CN110327949B - Carbon-supported rhodium/rhodium phosphide nanocomposite and preparation method and application thereof - Google Patents
Carbon-supported rhodium/rhodium phosphide nanocomposite and preparation method and application thereof Download PDFInfo
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- 239000010948 rhodium Substances 0.000 title claims abstract description 196
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 191
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 190
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000002114 nanocomposite Substances 0.000 title abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 97
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 97
- 239000002105 nanoparticle Substances 0.000 claims abstract description 68
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000002131 composite material Substances 0.000 claims abstract description 58
- QBERHIJABFXGRZ-UHFFFAOYSA-M rhodium;triphenylphosphane;chloride Chemical compound [Cl-].[Rh].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 QBERHIJABFXGRZ-UHFFFAOYSA-M 0.000 claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 59
- 238000006243 chemical reaction Methods 0.000 claims description 46
- 238000010438 heat treatment Methods 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 26
- 238000004140 cleaning Methods 0.000 claims description 25
- 238000004519 manufacturing process Methods 0.000 claims description 19
- 239000003054 catalyst Substances 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 13
- 238000001816 cooling Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000002829 reductive effect Effects 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000000354 decomposition reaction Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 11
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 11
- 239000011574 phosphorus Substances 0.000 abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 10
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 3
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 3
- 239000010453 quartz Substances 0.000 description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 21
- 229910052573 porcelain Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 11
- 238000005303 weighing Methods 0.000 description 10
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003623 transition metal compounds Chemical class 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1856—Phosphorus; Compounds thereof with iron group metals or platinum group metals with platinum group metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention provides a carbon-loaded rhodium/rhodium phosphide nano composite material and a preparation method and application thereof, wherein tris (triphenylphosphine) rhodium chloride simultaneously contains a phosphorus source and a rhodium source as initial reactants for the first time, and provides a simple, mild and controllable thermal decomposition method. The carbon-supported rhodium/rhodium phosphide nanoparticle composite material is completely expected to replace a commercial Pt/C hydrogen evolution electrocatalyst material, and has wide practical application prospect in the field of electrocatalytic hydrogen evolution.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of preparation of catalysts for hydrogen production by water electrolysis, and relates to a carbon-supported rhodium/rhodium phosphide nanocomposite and a preparation method and application thereof.
[ background of the invention ]
Hydrogen energy has attracted extensive attention as an efficient, environment-friendly and green energy source, and hydrogen production by water electrolysis is widely researched as an efficient and feasible preparation method. The catalyst is one of the important factors determining the hydrogen production rate of electrolyzed water, and various electrocatalysts have been studied in a large number, such as noble metal Pt, transition metal sulfide, transition metal phosphide and the like. Research reports that the phosphorus-rich transition metal compound has more excellent catalytic performance in hydrogen production by electrolysis than the transition metal compound without phosphorus. It is known that the hydrogen absorption activity and the catalyst surface hydrogen adsorption free energy (. DELTA.G)H*) Closely related, when Δ GH*When equal to 0eV, the catalytic activity is strongest, when Δ GH*When the amount is less than 0eV, hydrogen atoms are bonded to the surface of the catalyst too strongly, whereby hydrogen release is not favored, and when Δ G is usedH*When the energy barrier is larger than 0eV, the transmission of hydrogen atoms is not facilitated due to the higher energy barrier, and the calculation result shows that the hydrogen adsorption free energy of the rhodium phosphide is only 0.04eV and is very close to 0eV, so that the rhodium phosphide is particularly suitable for serving as a hydrogen production catalyst. At present, the common methods for preparing rhodium phosphide comprise a hydrothermal method, a thermal injection method, high-temperature phosphorization and the like, but various preparation methods are relatively complex and are not beneficial to large-scale production; common phosphorus sources such as elemental phosphorus and phosphorus compounds all have flammable risks, so that a safe and reliable phosphorus and rhodium-containing compound is foundThe material is very urgent, and the development of a simple and safe method for producing rhodium phosphide in a large scale is particularly important.
