semiconductor photocatalyst for photocatalytically reforming biomass derivatives to generate hydrogen.
The second technical problem to be solved by the present invention is to provide a method for preparing the above semiconductor photocatalyst.
The third technical problem to be solved by the present invention is to provide a system for photocatalytically reforming biomass derivatives to generate hydrogen, comprising the above semiconductor photocatalyst.
The fourth technical problem to be solved by the present invention is to provide a method for photocatalytically reforming biomass derivatives to generate hydrogen by using the above semiconductor photocatalyst.
To solve the above first technical problem, the present invention provides a semiconductor photocatalyst for photocatalytically reforming biomass derivatives to generate hydrogen, characterized in that:
the semiconductor photocatalyst has a formula of M˜N-Ax;
wherein, M˜N is group II element˜group VI element, or M˜N is group III element˜group V element;
wherein, A is one or two or more elements selected from the group consisting of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au and Ag; and 0.02%≦x≦1.0%.
In the present invention, M˜N means a group II element and a corresponding group VI element; or a group III element and a corresponding group V element.
The group II element may be Zn or Cd in group IIb; the group VI element may be S or Se in group VIa; the group III element may be In in group IIIa; and the group V element may be P or As in group Va.
Preferably, the biomass derivatives may be methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose, ascorbic acid, L-proline or L-cysteine.
Preferably, the semiconductor photocatalyst has a formula of TiO2-M˜N-Ax SnO2-M˜N-Ax or ZnO-M˜N-Ax. The biomass derivatives may be triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose or mannose.
To solve the second technical problem, the present invention provides a method for preparing the semiconductor photocatalyst of M˜N-Ax, comprising the steps of:
1) introducing quantum dots consisting of group II˜VI elements or group III˜V elements into a reactor;
2) introducing a solution of the salts or complexes of one or two or more elements selected from the group consisting of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au and Ag into the reactor to afford a mixed solution A;
3) introducing an aqueous solution of a biomass derivative into the mixed solution A to give a mixed solution B;
4) adjusting the pH value of the mixed solution B to 3˜10 to provide a mixed solution C, wherein the pH is adjusted by dropwise addition of 1 mol/L NaOH or 1 mol/L HCl;
5) degassing the solution. C of step 4) with an inert gas or vacuumizing the reactor; and irradiating the reactor with UV light, visible light or a mixed beam of UV and visible light to prepare in situ the semiconductor photcatalyst of formula M˜N-Ax under inert gas or vacuum atmosphere.
Furthermore, the present invention provides a method for preparing the semiconductor photocatalyst of TiO2-M˜N-Ax, SnO2-M˜N-Ax or ZnO-M˜N-Ax, comprising the steps of:
introducing quantum dots composed of group II˜VI elements or group III˜V elements into a reactor, then adding TiO2, SnO2 or ZnO, adjusting pH≧7, centrifuging and discarding the supernatant to keep the precipitates;
introducing into the precipitates one or two or more selected from group consisting of a cobalt salt, a cobalt complex, a nickel salt, a nickel complex, an iron salt, an iron complex, a copper salt and a chromium salt, or a solution of a salt of Pd, Pt, Ru, Rh, Ir, Au or Ag;
introducing an aqueous solution of a biomass derivative into the precipitates;
irradiating the reactor with UV light and/or visible light to prepare the semiconductor photocatalyst of formula TiO2-M˜N-Ax, SnO2-M˜N-Ax or ZnO-M˜N-Ax under inert gas or vacuum atmosphere;
wherein, the biomass derivatives may be triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose, ascorbic acid, L-proline or L-cysteine.
Preferably, the quantum dots composed of group II˜VI elements or group III˜V elements in step 1) have the concentration larger than 1×104 g/L; and the concentration of the quantum dots refers to that of a system which has added all the materials into the reactor and fixed the volume.
The quantum dots composed of group II˜VI elements includes the composite quantum dots composed of one or two or more selected from the group consisting of CdS, CdSe, CdTe, PbS, PbSe, ZnS and ZnSe
The quantum dots composed of group III˜V elements includes the composite quantum dots composed of one or two selected from the group consisting of InP and InAs.
Preferably, the solution of the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag in step 2) has a concentration larger than 1×10−6 mol/L, that is, the concentration of the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag in the whole reaction system may be up to the saturated concentration of the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag. Theoretically, the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag may be further added without any theoretical and economy values.
The cobalt salt may be cobalt halide, cobalt sulphate, cobalt nitrate, cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt phosphate or cobalt chromate.
The cobalt complex may be cobalt-ammonia complex ([Co(NH3)6]3+), cobalt-cyanogen complex ([Co(CN)6]4−), cobalt-thiocyanate complex ([Co(SCN)4]2−), cobalt-carbonyl complex ([Co(CO)4]−), cobalt-nitrate complex ([Co(NO3)4]2−), cobalt-nitrite complex ([Co(NO2)6]3−) or cobalt-diacetyldioxime complex; wherein the cobalt-diacetyldioxime complex and derivatives thereof have the following formulae:
wherein, L is H2O or CH3CN; R is H, N(CH3)2 or (COOCH3)2.
The nickel salt may be nickel halide, nickel sulphate, nickel nitrate, nickel carbonate, nickel oxalate, nickel acetate, nickel phosphate or nickel chromite.
