CN114645283B - 一种高效氮化钒/碳化钼异质结产氢电催化剂及其制备方法与应用 - Google Patents
一种高效氮化钒/碳化钼异质结产氢电催化剂及其制备方法与应用 Download PDFInfo
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- CN114645283B CN114645283B CN202011480813.7A CN202011480813A CN114645283B CN 114645283 B CN114645283 B CN 114645283B CN 202011480813 A CN202011480813 A CN 202011480813A CN 114645283 B CN114645283 B CN 114645283B
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000001257 hydrogen Substances 0.000 title claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 55
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 title abstract description 85
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title abstract description 4
- 229910039444 MoC Inorganic materials 0.000 title abstract description 4
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 38
- 150000001875 compounds Chemical class 0.000 claims description 31
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 26
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 14
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- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 14
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- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 9
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- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
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- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical group [V].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MFWFDRBPQDXFRC-LNTINUHCSA-N 0.000 claims description 2
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 claims description 2
- 150000001412 amines Chemical group 0.000 claims 1
- TVAATYMJWZHIQJ-UHFFFAOYSA-N molybdenum;tetrahydrate Chemical compound O.O.O.O.[Mo] TVAATYMJWZHIQJ-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 7
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 22
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 18
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- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 7
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
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- 239000000463 material Substances 0.000 description 3