On the other hand, when the existing rhodium phosphide is used as a hydrogen production catalyst, the existing rhodium phosphide is a single-phase hydrogen production catalyst, and if a composite-phase hydrogen production catalyst can be prepared, the hydrogen production catalytic performance of the existing rhodium phosphide can be further improved.
[ summary of the invention ]
The invention aims to overcome the defects of the prior art and provides a carbon-supported rhodium/rhodium phosphide nanocomposite and a preparation method and application thereof; the carbon-supported rhodium/rhodium phosphide nanocomposite prepared by the method improves the electron transport capability of the carbon-supported rhodium/rhodium phosphide nanocomposite as a hydrogen production catalyst, has good overall stability, and can solve the problems of flammability of a phosphorus source, complex preparation process, inconvenience for large-scale production and the like.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
a carbon-supported rhodium/rhodium phosphide nanoparticle composite material is characterized in that rhodium/rhodium phosphide nanoparticles are supported on a carbon chain framework, and the surfaces of the rhodium/rhodium phosphide nanoparticles are coated by carbon layers.
The invention is further improved in that:
preferably, the rhodium/rhodium phosphide nanoparticles have a heterogeneous interface between rhodium and rhodium phosphide.
A preparation method of a carbon-supported rhodium/rhodium phosphide nanoparticle composite material is characterized in that the carbon-supported rhodium/rhodium phosphide nanoparticle composite material is prepared by decomposing tris (triphenylphosphine) rhodium chloride after being reduced by hydrogen.
Preferably, the reductive decomposition of tris (triphenylphosphine) rhodium chloride by hydrogen specifically comprises the following steps: and (2) placing the tris (triphenylphosphine) rhodium chloride in a closed reaction vessel, introducing argon-hydrogen mixed gas into the closed reaction vessel, heating the reaction vessel to perform a reduction reaction, and naturally cooling to room temperature after the reaction is finished to prepare the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
Preferably, before the argon-hydrogen mixed gas is introduced into the reaction vessel, the gas atmosphere in the reaction vessel is purged with the argon-hydrogen mixed gas.
Preferably, before the argon-hydrogen mixed gas is used for cleaning the gas atmosphere of the reaction vessel, the reaction vessel is vacuumized until the vacuum degree in the reaction vessel is less than 5Pa, and then the argon-hydrogen mixed gas is introduced for cleaning the gas atmosphere in the reaction vessel.
Preferably, the hydrogen reduction reaction temperature is 400-600 ℃, and the reaction time is 2-4 h.
Preferably, the argon-hydrogen mixed gas has a hydrogen content of 5% and an argon content of 95%.
Preferably, the flow rate of the argon-hydrogen mixed gas introduced per 50mg of tris (triphenylphosphine) rhodium chloride is (80-100) ppm.
The carbon-supported rhodium/rhodium phosphide nanoparticle composite material is used as a hydrogen production catalyst in the process of hydrogen production by electrolyzing water.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a carbon-loaded rhodium/rhodium phosphide nano composite material, which is characterized in that rhodium/rhodium phosphide nano particles are loaded on a carbon chain framework, and the surfaces of the rhodium/rhodium phosphide nano particles are coated by a carbon layer; firstly, compared with the existing pure rhodium phosphide nano-particles, rhodium phosphide and a carbon layer in the ternary structure have the capability of transmitting electrons, and the electrons can pass through the ternary structure; secondly, the surface of the composite nano particle formed by rhodium and rhodium phosphide is wrapped by a carbon layer, the overall stability of the material can be enhanced due to the strong acting force of the carbon bond, and the carbon layer is wrapped by rhodium and rhodium phosphide, so that the agglomeration of the same elements is avoided, and the microstructure of the material is more uniform; thirdly, as the rhodium/rhodium phosphide nanoparticles are loaded on the carbon chain skeleton, more active site positions of the rhodium/rhodium phosphide nanoparticles are exposed (agglomeration is reduced), and the catalytic performance of the composite material is improved; therefore, compared with the existing rhodium phosphide, the composite material has more excellent conductivity and stronger stability.