The nickel complex may be nickel-ammonia complex ([Ni(NH3)6]2+), nickel-cyanogen complex ([Ni(CN)4]2−), nickel-chelate ([Ni(en)3]2+), nickel-carbonyl complex (Ni(CO)4), nickel-ethyl complex (C2H5)2Ni).
The iron salt may be iron halide, iron sulphate, iron nitrate, iron carbonate, iron oxalate, iron acetate, iron phosphate, iron chromate, ferrous halide, ferrous sulphate, ferrous nitrate, ferrous carbonate, ferrous oxalate, ferrous acetate, ferrous phosphate, ferrous chromate or ferrous ammonium sulphate.
The iron complex may be iron-cyanogen complex ([Fe(CN)6]3−), ferrous-cyanogen complex ([Fe(CN)6]4−), iron-thiocyanate complex ([Fe(SCN)3]), iron-sulfur complex ([Fe2S2(CO)6]), iron-carbonyl complex (Fe(CO)5), iron-carbonyl complex (Fe2(CO)9), or iron-carbonyl complex (Fe3(CO)12).
The copper salt may be copper halide, copper sulphate (pentahydrate, monohydrate or anhydrous), copper nitrate, copper carbonate, copper oxalate, copper acetate, copper phosphate, copper chromate, copper pyrophosphate, copper cyanide, copper stearate, copper naphthenate, cuprous halide, cuprous sulphate, cuprous carbonate, or cuprous acetate.
The chromium salt may be chromium halide, chromium sulphate, chromium nitrate, chromium carbonate, chromium oxalate, chromium acetate, or chromium phosphate.
The palladium salt may be potassium palladochloride, palladium halide, palladium sulphate, palladium nitrate, or palladium acetate.
The platinum salt may be potassium platinochloride, platinum halide, or platinum nitrate.
The ruthenium salt may be ruthenium halide, ruthenium sulphate, ruthenium nitrate, or ruthenium acetate.
The rhodium salt may be rhodium halide, rhodium sulphate, rhodium nitrate, or rhodium acetate.
The gold salt may be gold halide or chloroauric acid.
The silver salt may be silver halide, silver sulphate, silver nitrate, or silver acetate.
Preferably, the biomass derivative in step 3) has a concentration equal to or larger than 1×10−4 mol/L or a molar percentage of equal to or larger than 0.01%; and the concentration or molar percentage of the biomass derivative may be up to the saturated concentration thereof in the system. Theoretically, the biomass derivative may be further added without any theoretical and economy values.
To solve the third technical problem, the present invention provides a system for photocatalytically reforming biomass derivatives to generate hydrogen containing the semiconductor photocatalyst of M˜N-Ax, which comprises the following components:
1) quantum dots composed of group II˜VI elements or group III˜V elements; and
2) one or a mixture of two or more selected from group consisting of a cobalt salt, a cobalt complex, a nickel salt, a nickel complex, an iron salt, an iron complex, a copper salt and a chromium salt, or a solution of a salt of Pd, Pt, Ru, Rh, Ir, Au or Ag;
3) an aqueous solution of a biomass derivative;
and includes the following conditions:
The present invention provides a system for photocatalytically reforming biomass derivatives to generate hydrogen containing the semiconductor photocatalyst of TiO2-M˜N-Ax, SnO2-M˜N-Ax or ZnO-M˜N-Ax, which includes the following materials:
1) quantum dots composed of group II˜VI elements or group III˜V elements;
2) TiO2, SnO2 or ZnO;
3) one or a mixture of two or more selected from group consisting of a cobalt salt, a cobalt complex, a nickel salt, a nickel complex, an iron salt, an iron complex, a copper salt and a chromium salt, or a solution of a salt of Pd, Pt, Ru, Rh, Ir, Au or Ag;
4) an aqueous solution of a biomass derivative;
and includes the following conditions:
under basic condition and irradiation of UV and/or visible light.
Preferably, the quantum dots composed of group II˜VI elements or group III˜V elements have a concentration larger than 1×10−4 g/L; and the concentration of the quantum dots refers to that of a system which has added all the materials into the reactor and fixed the volume.
The quantum dots composed of group II˜VI elements includes the composite quantum dots composed of one or two or more selected from the group consisting of CdS, CdSe, CdTe, PbS, PbSe, ZnS and ZnSe
The quantum dots composed of group III˜V elements includes the composite quantum dots composed of one or two selected from the group consisting of InP and InAs.
Preferably, the solution of the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag has a concentration equal to or larger than 1×10−6 mol/L, that is, the concentration of the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag in the whole reaction system may be up to the saturated concentration of the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag. Theoretically, the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag may be further added without any theoretical and economy values.
The cobalt salt may be cobalt halide, cobalt sulphate, cobalt nitrate, cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt phosphate or cobalt chromate.
The cobalt complex may be cobalt-ammonia complex ([Co(NH3)6]3+), cobalt-cyanogen complex ([Co(CN)6]4−), cobalt-thiocyanate complex ([Co(SCN)4]2−), cobalt-carbonyl complex ([Co(CO)4]−), cobalt-nitrate complex ([Co(NO3)4]2−), cobalt-nitrite complex ([Co(NO2)6]3−) or cobalt-diacetyldioxime complex; wherein the cobalt-diacetyldioxime complex and derivatives thereof have the following formulae:
wherein, L is H2O or CH3CN; R is H, N(CH3)2 or (COOCH3).