- 239000011858 nanopowder Substances 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000000197 pyrolysis Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 2
- INZDTEICWPZYJM-UHFFFAOYSA-N 1-(chloromethyl)-4-[4-(chloromethyl)phenyl]benzene Chemical compound C1=CC(CCl)=CC=C1C1=CC=C(CCl)C=C1 INZDTEICWPZYJM-UHFFFAOYSA-N 0.000 description 2
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
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- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 2
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229910017263 Mo—C Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
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- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 description 1
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- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 1
- CFJRGWXELQQLSA-UHFFFAOYSA-N azanylidyneniobium Chemical compound [Nb]#N CFJRGWXELQQLSA-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
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- QWJNFFYFEKXZBF-UHFFFAOYSA-N cyanocyanamide Chemical compound N#CNC#N QWJNFFYFEKXZBF-UHFFFAOYSA-N 0.000 description 1
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- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- JAGQSESDQXCFCH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo].[Mo] JAGQSESDQXCFCH-UHFFFAOYSA-N 0.000 description 1
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- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 description 1
- 229910001456 vanadium ion Inorganic materials 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- ZVWKZXLXHLZXLS-UHFFFAOYSA-N zirconium nitride Chemical compound [Zr]#N ZVWKZXLXHLZXLS-UHFFFAOYSA-N 0.000 description 1
Classifications
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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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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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
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1275—Process of deposition of the inorganic material performed under inert atmosphere
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
- C23C18/1283—Control of temperature, e.g. gradual temperature increase, modulation of temperature