Furthermore, a heterogeneous interface is formed between rhodium and rhodium phosphide in the rhodium/rhodium phosphide nano-particles, more defects exist in the heterogeneous interface, and the heterogeneous interface is mainly a dangling bond of phosphorus and rhodium atoms, so that electrons are very easily adsorbed, and the electron transport capability of the composite material can be improved.
The invention also discloses a preparation method of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material, which selects tris (triphenylphosphine) rhodium chloride and simultaneously contains a phosphorus source and a rhodium source as initial reactants for the first time, and provides a simple, mild and controllable thermal decomposition method, wherein tris (triphenylphosphine) rhodium chloride is decomposed into the high-quality rhodium/rhodium phosphide nanoparticle composite material in a reaction vessel in a reducing atmosphere in one step; the preparation method well solves the problems that the phosphorus source is inflammable, the preparation process is complex, and the large-scale production is not facilitated.
Furthermore, before the reaction, vacuumizing and gas washing of protective gas are carried out, so that the reaction process is carried out in a reducing atmosphere, and the purity of the reaction product is improved.
Further, the reaction temperature and reaction time are limited, and the preparation process finds that the higher the temperature is, the better the crystallinity of the produced composite material is.
Further, the proportional relationship between the raw materials is limited, if the flow rate of the mixed gas is too small, the reaction is not complete relative to a certain amount of tris (triphenylphosphine) rhodium chloride, and if the flow rate of the mixed gas is too large, reactants or reaction products may be taken away, and the yield of the reaction products is reduced.
The invention also discloses an application of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material in hydrogen production by water electrolysis, and the material has wide application prospect as a hydrogen catalyst in hydrogen production by water electrolysis due to the excellent conductivity and stability of the material. Experimental verification shows that the hydrogen evolution current density of the prepared carbon-supported rhodium/rhodium phosphide nanoparticle composite material reaches 10mv/cm2The over-potential value of the catalyst is only 4.37mv, which is also the alkali in all the reported same material systems at presentThe hydrogen evolution overpotential in the polar electrolyte is the lowest. The carbon-supported rhodium/rhodium phosphide nanoparticle composite material is completely expected to replace a commercial Pt/C hydrogen evolution electrocatalyst material, and has wide practical application prospect in the field of electrocatalytic hydrogen evolution.
[ description of the drawings ]
FIG. 1 is an XRD pattern of the product shown in example 1;
FIG. 2 is an SEM photograph of the morphology of the product shown in example 1;
FIG. 3 is an EDX spectrum of the product set forth in example 1;
FIG. 4 is a HRTEM topography of the product shown in example 1;
FIG. 5 is a graph of the electrocatalytic oxygen evolution performance of the product shown in example 1;
wherein (a) is a LSV curve of the product for hydrogen evolution in 1M KOH solution, and (b) is a tafel slope curve of the product;
FIG. 6 is an SEM picture of the morphology of the product shown in example 2;
FIG. 7 is an SEM picture of the morphology of the product shown in example 3.
[ detailed description ] embodiments
The invention is further described in detail with reference to the accompanying drawings, and discloses a carbon-supported rhodium/rhodium phosphide nanocomposite material and a preparation method and application thereof; the method specifically comprises the following steps:
step 1, weighing a certain amount of tris (triphenylphosphine) rhodium chloride, and placing the tris (triphenylphosphine) rhodium chloride in a reaction vessel, wherein the reaction vessel is preferably a quartz tube of a tube furnace;
step 3, introducing reaction gas, wherein the reaction gas is argon-hydrogen mixed gas, and the flow rate of the reaction gas used by 50mg of tris (triphenylphosphine) rhodium chloride is (80-100) ppm; in the argon-hydrogen mixed gas, the hydrogen content is 5%, and the argon content is 95%;
step 4, after reaction gas is introduced, starting to heat a quartz tube in the tube furnace, wherein the heating rate is 2 ℃/min, the reaction temperature is 400-; .