The nickel salt may be nickel halide, nickel sulphate, nickel nitrate, nickel carbonate, nickel oxalate, nickel acetate, nickel phosphate or nickel chromite.
The nickel complex may be nickel-ammonia complex [Ni(NH3)6]2+), nickel-cyanogen complex ([Ni(CN)4]2−), nickel-chelate ([Ni(en)3]2+), nickel-carbonyl complex (Ni(CO)4), nickel-ethyl complex (C2H5)2Ni).
The iron salt may be iron halide, iron sulphate, iron nitrate, iron carbonate, iron oxalate, iron acetate, iron phosphate, iron chromate, ferrous halide, ferrous sulphate, ferrous nitrate, ferrous carbonate, ferrous oxalate, ferrous acetate, ferrous phosphate, ferrous chromate or ferrous ammonium sulphate.
The iron complex may be iron-cyanogen complex ([Fe(CN)6]3−), ferrous-cyanogen complex ([Fe(CN)6]4−), iron-thiocyanate complex ([Fe(SCN)3]), iron-sulfur complex ([Fe2S2(CO)6]), iron-carbonyl complex (Fe(CO)5), iron-carbonyl complex (Fe2(CO)9), or iron-carbonyl complex (Fe3(CO)12).
The copper salt may be copper halide, copper sulphate (pentahydrate, monohydrate or anhydrous), copper nitrate, copper carbonate, copper oxalate, copper acetate, copper phosphate, copper chromate, copper pyrophosphate, copper cyanide, copper stearate, copper naphthenate, cuprous halide, cuprous sulphate, cuprous carbonate, or cuprous acetate.
The chromium salt may be chromium halide, chromium sulphate, chromium nitrate, chromium carbonate, chromium oxalate, chromium acetate, or chromium phosphate.
The palladium salt may be potassium palladochloride, palladium halide, palladium sulphate, palladium nitrate, or palladium acetate.
The platinum salt may be potassium platinochloride, platinum halide, or platinum nitrate.
The ruthenium salt may be ruthenium halide, ruthenium sulphate, ruthenium nitrate, or ruthenium acetate.
The rhodium salt may be rhodium halide, rhodium sulphate, rhodium nitrate, or rhodium acetate.
The gold salt may be gold halide or chloroauric acid.
The silver salt may be silver halide, silver sulphate, silver nitrate, or silver acetate.
Preferably, the biomass derivative has a concentration equal to or larger than 1×10−4 mol/L or a molar percentage of equal to or larger than 0.01%; and the concentration or molar percentage of the biomass derivative may be up to the saturated concentration thereof in the system. Theoretically, the biomass derivative may be further added without any theoretical and economy values. The biomass derivative may be methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose, ascorbic acid, L-proline or L-cysteine.
To solve the Fourth technical problem, the present invention provides a method for photocatalytically reforming biomass derivatives to generate hydrogen using the semiconductor photocatalyst of M˜N-Ax, comprising the following steps:
1) introducing quantum dots composed of group II˜VI elements or group III˜V elements into a reactor;
2) introducing into the reactor one or more selected from group consisting of a cobalt salt, a nickel salt, an iron salt, a cobalt complex, a nickel complex, an iron complex, a copper salt and a chromium salt, or a salt of Pd, Pt, Ru, Rh, Ir, Au or Ag, to obtain a mixed solution A;
3) introducing an aqueous solution of a biomass derivative into the mixed solution A to give a mixed solution B;
4) adjusting the pH value of the mixed solution B to 3˜10 to provide a mixed solution C, wherein the pH is adjusted by dropwise addition of 1 mol/L NaOH or 1 mol/L HCl;
5) degassing the solution C of step 4) with an inert gas or vacuumizing the reactor; and irradiating the reactor with UV light, visible light or a mixed beam of UV and visible light under inert gas or vacuum atmosphere to prepare a catalyst in situ, which can be used for photocatalytically reforming biomass derivatives to generate hydrogen.
The biomass derivatives may be methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose, mannose, ascorbic acid, L-proline or L-cysteine.
The present invention provides a method for photocatalytically reforming biomass derivatives to generate hydrogen using the semiconductor photocatalyst of TiO2-M˜N-Ax, SnO2-M˜N-Ax or ZnO-M˜N-Ax, comprising the following steps:
1) introducing quantum dots composed of group II˜VI elements or group III˜V elements into a reactor, then adding TiO2, SnO2 or ZnO, adjusting pH≧7, centrifuging and discarding the supernatant to keep the precipitates;
2) introducing into the precipitates one or two or more selected from group consisting of a cobalt salt, a cobalt complex, a nickel salt, a nickel complex, an iron salt, an iron complex, a copper salt and a chromium salt, or a solution of a salt of Pd, Pt, Ru, Rh, Ir, Au or Ag;
3) introducing an aqueous solution of a biomass derivative into the precipitates, and adjusting pH≧7;
4) irradiating the reactor with UV and/or visible light under inert gas or vacuum atmosphere to prepare a composite semiconductor photocatalyst, which can be used for photocatalytically reforming biomass derivatives to generate hydrogen.
The biomass derivatives may be triethanolamine, triethylamine, methanol, ethanol, propanol, butanol, ethylene glycol, glycerol, glucose, sucrose, fructose, maltose or mannose. Preferably, the quantum dots composed of group II˜VI elements or group III˜V elements in step 1) have the concentration larger than 1×10−4 g/L; and the concentration of the quantum dots refers to that of a system, which has added all the materials into the reactor and fixed the volume.
