Patent Application
20180345265
This disclosure relates generally to carbon-based nanoparticles. In particular, it relates to nanoparticles for use as electrocatalysts.
Carbon black is often used as support for platinum-based nanocatalysts in polymer electrolyte membrane fuel cells (PEMFCs) because of its high specific surface area, high electrical conductivity and low cost. However, the corrosion of the carbon may occur, especially under automotive start/stop conditions. The high transient voltage up to 1.5 V at the cathode may accelerate the carbon degradation, resulting in agglomeration of Pt particles due to their detachment from the carbon surface. The loss of electrochemical surface area of Pt catalysts, together with lowered transport properties of the porous catalyst layer, may result in PEMFC performance decay. [Yu, X.; Ye, S. J. Power Sources 2007, 172 (1), 145-154]
Therefore, there remains a need for platinum or metallic-based nanocatalysts having corrosion resistance at high potentials and improved durability.
In one embodiment, the present carbon support comprising carbon particles having a surface with a plurality of pores. These surface pores are utilized for embedding first metal or first metal compound particles into the conductive carbon surface with the size of embedded particles controlled by the amount of metal precursor being put into the surface pores. The embedded particles can be catalytically active or inactive. In the latter case, another second metal or second metal compound, for example, a catalytic active material is deposited on top of the embedded inactive particles, thereby capping the pores. As schematically illustrated in
In another embodiment, the present particles, comprise, consist essentially of, or consist of a carbon support particle having a surface with a plurality of pores, filled by amorphous NbOx wherein 0≤x≤2 is the average number of oxygen per niobium and x can be an integer or non-integer. Each of the majority NbOx particles is enclosed by the carbon wall around it and a metal hemisphere on top of it. The metal hemisphere may be Pt. While Pt/C is commonly used for Pt nanoparticles weakly attached on a larger carbon particle, such a catalyst is termed as Pt—NbOx-C, in which “-” expresses a strong binding rather than a weak attachment. This type of core-shell structure increases utilization of precious metal by having them only on the top hemisphere. NbOx serves as an inexpensive and stable core for anchoring down Pt nanoparticles to minimize particle agglomeration after wide-range potential cycles. Tested for application as a catalyst for oxygen reduction reaction (ORR) in acidic media, the Pt mass activity of Pt—NbOx-C is more than twofold and sevenfold of that for Pt/C measured prior and post 50,000 potential cycles between 0.6 and 1.0 V at 50 mV s−1. There is no loss in activity after 5,000 potential cycles between 1 and 1.5 V at 500 mV
In another embodiment, the present methods for forming the Pt—NbOx—C catalyst are described, the methods comprising, consisting essentially of, or consisting of providing a carbon based support particle having a surface with a plurality of about 4 nm pores; creating a mixture by adding the carbon based support particle to a solution or slurry of a Nb(V) precursor compound in a solvent; agitating the mixture; drying the particles of the mixture; exposing the particles to heat and a reducing gas; combining the particles with a metal salt solution; and reducing the metal of the metal salt solution.
In another embodiment, the present methods for forming an electrocatalytic particle, the methods comprising, consisting essentially of, or consisting of providing a carbon support particle having a surface with a plurality of pores; creating a mixture by adding the carbon support particle to a liquid solution of a Nb(V) compound with a specified ratio of carbon weight to solution volume; sonicating the slurry for sufficient time until all of the liquid is absorbed into the carbon; drying the mixture in a vacuum oven; exposing the dried mixture to heat and reducing gas; combining the NbOx-embedded particles with a solution containing Pt ions; and letting Pt spontaneous deposition on NbOx to occur or with asserted by adding mild reducing agent (e.g., ethanol).
The present invention provides a carbon support particle having a metal or metal compound embedded therein and a carbon support having a catalytically inactive material embedded therein and a catalytically active metal or metal compound deposited on top of the catalytically inactive material, and methods of making the same.
The carbon support particle includes a surface having a plurality of pores. The pores may be uniform in distribution across the particle surface, diameter, and depth. Carbon support particles can have a spherical shape, non-spherical shape, polyhedral shape, or octahedral shape. The carbon support particles may be in the form of sheets, tubes, or hollow tubes.
In one embodiment, the carbon support particle has a minimum average diameter of about 10 nm, about 20 nm, or about 30 nm. In one embodiment, the carbon support particle has a maximum diameter of about 100 nm, about 80 nm, about 50 nm, or about 40 nm. In one embodiment, the average diameter is 30 nm.
In one embodiment, the carbon support particle has an average diameter between about 10 nm to about 100 nm, about 20 nm to about 80 nm, or between about 20 nm to about 50 nm. The carbon support particle may be a nanoparticle.