In the reaction process of the step 4, the set reaction temperature is reached, and the tris (triphenylphosphine) rhodium chloride [ (C)6H5)3P]3RhCl reacts, and the reaction equation is as follows: [ (C)6H5)3P]3RhCl→[(C6H5)3P]3+Rh/Rh2P+HCl(g)
Obtaining metal rhodium and rhodium phosphide in the reaction process, wherein by-products are triphenylphosphine and HCl, and benzene rings in triphenyl are carbonized at high temperature to form a carbon chain framework; the produced metal rhodium and rhodium phosphide are attached to a carbon chain framework, and the metal rhodium and the rhodium phosphide are coated by a carbon layer.
Example 1
Weighing 50mg of tris (triphenylphosphine) rhodium chloride, placing the tris (triphenylphosphine) rhodium chloride in a porcelain boat, and moving the porcelain boat to a heating area in a quartz tube of a tube furnace; vacuumizing the quartz tube, introducing argon-hydrogen mixed gas when the vacuum degree reaches 5Pa, wherein the hydrogen accounts for 5 percent, and the rest is argon, and cleaning for 10 min; after cleaning is finished, setting the gas flow of the argon-hydrogen mixed gas to be 85ppm, and ventilating normally; and then setting the heating rate to be 2 ℃/min, heating from room temperature to 500 ℃, reacting for 2 hours at 500 ℃, and naturally cooling to room temperature along with the furnace after the reaction is finished to obtain the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
XRD, SEM, EDX and HRTEM characterization and analysis are carried out on the carbon-supported rhodium/rhodium phosphide nanoparticle composite material obtained in example 1, and the results are shown in figures 1-4.
FIG. 1 is an XRD pattern of a carbon-supported rhodium/rhodium phosphide nanoparticle composite material prepared in example 1 of the present invention, which has characteristic diffraction peaks corresponding to phases of metal rhodium and rhodium phosphide, in accordance with standard cards of Rh-PDF-87-0714 and Rh2P-PDF-65-6417, and amorphous peaks at 30-35 ℃ which are characteristic of carbon.
Fig. 2 is an SEM photograph of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material prepared in example 1 of the present invention, and it can be seen that the carbon-supported rhodium/rhodium phosphide nanoparticle composite material prepared in example 1 is a porous distribution having a carbon skeleton on which rhodium and rhodium phosphide are supported and at the same time, rhodium and rhodium phosphide composite nanoparticles are wrapped by a carbon layer.
FIG. 3 is an EDX energy spectrum of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material prepared in example 1 of the present invention, wherein the carbon-supported rhodium/rhodium phosphide nanoparticle composite material mainly contains three elements of carbon, rhodium and phosphorus, and the EDX energy spectrum is consistent with an XRD spectrum.
FIG. 4 is a HRTEM photograph of a carbon-supported rhodium/rhodium phosphide nanoparticle composite material prepared in example 1 of the present invention, Rh and Rh2The lattice fringes of P are clearly discernable, with interplanar spacings of 0.2723nm and 0.1946nm corresponding to Rh2The (200) and (220) crystal planes of P and the (111) crystal plane of Rh corresponding to the interplanar spacing of 0.2193nm are consistent with the result of XRD pattern, two phases of rhodium and rhodium phosphide are indeed present, and a heterogeneous interface is formed between the rhodium and rhodium phosphide composite nanoparticles.