The quantum dots composed of group II˜VI elements includes the composite quantum dots composed of one or two or more selected from the group consisting of CdS, CdSe, CdTe, PbS, PbSe, ZnS and ZnSe.
The quantum dots composed of group III˜V elements includes the composite quantum dots composed of one or two selected from the group consisting of InP and InAs.
Preferably, the solution of the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag in step 2) has a concentration of equal to or larger than 1×10−6 mol/L, that is, the concentration of the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag in the whole reaction system may be up to the saturated concentration of the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag. Theoretically, the salts or complexes of Co, Ni, Fe, Cu, Cr, Pd, Pt, Ru, Rh, Ir, Au or Ag may be further added without any theoretical and economic values.
The cobalt salt may be cobalt halide, cobalt sulphate, cobalt nitrate, cobalt carbonate, cobalt oxalate, cobalt acetate, cobalt phosphate or cobalt chromate.
The cobalt complex may be cobalt-ammonia complex ([Co(NH3)6]3+), cobalt-cyanogen complex ([Co(CN)6]4−), cobalt-thiocyanate complex ([Co(SCN)4]2−), cobalt-carbonyl complex ([Co(CO)4]−), cobalt-nitrate complex ([Co(NO3)4]2−), cobalt-nitrite complex ([Co(NO2)6]3−) or cobalt-diacetyldioxime complex; wherein the cobalt-diacetyldioxime complex and derivatives thereof have the following formulae:
wherein, L is H2O or CH3CN; R is H, N(CH3)2 or (COOCH3).
The nickel salt may be nickel halide, nickel sulphate, nickel nitrate, nickel carbonate, nickel oxalate, nickel acetate, nickel phosphate or nickel chromite.
The nickel complex may be nickel-ammonia complex ([Ni(NH3)6]2+), nickel-cyanogen complex ([Ni(CN)6]2−), nickel-chelate ([Ni(en)3]2+), nickel-carbonyl complex (Ni(CO)4), nickel-ethyl complex (C2H5)2Ni).
The iron salt may be iron halide, iron sulphate, iron nitrate, iron carbonate, iron oxalate, iron acetate, iron phosphate, iron chromate, ferrous halide, ferrous sulphate, ferrous nitrate, ferrous carbonate, ferrous oxalate, ferrous acetate, ferrous phosphate, ferrous chromate or ferrous ammonium sulphate.
The iron complex may be iron-cyanogen complex ([Fe(CN)6]3−), ferrous-cyanogen complex ([Fe(CN)6]4−), iron-thiocyanate complex ([Fe(SCN)3]), iron-sulfur complex ([Fe2S2(CO)6]), iron-carbonyl complex (Fe(CO)5), iron-carbonyl complex (Fe2(CO)9), or iron-carbonyl complex (Fe3(CO)12).
The copper salt may be copper halide, copper sulphate (pentahydrate, monohydrate or anhydrous), copper nitrate, copper carbonate, copper oxalate, copper acetate, copper phosphate, copper chromate, copper pyrophosphate, copper cyanide, copper stearate, copper naphthenate, cuprous halide, cuprous sulphate, cuprous carbonate, or cuprous acetate.
The chromium salt may be chromium halide, chromium sulphate, chromium nitrate, chromium carbonate, chromium oxalate, chromium acetate, or chromium phosphate.
The palladium salt may be potassium palladochloride, palladium halide, palladium sulphate, palladium nitrate, or palladium acetate.
The platinum salt may be potassium platinochloride, platinum halide, or platinum nitrate.
The ruthenium salt may be ruthenium halide, ruthenium sulphate, ruthenium nitrate, or ruthenium acetate.
The rhodium salt may be rhodium halide, rhodium sulphate, rhodium nitrate, or rhodium acetate.
The gold salt may be gold halide or chloroauric acid.
The silver salt may be silver halide, silver sulphate, silver nitrate, or silver acetate.
Preferably, the biomass derivative in step 3) has a concentration equal to or larger than 1×10−4 mol/L or a molar percentage of equal to or larger than 0.01%; and the concentration or molar percentage of the biomass derivative may be up to the saturated concentration thereof in the system Theoretically, the biomass derivative may be further added without any theoretical and economic values.
The refoiniing of biomass refers to the reformation and decomposition of biomass derivatives (mainly composed of C, H and O) into H2 and other small molecules, like CO2, CO, CH4, and so on, meanwhile, there are many intermediates left in the reaction solution. It should be explained that the kind and the ratio of the products are different with respect to different reaction materials.
The intermediates that may be generated in the reaction solution are complex, and both the species and the ratio of the products may differ a lot with different biomass derivatives, different reaction conditions (concentration, temperature, pH and so on) and different quantum dots, which are not listed here in detail, but it is for sure that H2 and CO2 are the main products.
The present invention has the following advantages.
The present invention can prepare a highly efficient semiconductor photocatalyst for photocatalytically reforming biomass derivatives to generate hydrogen through a photochemical method in situ from quantum dots and the salts or complexes of transition metals, particularly cheap transition metals such as nickel, cobalt and iron under mild conditions. More importantly, the method of the present invention can prepare a semiconductor photocatalyst in situ, which is highly efficient, stable, cheap and easily made under light irradiation without any severe conditions such as calcination. The method of the present invention is efficient in reaction, simple in operation, cheap and practical for application.