In one embodiment, the pores of the carbon support particle have a minimum average diameter of about 1 nm, about 2 nm, or about 3 nm. In one embodiment, the pores of the carbon support particle have a maximum diameter of about 50 nm, about 20 nm, about 10 nm, or about 5 nm.
The pores have a depth of between about 1 nm and about 7 nm. In one embodiment, the pores have an average depth of between about 2 nm and about 5 nm. In one embodiment, the pores have an average depth of between about 3 nm and about 4 nm.
In one embodiment, the pores of the carbon support particle have an average diameter of between about 1 nm to about 50 nm, between about 1 nm to about 20 nm, between about 1 nm to about 10 nm, or between about 2 nm to about 5 nm. In one embodiment, the pores of the carbon support particle have an average diameter of about 4 nm.
In one embodiment, the carbon support particle has a diameter of about 30 nm, an average pore size of about 4 nm, and pore depth of about 3 nm to about 4 nm.
Examples of carbon support particles include superconductive carbon black, such as for example Ketjenblack EC 600JD and Ketjenblack 300J (KB). The carbon support particle may be in the form of a soft pellet or a fine powder. These carbon support particles have similar particles sizes, about 30 nm in diameter, differing in specific surface area, as measured by N2 adsorption. These carbon support particles may have uniformly distributed or substantially uniformly distributed pores on the surface. The pores may be an average diameter of about 4 nm and an average depth of about 3-4 nm. The specific surface area of KB may be due to its pore size diameter, i.e., about 4 nm pores, on its surface. Ketjenblack EC 600JD has a BET surface area of approximately 1270 m2/g and Ketjenblack 300J has a BET surface area of approximately 800 m2/g. Smaller sized particles yield higher specific surface area, which may be particularly useful for catalytic and battery applications.
A metal or metal compound is embedded into the pores of the carbon support particle. In one embodiment, the metal or metal compound is embedded into substantially all of the pores of the carbon support particle. Embedding metal or metal compound into the pores of a carbon surface can promote activity and durability of metal catalysts for electrochemical reactions. As used herein, “embedded” refers to a positional relation in which a guest object (metals or metal compounds) is at least partially enclosed by walls in a host object (carbon based support particle having a plurality of pores, said pores providing inner walls) such that the guest object is in contact with the walls, wherein the walls are all made of the same material composition (carbon). The guest object is therefore within the pores of the host object with the top surface exposed.
In one embodiment, the guest object may be a catalytic active metal, a metal alloy, or a metal compound being deposited in the small and uniformly distributed surface pores on carbon support particles by firstly filling the pores with solutions containing the metal salts. The metal precursors dried inside the pores are reduced to metal or metal alloy or metal compound particles by exposure to heat and a reducing gas, such as hydrogen, carbon monoxide, ammonia, and methane. The guest particles embedded in the surface pores can be metal, metal alloy, oxides, nitrides, and carbides.
In one embodiment, the catalytically active metal includes any catalytically active metal capable of being reduced.
In one embodiment, the catalytically active metal includes any noble metal. In another embodiment, the catalytically active metal includes any platinum group metal.
Examples of suitable catalytically active metals include noble metals, such as, ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au).
In one embodiment, the guest object includes more than one noble metal. For example, the guest object includes Pt and Pd. In another embodiment, the guest object is Pt and Ir. In another embodiment, the guest object is Pt and Ru.
In another embodiment, a carbon support particle may have a catalytically inactive material embedded in the surface pores and a catalytically active metal deposited thereon. Examples of catalytically inactive material include conductive metal oxides, nitrides, and carbides or non-precious metals.
As used herein, NbOx is used for Nb oxide without being specific for an oxidation state, or the number of O per Nb. NbOx includes NbO, NbO2, or both, wherein x is an average number of oxygen (O) atoms per niobium (Nb) atom, where x may represent a mix between greater than 0 and less than or equal to 2. In one embodiment, x may be a non-integer value equal to or greater than 1 and less than or equal to 2. In one embodiment, x is 1 or 2, or a combination of 1 and 2.
In one embodiment, the NbOx embedded on the surface of the carbon support includes a mixture of NbOx having different values for x, wherein the value for x ranges from greater than 0 to less than or equal to 2.
As used herein “deposited” means the addition of one or more materials on a substrate, including, for example, the addition of a metal or metal compound onto NbOx.