Fig. 5 is a graph of hydrogen evolution electrocatalytic performance of carbon supported rhodium/rhodium phosphide nanoparticle composites prepared in example 1 of the present invention, wherein (a) is a graph of hydrogen evolution LSV of the product in 1M KOH solution, all tests were tested in a standard three-electrode system, wherein the counter electrode was platinum mesh, the reference electrode was silver/silver chloride electrode, and the working electrode was glassy carbon electrode. The hydrogen evolution current density of the sample carbon-supported rhodium/rhodium phosphide nanoparticle composite material in the example 1 reaches 10mv/cm2Over-potential of 4.37mv, whereas commercial Pt/C catalyst materials reach 10mv/cm2The overpotential of oxygen evolution of the catalyst is 31.52mv, and the overpotential value of hydrogen evolution of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material is far smaller than that of a commercial Pt/C catalyst; (b) the plots are the tafel slope plots corresponding to the products, from which it can be seen that the tafel slopes for the carbon-supported rhodium/rhodium phosphide nanoparticle composites and the commercial Pt/C are 36.11 and 79.41mv dec, respectively-1The hydrogen evolution rate of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material is obviously superior to that of commercial Pt/C.
The hydrogen evolution current density of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material prepared in the example 1 reaches 10mv/cm2Over-potential value ofIt is only 4.37mv, which is the lowest hydrogen evolution overpotential in alkaline electrolyte in all the reported same material systems. The carbon-supported rhodium/rhodium phosphide nanoparticle composite material is completely expected to replace a commercial Pt/C hydrogen evolution electrocatalyst material, and has wide practical application prospect in the field of electrocatalytic hydrogen evolution.
Example 2
Weighing 50mg of tris (triphenylphosphine) rhodium chloride, placing the tris (triphenylphosphine) rhodium chloride in a porcelain boat, and moving the porcelain boat to a heating area in a quartz tube of a tube furnace; vacuumizing the quartz tube, introducing argon-hydrogen mixed gas when the vacuum degree reaches 5Pa, wherein the hydrogen accounts for 5 percent, and the rest is argon, and cleaning for 10 min; after cleaning is finished, setting the gas flow of the argon-hydrogen mixed gas to be 85ppm, and ventilating normally; and then setting the heating rate to be 2 ℃/min, heating from room temperature to 400 ℃, reacting for 2 hours at 400 ℃, and naturally cooling to room temperature along with the furnace after the reaction is finished to obtain the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
Fig. 6 is an SEM photograph of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material prepared in example 2 of the present invention, wherein the carbon-supported rhodium/rhodium phosphide nanoparticles are distributed in a scattered manner, and compared with example 1, the crystallinity is inferior, mainly the reaction temperature is lower, and the lower the reaction temperature is, the lower the connection effect of the carbon layer is, so that the carbon layer has no way to coat the rhodium/rhodium phosphide nanoparticles well, so that the rhodium/rhodium phosphide nanoparticles are distributed in a scattered manner.
Example 3
Weighing 50mg of tris (triphenylphosphine) rhodium chloride, placing the tris (triphenylphosphine) rhodium chloride in a porcelain boat, and moving the porcelain boat to a heating area in a quartz tube of a tube furnace; vacuumizing the quartz tube, introducing argon-hydrogen mixed gas when the vacuum degree reaches 5Pa, wherein the hydrogen accounts for 5 percent, and the rest is argon, and cleaning for 10 min; after cleaning is finished, setting the gas flow of the argon-hydrogen mixed gas to be 85ppm, and ventilating normally; and then setting the heating rate to be 2 ℃/min, heating from room temperature to 600 ℃, reacting for 2 hours at 600 ℃, and naturally cooling to room temperature along with the furnace after the reaction is finished to obtain the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
Fig. 7 is an SEM photograph of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material prepared in example 3 of the present invention, in which rhodium and rhodium phosphide are supported on the carbon chain skeleton and are distributed in a loose porous manner, and the crystallinity is better than that of examples 1 and 2, mainly due to higher reaction temperature, the higher reaction temperature is, the better the connectivity of the carbon chain skeleton is, and the better the coating effect of the carbon layer on rhodium and rhodium phosphide is, so that the crystallinity of the whole composite material is better.