The present invention will be further explained with reference to the following Examples, but is not limited thereto.
A method for photocatalytically reforming a biomass derivative using a semiconductor photocatalyst to generate hydrogen:
1×10−1 g/L of CdSe quantum dots (the concentration of CdSe stock solution: 2×10−1 g/L) was added into a Pyrex tube, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of methanol (original concentration: 24.75 mol/L at 20° C.). Then the pH was adjusted to 4, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector).
After irradiation, synthesized in situ was a semiconductor material with a hollow sphere structure having an outer diameter of 10˜20 nm and a shell thickness of 2˜5 nm. The semiconductor photocatalyst has a formula of CdCoxSe, wherein x was determined to 0.13% through ICP (inductive coupled plasma emission spectrometer).
A method for photocatalytically reforming a biomass derivative using a semiconductor photocatalyst to generate hydrogen:
1×10−1 g/L of CdSe quantum dots (the concentration of CdSe stock solution: 2×10−1 g/L) was added into a Pyrex tube, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of ethanol (original concentration: 17.16 mol/L at 20° C.). Then the pH was adjusted to 5, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
As can be seen from the figure, after irradiation, synthesized in situ was a semiconductor material with a hollow sphere structure having an outer diameter of 10˜20 nm and a shell thickness of 2˜5 nm. The semiconductor photocatalyst has a formula of CdCoxSe, wherein x was determined to 0.16% through ICP (inductive coupled plasma emission spectrometer).
Ethanol can be prepared in large scale from fermentation of biomass, and therefore, it is of practical interest to photocatalytically reforming of ethanol to generate hydrogen. During the reformation of ethanol aqueous solution, ethanol was first oxidized to acetaldehyde during the initial stage of the photocatalytic reaction, and meanwhile H+ was reduced to H2. The acetaldehyde reacted with water to generate acetic acid, which was finally oxidized to CO2 and H2. Besides, acetaldehyde could react with hydroxyl radicals to yield CO2 and H2.
The method of example 1 was repeated except that the dopant is cobalt sulphate and the biomass derivative is ethanol.
The method of example 1 was repeated except that the dopant is cobalt nitrate and the biomass derivative is ethanol.
The method of example 1 was repeated except that the dopant is nickel chloride and the biomass derivative is ethanol.
The method of example 1 was repeated except that the dopant is nickel sulphate and the biomass derivative is ethanol.
The method of example 1 was repeated except that the biomass derivative is sucrose with a concentration of 0.1 mol/L.
The method of example 1 was repeated except that the biomass derivative is glucose with a concentration of 0.1 mol/L.
The method of example 1 was repeated except that the biomass derivative is glycerol.
The method of example 1 was repeated except that the biomass derivative is L-cysteine with a concentration of 0.1 mol/L.
A method for photocatalytically reforming a biomass derivative using a semiconductor photocatalyst to generate hydrogen:
Into a Pyrex tube, were added CdSe quantum dots (the concentration of CdSe stock solution: 2×10−1 g/L) to be 1×10−4 g/L in the whole reaction system, CoCrO4 aqueous solution to be 1×10−6 mol/L in the whole reaction system, and ethylene glycol to be 1×10−4 mol/L in the whole reaction system. Then the pH was adjusted to 3. The reactor was vacummized and irradiated with a 500 W high pressure mercury lamp using a 400 nm short wave pass glass filter.
A method for photocatalytically reforming a biomass derivative using a semiconductor photocatalyst to generate hydrogen:
Into a Pyrex tube, were added CdSe quantum dots (the concentration of CdSe stock solution: 2×10−1 g/L) to be 1×10−3 g/L in the whole reaction system, Cobalt-nitrate complex ([Co(NO3)4]2−) to be 1×10−5 mol/L in the whole reaction system, and sucrose to be 1×10−3 mol/L in the whole reaction system. Then the pH was adjusted to 10. The reactor was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp. The glass tube itself can pass through UV and visible light.
A method for photocatalytically reforming a biomass derivative using a semiconductor photocatalyst to generate hydrogen:
Into a Pyrex tube, were added CdSe quantum dots (the concentration of CdSe stock solution: 2×10−1 g/L) to be 1×10−2 g/L in the whole reaction system, cobalt-nitride complex ([Co(NO2)6]3−) to be 2.1×10−4 mol/L in the whole reaction system, and glucose to be 0.1 mol/L in the whole reaction system. Then the pH was adjusted to 8. The reactor was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
After irradiation, synthesized in situ was a semiconductor material with a hollow sphere structure having an outer diameter of 10˜20 nm and a shell thickness of 2˜5 nm. The semiconductor photocatalyst has a formula of CdCoxSe, wherein x was determined to be 0.10% through ICP (inductive coupled plasma emission spectrometer).
The method of example 1 was repeated except that the dopant is nickel bromide and the biomass derivative is L-proline with a concentration of 0.1 mol/L.
The method of example 1 was repeated except that the dopant is nickel sulphate and the biomass derivative is L-cysteine with a concentration of 0.1 mol/L.
The method of example 1 was repeated except that the dopant is nickel oxalate and the biomass derivative is propanol.
The method of example 1 was repeated except that the dopant is nickel acetate and the biomass derivative is n-butanol.