The catalytically active metal can be deposited on a surface (e.g., a substrate surface, or exposed surface of NbOx) by methods that are well known to one of skill in the art. As used herein, “deposited on” a surface is intended to be broadly interpreted to include any suitable means of applying a catalytically active metal to the surface including, for example, deposition methods, coating methods, transfer methods, and/or other available application methods.
In one embodiment, at least one catalytically active metal described herein is deposited on NbOx, wherein the NbOx is first embedded onto a carbon support particle as described herein. Further description of depositing a metal on NbOx is described below.
The embedded NbOx and catalytically active metal thereupon is in substantially all of the pores of the carbon support particle to provide a substantially uniform surface.
In one embodiment, a carbon support particle may have NbOx and a catalytically active metal deposited thereupon. Such particle may define an electrocatalytic particle or electrocatalyst.
In another embodiment, a carbon support particle may have a catalytic inactive NbOx (0≤x≤2 on average for amorphous niobium oxide) embedded in the surface pores and is further covered by Pt on top (of the NBOx) to form a Pt—NbOx—C catalyst for ORR, which exhibits high Pt mass activity and excellent durability against potential cycles to 1 and 1.5 V.
Without wishing to be bound by theory, the catalytic active particles are formed on each of the surface pores via strong binding with the embedded material (e.g., NbOx) on the carbon support. In such a way, the metals are all in the top hemisphere (e.g., capping the pores) and thus better utilized, which may lead to higher mass activity and concurrently high stability against particle agglomeration. In one embodiment, the surface of the embedded material is partially capped. In another embodiment, the exposed embedded material is completely capped. In one embodiment, substantially all of the pores are capped with a metal.
Without wishing to be bound by theory, it is believed that it is the uniform pore size and uniform distribution across the entire surface of the carbon support particle, coupled with the uniform distribution of the NbOx and deposited metal thereupon, which provides the superior characteristics over the prior art.
Preferably, the amount of Nb2O5 in the particles described above should be minimized. Even more preferably, there is no Nb2O5 in the particles described above.
In one embodiment, the present composition includes a particle composition including a plurality of the particles described above.
In one embodiment, a method is provided for forming metal-Nbx-C electrocatalyst for ORR.
A carbon particle with embedded NbOx may be formed by first providing a carbon support particle, as described above. The carbon support particle is added to an ethanolic solution of a Nb(V) precursor compound to form a slurry containing carbon support particles and Nb(V) precursor. Suitable Nb(V) precursors include niobium (V) pentachloride or NbCl5 and niobium (V) ethoxide or Nb(EtO)5. The former, NbCl5 (yellow) reacts with solvent ethanol to form Nb(EtO)5 (colorless). Water and moisture can cause formation of highly stable Nb2O5 (white solid), which needs to be avoided. Preferably, the amount of Nb2O5 should be minimized. Even more preferably, there is no Nb2O5.
The slurry is agitated to aid in absorption of the solution into the carbon surface pores. Agitation may be accomplished by any method known in the art. An example of a suitable agitation method includes sonication. The slurry is agitated for a time sufficient for the solution to be absorbed into the carbon support particle. In one embodiment, the slurry is agitated for at least 1 hour, at least 2 hours, at least 3 hours, or at least 5 hours.
Without wishing to be bound by theory, it is believed that complete absorption of the solution into the carbon support provides the superior results over the prior art, as shown herein. On this basis, it is important to match the volume of metal precursor solution with the total pore volume of added carbon particles. The volume of metal precursor solution with the total pore volume may vary depending upon the specific characteristics of the carbon support and the nature of the metal precursor. The specific amount can be determined by a person of ordinary skill in the art, in view of the present disclosure.
For using Ketjenblack EC 600JD (KB) as the carbon support particles, the suitable carbon weight per solvent volume is in the range of 12 to 25 g L−1; mostly likely about 20 g L−1 for achieving no excess liquid at top of the slurry after more than 2 hours sonication. This ensures all metal precursors are absorbed into the surface pores so that no large metal particles form outside carbon particles during heat treatment.
The molar amount of Nb precursor per gram of KB may be 1 to 6 mmol; the suitable value is about 3 mmol
Without wishing to be bound by theory, confinement of the Nb(V) precursor in the nm-sized pores on the surface of the carbon based support particle maximizes the formation of NbOx particles with x being 1 or 0. Low oxidation state is preferred because conductivity and reducing power of NbOx increase with lowering x.
The slurry is dried in vacuum oven at about 70° C. to minimize moisture in air that can cause formation of hard to reduce Nb2O5. Drying may occur at any temperature suitable for this purpose. Additional examples of suitable drying temperatures include about 50° C. to 100° C. or 60° C. to 80° C. The resulting solid is ground into a fine powder. The particles are then exposed to heat and a reducing gas. A suitable reducing gas includes H2. Examples of other suitable reducing gasses include ammonia, methane, and carbon monoxide.