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- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/052—Electrodes comprising one or more electrocatalytic coatings on a substrate
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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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/065—Carbon
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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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
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Abstract
本发明公开一种高效氮化钒/碳化钼异质结产氢电催化剂及其制备方法与应用。所述电催化剂具有由VN和Mo2C偶联形成的异质结结构，其中VN和Mo2C的质量比为20：1~50：1。所述催化剂将纳米VN与Mo2C偶联形成VN/Mo2C异质结，使得活性中心增加，还利于H+吸附/H2解吸动力学的平衡，从而在很大程度上提高催化剂的活性。
Description
技术领域
本发明属于纳米粉体催化材料领域，具体涉及一种高效VN/Mo2C异质结产氢电催化剂及其制备方法与应用。
背景技术
随着化石能源问题的日益突出，人类面临新一轮的机遇和挑战。氢能作为一种绿色、可循环利用、丰富的资源，越来越受到广大学者的关注。虽然铂族金属(PFMs)具有优异的催化性能，但铂基催化剂的价格高、含量低、不稳定等缺点严重阻碍其在全球范围的应用。探索优异的产氢催化剂是水裂解制氢的关键技术点所在。
近些年来，研究人员发现一些重要的非贵金属催化剂，比如过渡金属碳化物(TMCs)和过渡金属氮化物(TMNs)。其中，TMCs主要包括碳化钼(Mo2C)、碳化镍(Ni3C)、碳化钨(WC和W2C)、碳化钒(VC)等。TMNs主要包括氮化钒(VN)、氮化钛(TiN)、氮化锆(ZrN)和氮化铌(NbN)。上述非贵金属催化剂具有与Pt相似的电子结构，这引起了科研人员的广泛关注。但是单相TMCs或TMNs的HER特性受到电子结构不足和氢结合能不匹配的限制。对此研究人员已经采取一系列手段来提高TMCs或TMNS催化剂的HER性能，例如引入具有一定形貌的碳材料，如碳纳米管或石墨烯，来诱导材料的碳化生长以及特定形貌金属氧化物的合成，或者将TMCs与TMNs杂交以促进协同效应。
在上述非贵金属催化剂中，氮化钒具有良好的导电性、导热性和催化性能，对H2的解吸有很强的辅助作用，然而其合成温度较高且形貌难以控制；碳化钼具有优异的催化性能和氢结合能，有利于H+的吸附，不过导电性能较差，从而影响电极上电子传输速率。
发明内容
鉴于此，本发明的目的在于提供一种高效VN/Mo2C异质结产氢电催化剂及其制备方法与应用。所述催化剂将纳米VN与Mo2C偶联形成VN/Mo2C异质结，使得活性中心增加，还利于H+吸附/H2解吸动力学的平衡，从而在很大程度上提高催化剂的活性。
第一方面，本发明提供一种高效VN/Mo2C异质结产氢电催化剂。所述高效VN/Mo2C异质结产氢电催化剂具有由VN和Mo2C偶联形成的异质结结构。异质结结构形成更多缺陷，同时提供更多活性位点，促进VN和Mo2C的催化协同效应，进而提升催化性能。
较佳地，所述高效VN/Mo2C异质结产氢电催化剂呈现为VN颗粒和Mo2C颗粒均匀分布形成的类珊瑚虫形貌。
较佳地，所述VN颗粒和Mo2C颗粒的粒径分别为30～100nm和50～100nm。
第二方面，本发明提供上述任一项所述的高效VN/Mo2C异质结产氢电催化剂的制备方法。所述制备方法包括：将包含碳氮同源化合物、钒源、钼源的原料称料后混合，于惰性气氛下在400～500℃保温50～200min，然后在700～900℃保温120～180min，获得高效VN/Mo2C异质结产氢电催化剂。优选地，在400～500℃保温120min。
较佳地，所述碳氮同源化合物、钒源、钼源的质量比为(18～20)：(3～5)：(1～3)。
较佳地，所述碳氮同源化合物中氮的质量百分比在30％以上。碳氮同源化合物中含氮的质量百分比30％以上，氮含量越高，活性位点暴露越多，有利于电解水过程中H+的结合，从而促进H2的释放。碳氮同源化合物中氮的质量百分比优选为40～70％。
较佳地，所述碳氮同源化合物在保温过程中热解产生还原性气体并使VN/Mo2C异质结产氢电催化剂的各组成均匀分散。一些技术方案中，所述还原性气体为NH3。这避免了在制备过程中额外引入还原性气体造成资源浪费和成本提高。
较佳地，所述碳氮同源化合物选自双氰铵、三聚氰胺、尿素中的至少一种。