The method of example 1 was repeated except that the dopant is nickel phosphate.
The method of example 1 was repeated except that the dopant is nickel-ammonia complex, [Ni(NH3)6]2+.
The method of example 1 was repeated except that the dopant is nickel-cyanogen complex, [Ni(CN)4]2−.
The method of example 1 was repeated except that the dopant is nickel-chelate, [Ni(en)3]2+.
The method of example 1 was repeated except that the dopant is nickel tetracarbonyl, Ni(CO)4.
The method of example 1 was repeated except that the dopant is nickel-ethyl complex, (C2H5)2Ni.
The method of example 1 was repeated except that the dopant is iron chloride.
The method of example 1 was repeated except that the dopant is ferrous chloride.
The method of example 1 was repeated except that the dopant is ferrous bromide.
The method of example 1 was repeated except that the dopant is ferrous sulphate.
The method of example 1 was repeated except that the dopant is iron fluoride.
The method of example 1 was repeated except that the dopant is iron bromide.
The method of example 1 was repeated except that the dopant is iron iodide.
The method of example 1 was repeated except that the dopant is iron sulphate.
The method of example 1 was repeated except that the dopant is iron nitrate.
The method of example 1 was repeated except that the dopant is iron carbonate.
The method of example 1 was repeated except that the dopant is iron oxalate.
The method of example 1 was repeated except that the dopant is iron acetate.
The method of example 1 was repeated except that the dopant is iron phosphate.
The method of example 1 was repeated except that the dopant is iron chromate.
The method of example 1 was repeated except that the dopant is ferrous fluoride.
The method of example 1 was repeated except that the dopant is ferrous iodide.
The method of example 1 was repeated except that the dopant is ferrous nitrate.
The method of example 1 was repeated except that the dopant is ferrous carbonate.
The method of example 1 was repeated except that the dopant is ferrous oxalate.
The method of example 1 was repeated except that the dopant is ferrous acetate.
The method of example 1 was repeated except that the dopant is ferrous phosphate.
The method of example 1 was repeated except that the dopant is ferrous chromate.
The method of example 1 was repeated except that the dopant is ferrous ammonium sulphate.
The method of example 1 was repeated except that the dopant is ferrous ammonium sulphate.
The method of example 1 was repeated except that the dopant is iron-cyanogen complex, [Fe(CN)6]3−.
The method of example 1 was repeated except that the dopant is ferrous-cyanogen complex, [Fe(CN)6]4−.
The method of example 1 was repeated except that the dopant is iron-thiocyanate complex, Fe(SCN)3.
The method of example 1 was repeated except that the dopant is iron-carbonyl complex, Fe(CO)5.
The method of example 1 was repeated except that the dopant is iron-carbonyl complex, Fe2(CO)9.
The method of example 1 was repeated except that the dopant is iron-carbonyl complex, Fe3(CO)12.
The method of example 1 was repeated except that the dopant is nickel nitrate.
The method of example 1 was repeated except that the dopant is nickel carbonate.
The method of example 1 was repeated except that the dopant is nickel chromite.
The method of example 1 was repeated except that the dopant is nickel fluoride.
The method of example 1 was repeated except that the dopant is nickel iodide.
The method of example 1 was repeated except that the dopant is cobalt fluoride.
The method of example 1 was repeated except that the dopant is cobalt bromide.
The method of example 1 was repeated except that the dopant is cobalt iodide.
The method of example 1 was repeated except that the dopant is cobalt carbonate.
The method of example 1 was repeated except that the dopant is cobalt oxalate.
The method of example 1 was repeated except that the dopant is cobalt acetate.
The method of example 1 was repeated except that the dopant is cobalt phosphate.
The method of example 1 was repeated except that the dopant is cobalt-ammonia complex, [Co(NH3)6]3+.
The method of example 1 was repeated except that the dopant is cobalt-cyanogen complex, [Co(CN)6]4−.
The method of example 1 was repeated except that the dopant is cobalt-thiocyanate complex, [Co(SCN)4]2−.
The method of example 1 was repeated except that the dopant is cobalt-carbonyl complex, [Co(CO)4]−.
The method of example 1 was repeated except that the dopant is cobalt-nitrate complex, [Co(NO3)4]2−.
The method of example 1 was repeated except that the dopant is cobalt-nitrite complex, [Co(NO2)6]3−.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
wherein L=H2O.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
wherein L=CH3CN.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
wherein L=H2O.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
wherein L=CH3CN.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
wherein R═H.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
wherein R═N(CH3)2.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
wherein R═COOCH3.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
wherein. L=H2O.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
wherein L=CH3CN.
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
The method of example 1 was repeated except that the dopant is cobalt-diacetyldioxime complex represented by the following structure:
A method for photocatalytically reforming a biomass derivative using a semiconductor photocatalyst to generate hydrogen:
1×10−1 g/L of CdS quantum dots (the concentration of CdS stock solution: 1 g/L) was added into a Pyrex tube, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of ethanol (original concentration: 17.16 mol/L at 20° C.). Then the pH was adjusted to 8, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
As can be seen from the figure, after irradiation, synthesized in situ was a semiconductor material with a hollow sphere structure having an outer diameter of 10˜20 nm and a shell thickness of 2˜5 nm. The semiconductor photocatalyst has a formula of CdCoxS, wherein x was determined to be 1.0% through ICP (inductive coupled plasma emission spectrometer).