Example 4
Weighing 50mg of tris (triphenylphosphine) rhodium chloride, placing the tris (triphenylphosphine) rhodium chloride in a porcelain boat, and moving the porcelain boat to a heating area in a quartz tube of a tube furnace; vacuumizing the quartz tube, introducing argon-hydrogen mixed gas when the vacuum degree reaches 5Pa, wherein the hydrogen accounts for 5 percent, and the rest is argon, and cleaning for 20 min; after the cleaning is finished, setting the gas flow of the argon-hydrogen mixed gas to be 80ppm, and ventilating normally; and then setting the heating rate to be 2 ℃/min, heating to 450 ℃ from room temperature, reacting for 3 hours at 450 ℃, and naturally cooling to room temperature along with the furnace after the reaction is finished to obtain the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
Example 5
Weighing 50mg of tris (triphenylphosphine) rhodium chloride, placing the tris (triphenylphosphine) rhodium chloride in a porcelain boat, and moving the porcelain boat to a heating area in a quartz tube of a tube furnace; vacuumizing the quartz tube, introducing argon-hydrogen mixed gas when the vacuum degree reaches 5Pa, wherein the hydrogen accounts for 5 percent, and the rest is argon, and cleaning for 15 min; after cleaning is finished, setting the gas flow of the argon-hydrogen mixed gas to be 90ppm, and ventilating normally; and then setting the heating rate to be 2 ℃/min, heating from room temperature to 550 ℃, reacting for 2.5 hours at 550 ℃, and naturally cooling to room temperature along with the furnace after the reaction is finished to obtain the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
Example 6
Weighing 50mg of tris (triphenylphosphine) rhodium chloride, placing the tris (triphenylphosphine) rhodium chloride in a porcelain boat, and moving the porcelain boat to a heating area in a quartz tube of a tube furnace; vacuumizing the quartz tube, introducing argon-hydrogen mixed gas when the vacuum degree reaches 3Pa, wherein the hydrogen accounts for 5 percent, and the rest is argon, and cleaning for 10 min; after the cleaning is finished, setting the gas flow of the argon-hydrogen mixed gas to 88ppm, and ventilating normally; and then setting the heating rate to be 2 ℃/min, heating from room temperature to 580 ℃, reacting for 2 hours at 580 ℃, and naturally cooling to room temperature along with the furnace after the reaction is finished to obtain the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
Example 7
Weighing 50mg of tris (triphenylphosphine) rhodium chloride, placing the tris (triphenylphosphine) rhodium chloride in a porcelain boat, and moving the porcelain boat to a heating area in a quartz tube of a tube furnace; vacuumizing the quartz tube, introducing argon-hydrogen mixed gas when the vacuum degree reaches 5Pa, wherein the hydrogen accounts for 5 percent, and the rest is argon, and cleaning for 25 min; after cleaning is finished, setting the gas flow of the argon-hydrogen mixed gas to be 85ppm, and ventilating normally; and then setting the heating rate to be 2 ℃/min, heating from room temperature to 600 ℃, reacting for 2 hours at 600 ℃, and naturally cooling to room temperature along with the furnace after the reaction is finished to obtain the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
Example 8
Weighing 50mg of tris (triphenylphosphine) rhodium chloride, placing the tris (triphenylphosphine) rhodium chloride in a porcelain boat, and moving the porcelain boat to a heating area in a quartz tube of a tube furnace; vacuumizing the quartz tube, introducing argon-hydrogen mixed gas when the vacuum degree reaches 5Pa, wherein the hydrogen accounts for 5 percent, and the rest is argon, and cleaning for 10 min; after the cleaning is finished, setting the gas flow of the argon-hydrogen mixed gas to be 92ppm, and ventilating normally; and then setting the heating rate to be 2 ℃/min, heating the mixture to 480 ℃ from room temperature, reacting for 4 hours at 480 ℃, and naturally cooling the mixture to room temperature along with the furnace after the reaction is finished to obtain the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
Example 9