The NbOx embedded carbon particles are then immediately combined with a metal salt solution after taking out of a tube furnace to avoid surface oxidation of NbOx. Examples of suitable metals include a noble metal, such as ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), and gold (Au). For example, suitable metal salt solutions include H2PtCl6 or K2PtCl4 or HAuCl4.
Next, the metal of the metal salt solution is reduced.
Without wishing to be bound by theory, embedded NbO particles act as metal or Pt nucleation sites due to its ability to reduce PtCl42− precursor in solution so that the growth of Pt nanoparticles are mostly on NbOx (x is close to 1, after Pt deposition, NbO likely becomes NbO2). This structure is ideal for maximizing Pt utilization and enhancing particle stability against agglomeration. At the same time, conductive NbO2 is protected by surrounding carbon and Pt on top so that its oxidation to non-conductive Nb2O5 is minimized. While many Nb-containing catalysts rarely match the Pt mass activity of Pt/C of the prior art, the present Pt-NbO2—C catalysts exceed the mass activity of the prior art by at least 100%, while providing excellent durability against 0.6-1V and 1-1.5V potential cycles.
The high degree of dispersion and uniformity of NbOx particles over the entire carbon surface may be achieved by utilizing the surface pores on carbon. Controlling particle size and distribution by size and density of surface pores allow wide temperature ranges to be used in synthesis for fabricating small and well dispersed particles. The concept may be applied for making other metal, alloy, and oxide particles. High quality production can be made at low cost because the method does not use any chemical agents to control particle size.
The high degree of dispersion and uniformity of NbOx particles over entire carbon surface may be achieved by utilizing the surface pores on carbon. Controlling particle size and distribution by size and density of surface pores allow wide temperature ranges to be used in synthesis for fabricating small and well dispersed particles. The concept may be applied for making other metal, alloy, and oxide particles. High quality production can be made at low cost because the method does not use any chemical agents to control particle size.
Throughout this specification, quantities are defined by ranges, and by lower and upper boundaries of ranges. Each lower boundary can be combined with each upper boundary to define a range. The lower and upper boundaries should each be taken as a separate element.
In this specification, groups of various parameters containing multiple members are described. Within a group of parameters, each member may be combined with any one or more of the other members to make additional sub-groups. For example, if the members of a group are a, b, c, d, and e, additional sub-groups specifically contemplated include any one, two, three, or four of the members, e.g., a and c; a, d, and e; b, c, d, and e; etc.
Reference throughout this specification to “one embodiment,” “an embodiment,” “one example,” or “an example” means that a particular feature, structure or characteristic described in connection with the embodiment or example is included in at least one embodiment of the present embodiments. Thus, appearances of the phrases “in one embodiment,” “in an embodiment,” “one example,” or “an example” in various places throughout this specification are not necessarily all referring to the same embodiment or example. Furthermore, the particular features, structures or characteristics may be combined in any suitable combinations and/or sub-combinations in one or more embodiments or examples. In addition, it is appreciated that the figures provided herewith are for explanation purposes to persons ordinarily skilled in the art and that the drawings are not necessarily drawn to scale.
Further, unless expressly stated to the contrary, “or” refers to an inclusive “or” and not to an exclusive “or”. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).
In the specification, numerous specific details are set forth in order to provide a thorough understanding of the present embodiments. It will be apparent, however, to one having ordinary skill in the art that the specific detail need not be employed to practice the present embodiments. In other instances, well-known materials or methods have not been described in detail in order to avoid obscuring the present embodiments.
Cited references, for which all their contents are incorporated herein in their entirety:
The present Pt—NbOx—C catalyst is illustrated in further details by the following non-limiting examples.
The pores on KB were filled with Nb precursor by sonication of ethanolic slurry containing 50 mg KB and 150 μmol of Nb(EtO)5 in 2.5 mL ethanol for 2 or more hours until liquid was completed absorbed. Water or moisture in air can react with Nb(V) compounds to form the most stable Nb2O5 (white solid) which should be avoid. The mixture was dried in vacuum oven for more than 3 hours and then grinded to fine powder. Thermal decomposition of Nb(EtO)5 and reduction of Nb(V) were carried out in a tube furnace with hydrogen as reductant for 1 hour at 220° C., 1 hour at 650° C., and 0.5 hour at 900° C.