A method for photocatalytically reforming a biomass derivative using a semiconductor photocatalyst to generate hydrogen:
1×10−1 g/L of CdTe quantum dots (the concentration of CdTe stock solution: 2×10−1 g/L) was added into a Pyrex tube, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of ethanol (original concentration: 17.16 mol/L at 20° C.). Then the pH was adjusted to 6, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
A method for photocatalytically reforming a biomass derivative using a semiconductor photocatalyst to generate hydrogen:
1×10−1 g/L of CdTe quantum dots (the concentration of CdTe stock solution: 2×10−1 g/L) was added into a Pyrex tube, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 200 mg of (1.14×10−1 mol/L). Then the pH was adjusted to 6, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
As can be seen from the figure, after irradiation, synthesized in situ was a semiconductor material with a hollow sphere structure having an outer diameter of 10˜20 nm and a shell thickness of 2˜5 nm. XRD patterns in
The method of example 85 was repeated except that the quantum dots are PbS and the biomass derivative is fructose.
The method of example 85 was repeated except that the quantum dots are PbSe and the biomass derivative is maltose.
The method of example 85 was repeated except that the quantum dots are InP and the biomass derivative is mannose.
The method of example 85 was repeated except that the quantum dots are InAs and the biomass derivative is ethanol.
The method of example 85 was repeated except that the quantum dots are ZnS and the biomass derivative is ethanol.
The method of example 85 was repeated except that the quantum dots are ZnSe and the biomass derivative is ethanol.
Mater. 2008, 20, 110-117.
Catalysis. 2009, 266, 165-168.
It can be seen from table 1 that the hydrogen generation rates in Example 1-10 of the present invention are larger than those in literature 1 and 2, and meanwhile the example 1 of the present invention has the largest hydrogen generation rate of 73 μmol·h−1·mg−1.
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdSe quantum dots (the concentration of CdSe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of methanol (original concentration 24.75 mol/L, 20° C.). Then the pH was adjusted to 11 with 1M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
Methanol is an important chemical material, and can be prepared not only from fossil resources using a chemical method, but also from biomass. Methanol has a simple structure with only one hydroxy functional group, and thus can be as a model compound of polyol biomass derivatives. Methanol is decomposed step by step. It is first oxidized into formaldehyde, while H+ is reduced into H2. The formaldehyde reacts with water to generate formic acid, which is finally oxidized into CO2 and H2.
In the present example, the semiconductor photocatalyst has a formula of TiO2—CdCoxSe, wherein x was determined to 0.13% through ICP (inductive coupled plasma emission spectrometer).
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdSe quantum dots (the concentration of CdSe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of ethanol (original concentration 17.16 mol/L, 20° C.). Then the pH was adjusted to 11 with 1M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
Ethanol can be prepared in large scale from fermentation of biomass, and therefore, it is of practical interest to photocatalytically reforming ethanol to generate hydrogen. During the refounation of ethanol aqueous solution, ethanol was first oxidized to acetaldehyde during the initial stage of the photocatalytic reaction, and meanwhile H+ was reduced to H2. The acetaldehyde reacted with water to generate acetic acid, which was finally oxidized to CO2 and H2. Besides, acetaldehyde could react with hydroxyl radicals to yield CO2 and H2.
In the present example, the semiconductor photocatalyst has a formula of TiO2—CdCoxSe, wherein x was determined to 0.26% through ICP (inductive coupled plasma emission spectrometer).
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdSe quantum dots (the concentration of CdSe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 ml of aqueous solution of sucrose (original concentration 0.25 mol/l, 20° C.). Then the pH was adjusted to 11 with 1 M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 21.7 μmol·h−1.
In the present example, the semiconductor photocatalyst has a formula of TiO2—CdCoxSe, wherein x was determined to 0.17% through ICP (inductive coupled plasma emission spectrometer).
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdSe quantum dots (the concentration of CdSe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of aqueous solution of glucose (original concentration 0.25 mol/L, 20° C.). Then the pH was adjusted to 7 with 1M NaOH or HCl, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
As the major component of biomass, it is of practical interest to study the photocatalytic reforming of glucose. During the initial stage of the photocatalytic reaction, glucose is first dehydrogenated to generate ═C═O, —CH═O or —COOH groups, and then the carbon chains are successively oxidized to CO2 by the holes on the surface of the catalysts, releasing H+ that is reduced to H2 at the same time. Since hydroxyl is the immediate, the reaction continues until all the carbons are oxidized to CO2.
In the present example, the semiconductor photocatalyst has a formula of TiO2—CdCoxSe, wherein x was determined to 0.16% through ICP (inductive coupled plasma emission spectrometer).
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdSe quantum dots (the concentration of CdSe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of NiCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of NiCl2.6H2O) and 4 mL of ethanol (original concentration 17.16 mol/L, 20° C.). Then the pH was adjusted to 14 with 1 M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 25.4 μmol·h−1.
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdSe quantum dots (the concentration of CdSe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of NiSO4 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.55 mg of NiSO4.6H2O) and 4 mL of ethanol (original concentration 17.16 mol/L, 20° C.). Then the pH was adjusted to 11 with 1 M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 28.7 μmol·h−1.
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdSe quantum dots (the concentration of CdSe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 1 mg of Fe3(CO)12 and 4 mL of methanol (original concentration 24.75 mol/L, 20° C.). Then the pH was adjusted to 11 with 1 M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 1.8 μmol·h−1.