Weighing 50mg of tris (triphenylphosphine) rhodium chloride, placing the tris (triphenylphosphine) rhodium chloride in a porcelain boat, and moving the porcelain boat to a heating area in a quartz tube of a tube furnace; vacuumizing the quartz tube, introducing argon-hydrogen mixed gas when the vacuum degree reaches 3Pa, wherein the hydrogen accounts for 5 percent, and the rest is argon, and cleaning for 10 min; after the cleaning is finished, setting the gas flow of the argon-hydrogen mixed gas to be 100ppm, and ventilating normally; and then setting the heating rate to be 2 ℃/min, heating from room temperature to 500 ℃, reacting for 3.5 hours at 500 ℃, and naturally cooling to room temperature along with the furnace after the reaction is finished to obtain the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
The preparation process adopted by the invention is simple, a thermal decomposition method with mild and controllable reaction conditions is adopted, and the uniform, dispersed and loose porous carbon-loaded rhodium/rhodium phosphide nanoparticle composite material is obtained in one step in a reducing atmosphere annealing furnace, and can be applied to the field of electrocatalytic hydrogen evolution.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The carbon-supported rhodium/rhodium phosphide nanoparticle composite material is characterized in that rhodium/rhodium phosphide nanoparticles are supported on a carbon chain framework, and the surfaces of the rhodium/rhodium phosphide nanoparticles are coated by carbon layers.
2. The carbon-supported rhodium/rhodium phosphide nanoparticle composite material as claimed in claim 1, wherein the rhodium/rhodium phosphide nanoparticle is characterized in that a heterogeneous interface is formed between rhodium and rhodium phosphide.
3. The preparation method of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material is characterized in that the carbon-supported rhodium/rhodium phosphide nanoparticle composite material is prepared by reducing tris (triphenylphosphine) rhodium chloride by hydrogen and then decomposing the reduced tris (triphenylphosphine) rhodium chloride.
4. The preparation method of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material as claimed in claim 3, wherein the reductive decomposition of tris (triphenylphosphine) rhodium chloride by hydrogen specifically comprises the following steps: and (2) placing the tris (triphenylphosphine) rhodium chloride in a closed reaction vessel, introducing argon-hydrogen mixed gas into the closed reaction vessel, heating the reaction vessel to perform a reduction reaction, and naturally cooling to room temperature after the reaction is finished to prepare the carbon-supported rhodium/rhodium phosphide nanoparticle composite material.
5. The preparation method of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material as claimed in claim 4, wherein before introducing the argon-hydrogen mixed gas into the reaction vessel, the argon-hydrogen mixed gas is used for cleaning the gas atmosphere in the reaction vessel.
6. The preparation method of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material as claimed in claim 4, wherein before the argon-hydrogen mixed gas is used for cleaning the gas atmosphere of the reaction vessel, the reaction vessel is vacuumized until the vacuum degree in the reaction vessel is less than 5Pa, and then the argon-hydrogen mixed gas is introduced for cleaning the gas atmosphere in the reaction vessel.
7. The method for preparing the carbon-supported rhodium/rhodium phosphide nanoparticle composite material as claimed in claim 3, wherein the hydrogen reduction reaction temperature is 400-600 ℃ and the reaction time is 2-4 h.
8. The preparation method of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material as claimed in claim 4, wherein the content of hydrogen in the argon-hydrogen mixed gas is 5% and the content of argon in the argon-hydrogen mixed gas is 95%.
9. The preparation method of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material as claimed in claim 4, wherein the flow rate of the argon-hydrogen mixed gas introduced per 50mg of tris (triphenylphosphine) rhodium chloride is (80-100) ppm.
10. The application of the carbon-supported rhodium/rhodium phosphide nanoparticle composite material in hydrogen production by electrolyzing water is characterized in that the carbon-supported rhodium/rhodium phosphide nanoparticle composite material is used as a hydrogen production catalyst in the hydrogen production process by electrolyzing water.
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