较佳地，所述钒源选自乙酰丙酮钒和/或偏钒酸铵；所述钼源包括四水合钼酸胺和/或二水合钼酸钠。应理解本发明制备方法使用的钒源和钼源包括但不局限于上述化合物。任何形式的、可提供钒元素和钼元素的化合物均可用于本发明。在实际应用中优选使用价格低廉、实用性好的钒源和钼源。
第三方面，本发明还提供上述任一项所述的高效VN/Mo2C异质结产氢电催化剂在电解水制氢方面的应用。
本发明具有以下有益效果：
1.本发明的VN/Mo2C电催化剂采用过渡金属碳化物与氮化物复合形成异质结结构。氮化物提供良好的导电性，有较低的H2反应势垒；碳化物提供更多活性位点，有利于H+的吸附。两者成功复合，平衡了H+吸附/H2脱附反应动力学，促进协同催化效应。
2.本发明通过固相法制备VN/Mo2C，为碳化物与氮化物的杂交提供新的合成策略，操作简单易行，容易控制，适合工业化生产。
3.本发明的VN/Mo2C催化剂可应用于电催化领域中水裂解产氢的全pH溶液，适用范围广，可以满足工业化规模生产的需求。
4.本发明的电催化剂具有过电势小的特点(例如电流10mA/cm2时，在碱性、酸性和中性环境的过电势分别为50mV、140mV和185mV)，稳定性好，塔菲尔斜率小，在水裂解方面的应用具备很大潜力。
附图说明
图1是实施例1制备的纳米VN/Mo2C的XRD图；
图2是实施例1制备的纳米VN/Mo2C的SEM图；
图3是实施例1制备的纳米VN/Mo2C的TEM图；
图4是实施例2制备的纳米VN/Mo2C在pH 14条件下的产氢性能图；
图5是实施例3制备的纳米VN/Mo2C在pH 14条件下的产氢性能图；
图6是实施例4制备的纳米VN/Mo2C在pH 14条件下的产氢性能图；
图7是实施例1制备的纳米VN/Mo2C在pH 0条件下的产氢性能图；
图8是实施例1制备的纳米VN/Mo2C在pH 14条件下的产氢性能图；
图9是实施例1制备的纳米VN/Mo2C在pH 7条件下的产氢性能图；
图10是对比例1制备的纳米VN/Mo2C的XRD图谱；
图11是对比例1制备的纳米VN/Mo2C在pH 14条件下的产氢性能图；
图12是对比例2将VN和Mo2C物理混合的复合材料在pH 14条件下的产氢性能图；
图13是实施例1制备的纳米VN/Mo2C的X射线光电子能谱图；
图14是对比例3制备的样品的XRD图；
图15是对比例3制备的样品在不同视野下的TEM图；
图16是对比例3制备的样品在pH 14条件下的产氢性能图。
具体实施方式
通过下述实施方式进一步说明本发明，应理解，下述实施方式仅用于说明本发明，而非限制本发明。
以下示例性说明本发明所述高效VN/Mo2C异质结产氢电催化剂(也可以称为“电催化功能VN/Mo2C异质结纳米粉体”)的制备方法。
按照一定质量比称量碳氮同源化合物、钒源和钼源。所述碳氮同源化合物、钒源、钼源的质量比可为(18～20)：(3～5)：(1～3)。当碳氮同源化合物、钒源、钼源的质量比超出上述范围时，例如为17：3：1时，氧化钒无法被完全还原，最终产物的组成中具有较多的氧化钒和其他杂相，从而影响VN的生成。
本发明的制备方法中，使用碳氮同源化合物引入碳元素和氮元素。碳氮同源化合物在后续反应过程中热解产生还原性气体(例如氨气)，不仅发挥还原剂的作用，还可实现复合结构中VN颗粒和Mo2C颗粒的均匀分散，不需要额外的还原剂和分散剂。另外，采用碳氮同源的化合物，减少参与反应的化合物种类，尽可能地避免高温碳化过程中发生聚集、引入杂质以及杂相堆积。又，碳氮同源化合物价格便宜，适合工业化生产，且反应安全。
优选地，所述碳氮同源化合物中氮的质量百分比在30％以上。在实验过程中意外发现，碳源氮源同源物中氮元素的质量百分比较高时，生成产物的产能高且催化性能优异。例如，发明人探究了不同氮源对VN/Mo2C催化剂的电催化性能的影响。结果发现，虽然使用不同氮源所得产物的物相、表面形貌差异较小，但是，当碳氮同源化合物中氮元素的质量百分比达到30％以上时，产物VN/Mo2C电催化剂呈现为异质结结构。该异质结结构有利于增强电子的传导和提高催化性能。一些实施方式中，碳氮同源化合物中氮的质量百分比为40-70％。在具体实施方式中，所述碳氮同源化合物包括但不限于双氰铵、三聚氰胺和尿素中的一种或几种。
将称量后的碳氮同源化合物、钒源和钼源混合，得到混合料。优选为干法混合。例如可通过搅拌、球磨等方式进行混合。混合的时间不受限制，使得所有原料混合均匀即可。将混合料通过固相合成的方式制备目标产物VN/Mo2C异质结产氢电催化剂。所述固相合成在惰性保护气氛下进行。惰性保护气氛可为氩气。作为优选，惰性保护气氛的流速为20-40sccm。
例如，将混合料放入玛瑙研钵中，研磨20～30min后装入瓷舟。将瓷舟置于管式气氛炉中，在管两端各放两个炉塞，炉塞间隔5cm。向管式气氛炉内通入惰性气氛，继而进行4～6次抽气补气，排尽管式气氛炉内空气，最后一次补气后不再抽气。惰性气氛可为氩气。所述固相合成分为两阶段进行。第一阶段为：以20～40sccm的流速通入保护气氛，以5～10℃/min升温加热至400～500℃，并在400～500℃保温120min。第二阶段为：继续升温至700～900℃，并在700～900℃保温120～180min。上述方案采取分段升温机制。第一阶段的目的是低温热解生成C3N4，第二阶段的作用是C3N4还原钒源中V并生成VN。随着温度继续升高，Mo6+和Mo4+被热解过程中产生的NH3还原成Mo2+后与C反应生成Mo-C，并进一步形成VN/Mo2C异质结结构。保温结束后，随炉冷却到室温，研磨黑色样品，即得到VN/Mo2C异质结产氢电催化剂。该异质结结构的VN/Mo2C产氢电催化剂，与物理混合的VN和Mo2C相比，在相同电流密度下，物理复合样品的性能远不及VN/Mo2C异质结样品的性能，凸显出异质结结构对样品电催化性能的协同催化作用。