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdSe quantum dots (the concentration of CdSe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 1 mg of Fe3(CO)12 and 4 mL of ethanol (original concentration 17.16 mol/L, 20° C.). Then the pH was adjusted to 11 with 1 M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 1.5 μmol·h−1.
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdSe quantum dots (the concentration of CdSe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.42 mg of Fe(CO)5 and 4 mL of ethanol (original concentration 17.16 mol/L, 20° C.). Then the pH was adjusted to 11 with 1M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 0.5 μmol·h−1.
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 1 mL of CdS quantum dots (the concentration of CdS stock solution is based on the concentration of cadmium ion, which is equal to 5×10−3 mol/L) and 4 mL of H2O were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of methanol (original concentration 24.75 mol/L, 20° C.). Then the pH was adjusted to 11 with 1M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 37.4 μmol·h−1. In the present example, the semiconductor photocatalyst has a formula of TiO2—CdCoxS, wherein x is 0.02%.
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 1 mL of CdS quantum dots (the concentration of CdS stock solution is based on the concentration of cadmium ion, which is equal to 5×10−3 mol/L) and 4 mL of H2O were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of ethanol (original concentration 17.16 mol/L, 20° C.). Then the pH was adjusted to 11 with 1M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 63.6 μmol·h−1.
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 1 mL of CdS quantum dots (the concentration of CdS stock solution is based on the concentration of cadmium ion, which is equal to 5×10−3 mol/L) and 4 mL of H2O were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of NiCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of NiCl2.6H2O) and 4 mL of ethanol (original concentration 17.16 mol/L, 20° C.). Then the pH was adjusted to 11 with 1 M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 129 μmol·h−1.
In the present example, the semiconductor photocatalyst has a formula of TiO2—CdNixS, wherein x was determined to 0.14% through ICP (inductive coupled plasma, emission spectrometer).
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 1 mL of CdS quantum dots (the concentration of CdS stock solution is based on the concentration of cadmium ion, which is equal to 5×10−3 mol/L) and 4 mL of H2O were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of NiSO4 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.55 mg of NiSO4.6H2O) and 4 mL of ethanol (original concentration 17.16 mol/L, 20° C.). Then the pH was adjusted to 11 with 1M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 59.3 μmol·h−1. In the present example, the semiconductor photocatalyst has a formula of TiO2—CdNixS, wherein x is 1.0%.
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdTe quantum dots (the concentration of CdTe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of methanol (original concentration 24.75 mol/L, 20° C.). Then the pH was adjusted to 11 with 1M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 3.58 μmol·h−1.
In the present example, the semiconductor photocatalyst has a formula of TiO2—CdCoxTe, wherein x was determined to 0.30% through ICP (inductive coupled plasma emission spectrometer).
A method for reforming a biomass derivative using a photocatalytic system comprising a composite semiconductor photocatalyst, comprising the following steps:
10 mg of P-25 TiO2, 5 mL of CdTe quantum dots (the concentration of CdTe stock solution is based on the concentration of cadmium ion, which is equal to 1×10−3 mol/L) were added into a Pyrex tube, and the pH of the mixture was adjusted to 11 with a 1 mol/L NaOH. The mixture was centrifuged, discarded the supernatant to keep the precipitates, followed by addition of 0.5 mL of CoCl2 aqueous solution (original concentration: 4.2×10−3 mol/L, containing 0.5 mg of CoCl2.6H2O) and 4 mL of ethanol (original concentration 17.16 mol/L, 20° C.). Then the pH was adjusted to 11 with 1M NaOH, and the total volume was adjusted to 10 mL. The tube was sealed under nitrogen atmosphere and irradiated with a 500 W high pressure mercury lamp using a 400 nm long wave pass glass filter.
During the reaction, the generated hydrogen was detected with GC equipped with TCD (thermal conductivity detector), and the hydrogen generation rate was 2.5 μmol·h−1.
It is apparently that the above examples of the present invention are only for illustration of the present invention without any limitation to the embodiments of the present invention. Various modifications or variations can be made for a skilled person in the art based on the above description. It is impossible to list all the embodiments here. Any obvious modification or variation derived from the embodiments of the present invention is still within the scope of the present invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010 1 0536574 | Nov 2010 | CN | national |
| 2011 1 0308867 | Oct 2011 | CN | national |
| 2011 1 0344439 | Nov 2011 | CN | national |
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/CN2011/001863 | 11/4/2011 | WO | 00 | 5/2/2013 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2012/058869 | 5/10/2012 | WO | A |
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| 6653356 | Sherman | Nov 2003 | B2 |
| 20040046168 | Andriessen | Mar 2004 | A1 |
| 20050191505 | Akarsu et al. | Sep 2005 | A1 |
| 20050265935 | Hollingsworth et al. | Dec 2005 | A1 |
| 20070137998 | Sykora et al. | Jun 2007 | A1 |
| Number | Date | Country |
|---|---|---|
| 101195475 | Jun 2008 | CN |
| 101745406 | Jun 2010 | CN |
| 57-156302 | Sep 1982 | JP |
| Entry |
|---|
| International Search Report of PCT/CN2011/001863 dated Feb. 16, 2012. |
| Number | Date | Country | |
|---|---|---|---|
| 20130224105 A1 | Aug 2013 | US |