To show the effect of surface pores on carbon on reducing Nb(V) precursor to low oxidation state oxide particles, samples were made, using the same procedure, with KB and VC, the latter does not have a plurality of small surface pores. These two carbon materials have similar particles sizes, about 30 nm in diameter, differing in specific surface area, as measured by N2 adsorption. The differing specific surface area between VC and KB is due to KB having many pores (≤4 nm in diameter) on the surface. [Liu et al., J. Electrochem. Soc. 2011, v 158, B614]. This is due to KB has a plurality of surface pores of about ˜4 nm in diameter as evidenced by the peak in the Barrett-Joyner-Halenda (BJH) pore-size distribution curve shown in
These samples exhibited different X-ray diffraction profiles as shown in
The high dispersion and uniformity of small NbOx particles on KB can be seen clearly by comparing the TEM images in
Further proof for the NbOx being embedded into carbon for the sample made with KB was obtained from thermogravimetric analysis (TGA) of three samples: C, C mixed with NbO2 particles, and NbOx-C synthesized using Nb salt and KB. As shown in
A thin layer of most stable Nb2O5 forms on low-oxidation-state NbOx once the samples were exposed to oxygen in air or brought into water, which then inhibits bulk oxidation at room temperature. To observe electro-oxidation of NbO surface, inks of freshly prepared NbOx—C samples were made using ethanol and iso-propanol in 6:1 volume ratio, and drop casted the ink on to a glassy carbon rotating disk electrode (RDE).
In summary, the examples above describe utilizing the small pores on KB to fabricate well dispersed NbO nanoparticles with size <5 nm stabilized in the sub-surface of carbon. More specifically, describing NbO nanoparticles embedded in the pores of the carbon based support particle.
The reducing power of the portion of embedded NbOx exposed on the surface was utilized to create Pt nucleation via galvanic reaction between NbOx and Pt precursor in solutions. Further Pt particle growth may be assisted by adding mild reducing agents, such as ethanol or citric acid.
The strong binding between Pt and NbOx is illustrated by a high-resolution STEM image of a single Pt particle shown in
Evaluation of the Pt—NbOx—C catalysts was performed on rotating disk electrode in 0.1 M HClO4 solutions with the Pt content in the catalyst determined catalyst as by inductive coupled plasma mass spectrometry (ICP). Compared to Pt nanoparticles attached on carbon support (Pt/C), the ORR polarization curve for Pt—NbOx—C catalyst exhibited larger ORR currents at higher potentials in
Durability against 1 to 1.5 V potential cycles at 50 mV s−1 that corresponds to the fuel cell startup-shutdown cycles is also tested. As shown in
The enhanced Pt mass activity and catalyst durability is ascribed to the high density of about 5 nm hemisphere Pt particles anchored down on carbon surface via embedded NbOx. A common issue for other catalysts involving conductive NbO or NbO2 is increased resistance of initially low-oxidation-state oxides being oxidized to nonconductive Nb2O5. This issue is largely alleviated by enclosing NbOx by surround carbon and Pt on top to prevent its oxidation to Nb2O5. Even Nb2O5 eventually form, the impact on ORR activity is limited because these particles are only about 5 nm and within conductive carbon.
In the example of a catalytic application, embedded NbO serves as the nucleation sites for growing Pt particles on it, not an inactive support. Pt particles formed are strongly bounded with NbOx with a semi-spherical shape. These particles are separated from each other as their location is determined by the surface pores. Conductive NbO or NbO2 are made less prone to electro-oxidation than non-conductive Nb2O5 by having them being protected by the surrounding carbon and Pt on top. These unique and desirable features may contribute to the high ORR activity and durability against potential cycles up to 1.5 V.
The high degree of dispersion and uniformity of NbO particles over entire carbon surface may be achieved by utilizing the surface pores on carbon. Controlling particle size and distribution by size and density of surface pores allow wide temperature ranges to be used in synthesis for fabricating small and well dispersed particles. The concept may be applied for making other metal, alloy, and oxide particles. High quality production can be made at low cost because the method does not use any chemical agents to control particle size.
While there have been described what are presently believed to be the preferred embodiments of the present invention, those skilled in the art will realize that other and further changes and modifications may be made thereto without departing from the spirit of the invention, and it is intended to claim all such modifications and changes as come within the true scope of the invention.
This application claims the benefit of U.S. Provisional Application No. 62/515,214, filed Jun. 5, 2017, which is hereby incorporated by reference in its entirety.
This invention was made with Government support under contract number DE-SC0012704 awarded by the U.S. Department of Energy. The Government has certain rights in the invention.
| Number | Date | Country | |
|---|---|---|---|
| 62515214 | Jun 2017 | US |