本发明所述VN/Mo2C异质结纳米粉体形貌尺寸均匀，导电性好、稳定性好，可以应用全pH溶液的电催化，为电解水提供另外一种绿色、丰富的能源，以替换目前工业最为广泛应用的高成本铂基材料。
本发明的高效VN/Mo2C异质结产氢电催化剂中，VN和Mo2C的质量比可为20：1～50：1。该质量比通过ICP测试获得。ICP测试使用的设备是Optima 7300V(美国珀金埃尔默公司)。ICP制样如下：(i)称取1mg的样品，溶解在20mL王水中(浓盐酸和浓硝酸按体积比为3:1配制)，在100℃下油浴加热，直至溶液挥发到1mL；(ii)将挥发后的溶液定容在100mL容量瓶中，调整溶液的pH呈弱酸性(pH 6左右)，装满在10mL的离心管中；(iii)测试钒离子和钼离子的ppm浓度(ppm表示溶质占溶液质量的百分比)，即可计算出VN和Mo2C的质量比。
电催化析氢测试采用三电极体系，在CHI660E B17060电化学工作站(上海辰华仪器有限公司)上进行，所使用的参比电极为饱和甘汞电极(SCE)，对电极为石墨碳棒，工作电极为玻碳电极。制备工作电极的步骤如下：(i)将10mg催化剂分散在异丙醇(200μL)中，超声形成均匀的混合物；(ii)将2μL混合物溶液滴到玻碳电极(GCE)上，催化剂的担载密度约为1.4mg cm-2；(iii)催化剂在空气中自然风干后，为了防止在测量过程中催化剂受到电解液影响而发生脱落，需要将2μL质量分数1％Nafion(粘结剂)溶液涂覆到已经干燥的催化剂表面。对所制备的样品在酸性(0.5M H2SO4)、中性(pH 7的磷酸盐缓冲溶液)、碱性(1M KOH)条件下分别进行电催化性能测试。线性扫描伏安曲线(LSV)以3mV s-1的扫描速率进行测试。
下面进一步例举实施例以详细说明本发明。同样应理解，以下实施例只用于对本发明进行进一步说明，不能理解为对本发明保护范围的限制，本领域的技术人员根据本发明的上述内容作出的一些非本质的改进和调整均属于本发明的保护范围。下述示例具体的工艺参数等也仅是合适范围中的一个示例，即本领域技术人员可以通过本文的说明做合适的范围内选择，而并非要限定于下文示例的具体数值。
实施例1
1)按照质量比为19：5：3称取三聚氰胺、偏钒酸铵和四水合钼酸铵。
2)将上述粉料干混并在玛瑙研钵中研磨30min,装入瓷舟中，将瓷舟置于管式气氛炉中，并在管两端各放两个炉塞，间隔5cm。
3)向管内通入氩气，继而进行6次抽气补气，排尽管内空气，最后一次补气后不再抽气。
以40sccm的流速通入惰性保护气氛(氩气)，以10℃/min升温至500℃，在500℃保温120min，继续升温至800℃并保温180min。
4)保温结束后，冷却到室温，研磨黑色样品，得到目标产物VN/Mo2C。
图1是实施例1制备的纳米VN/Mo2C的XRD图谱，可以看出VN和Mo2C衍射峰与标准卡片匹配良好，且强度高，说明VN/Mo2C结晶性很好。图2是实施例1制备的纳米VN/Mo2C的SEM图，可以看出样品形貌为类珊瑚虫结构，样品分散性良好。图3是实施例1制备的纳米VN/Mo2C的TEM图，可以看出VN/Mo2C具有明显的异质结结构，且0.21nm的晶格条纹对应VN的(200)晶面，0.23nm的晶格条纹对应Mo2C的(101)晶面。
图13是实施例1制备的纳米VN/Mo2C的X射线光电子能谱图，可以看到VN颗粒和Mo2C颗粒均匀分布。
图7是实施例1制备的纳米VN/Mo2C在pH 0条件下的产氢性能图，当电流密度为10mA/cm2，扫描速率为3mV/s时，该样品过电势为140mV。图8是实施例1制备的纳米VN/Mo2C在pH 14条件下的产氢性能图，当电流密度为10mA/cm2，扫描速率为3mV/s时，该样品过电势为50mV。图9是实施例1制备的纳米VN/Mo2C在pH 7条件下的产氢性能图，当电流密度为10mA/cm2，扫描速率为3mV/s时，该样品过电势为185mV。以上说明实施例1制备的VN/Mo2C异质结产氢电催化剂在全pH溶液下均具有优异的产氢性能。
实施例2
1)按照质量比为18：3：1称取尿素、偏钒酸铵和四水合钼酸铵。
2)将上述粉料干混并在玛瑙研钵中研磨20min,装入瓷舟中，将瓷舟置于管式气氛炉中，并在管两端各放两个炉塞，间隔5cm。
3)向管内通入氩气，继而进行4次抽气补气，排尽管内空气，最后一次补气后不再抽气。以20sccm的流速通入惰性保护气氛(氩气)，以5℃/min升温至400℃，在400℃保温120min，继续升温至700℃并保温120min。
4)保温结束后，冷却到室温，研磨黑色样品，得到目标产物VN/Mo2C。
图4是实施例2制备的纳米VN/Mo2C在pH 14条件下的产氢性能图，当电流密度为10mA/cm2，扫描速率为3mV/s时，该样品过电势为235mV，说明具有优异的产氢性能。
实施例3
1)按照质量比19：4：2称取双氰铵、偏钒酸铵和四水合钼酸铵。
2)将上述粉料干混并在玛瑙研钵中研磨30min,装入瓷舟中，将瓷舟置于管式气氛炉中，并在管两端各放两个炉塞，间隔5cm。
3)向管内通入氩气，继而进行5次抽气补气，排尽管内空气，最后一次补气后不再抽气。以30sccm的流速通入惰性保护气氛(氩气)，以10℃/min升温至500℃，在500℃保温120min，继续升温至800℃并保温180min。
4)保温结束后，冷却到室温，研磨黑色样品，得到目标产物VN/Mo2C。
图5是实施例3制备的纳米VN/Mo2C在pH 14条件下的产氢性能图，当电流密度为10mA/cm2，扫描速率为3mV/s时，该样品过电势为95mV，说明具有优异的产氢性能。
实施例4
1)按照质量比为20：3：1称取三聚氰胺、偏钒酸铵和四水合钼酸铵。
2)将上述粉料干混并在玛瑙研钵中研磨20min,装入瓷舟中，将瓷舟置于管式气氛炉中，并在管两端各放两个炉塞，间隔5cm。
3)向管内通入氩气，继而进行6次抽气补气，排尽管内空气，最后一次补气后不再抽气。以40sccm的流速通入惰性保护气氛(氩气)，以5℃/min升温至400℃，在400℃保温120min，继续升温在900℃并保温120min。
4)保温结束后，冷却到室温，研磨黑色样品，得到目标产物VN/Mo2C。
图6是实施例4制备的纳米VN/Mo2C在pH 14条件下的产氢性能图，当电流密度为10mA/cm2，扫描速率为3mV/s时，该样品过电势为117mV，说明具有优异的产氢性能。
实施例5
与实施例3基本相同，区别仅在于：步骤1)中尿素、偏钒酸铵和四水合钼酸铵的质量比为19：4：2。
实施例6
与实施例2基本相同，区别仅在于：以30sccm的流速通入惰性保护气氛(氩气)。
对比例1
与实施例1基本相同，区别仅在于：尿素、偏钒酸铵和四水合钼酸铵的质量比为17：3：1。图10是对比例1制备的纳米VN/Mo2C的XRD图谱，可以看出VN没有被完全还原，而且出现三氧化二钒峰和许多杂相峰。图11是对比例1制备的纳米VN/Mo2C在pH14下的产氢性能图，可以看出当电流密度为10mA/cm2，扫描速率为3mV/s时，该样品过电势为285mV大于图4的235mV，性能变差。
对比例2
将VN和Mo2C(V:Mo摩尔比为2:1)搅拌物理混匀。图12是对比例2将VN和Mo2C物理混合的复合材料在pH 14条件下的产氢性能图，可以看到在相同电流密度下，物理混合样品的性能(323mV)不及VN/Mo2C异质结样品的性能(50mV)。进一步验证了异质结结构可以暴露更多的活性位点，形成更大的电化学面积，拥有更优异的电催化性能。
对比例3
与实施例1基本相同，区别仅在于：以三聚硫氰酸作为碳氮同源化合物(氮含量在30％以下)。
当以三聚硫氰酸：偏钒酸铵：四水合钼酸铵按照质量比为19：5：3制备复合材料时，样品的XRD如图14所示，可以看出VN和Mo2C衍射峰与标准卡片匹配良好，但是VN的衍射峰强度很弱，说明碳氮同源化合物的氮含量在30％以下，不利于VN的生成。图15是该样品的TEM图，在样品的不同部位可以看到VN和Mo2C的晶格条纹，没有找到异质结结构。结合XRD和TEM分析可知，当碳氮同源化合物的氮含量在30％以下时，影响了VN的生成，同样没有生成VN和Mo2C的异质结结构，影响了样品的催化性能。图16为该样品的产氢性能图，从图中可以看出，在pH 14测试条件下，当电流密度为10mA/cm2，扫描速率为3mV/s时，该样品过电势为314mV，大于实施例1(235mV)，性能明显变差。
Claims (9)
1.一种VN/Mo2C异质结产氢电催化剂，其特征在于，所述电催化剂具有由VN和Mo2C偶联形成的异质结结构，其中VN和Mo2C的质量比为20：1～50：1。
2.根据权利要求1所述的VN/Mo2C异质结产氢电催化剂，其特征在于，所述电催化剂为VN颗粒和Mo2C颗粒均匀分布形成的类珊瑚虫形貌。
3.根据权利要求2所述的VN/Mo2C异质结产氢电催化剂，其特征在于，所述VN颗粒和Mo2C颗粒的粒径分别为30～100nm和50～100nm。
4.根据权利要求1至3中任一项所述的VN/Mo2C异质结产氢电催化剂的制备方法，其特征在于，所述制备方法包括：将包含碳氮同源化合物、钒源、钼源的原料称料后混合，于惰性气氛下在400～500℃保温50～200min，然后在700～900℃保温120～180min，获得VN/Mo2C异质结产氢电催化剂；所述碳氮同源化合物在保温过程中热解产生还原性气体并使VN/Mo2C异质结产氢电催化剂的各组成均匀分散；所述碳氮同源化合物选自双氰铵、三聚氰胺、尿素中的至少一种。
5.根据权利要求4所述的制备方法，其特征在于，所述碳氮同源化合物、钒源、钼源的质量比为(18～20)：(3～5)：(1～3)。
6.根据权利要求4或5所述的制备方法，其特征在于，所述碳氮同源化合物中氮的质量百分比在30％以上。
7.根据权利要求6所述的制备方法，其特征在于，所述碳氮同源化合物中氮的质量百分比为40～70％。
8.根据权利要求4或5所述的制备方法，其特征在于，所述钒源选自乙酰丙酮钒和/或偏钒酸铵；所述钼源选自四水合钼酸胺和/或二水合钼酸钠。
9.权利要求1至3中任一项所述的VN/Mo2C异质结产氢电催化剂在全pH溶液环境下电解水制氢方面的应用。
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