CN114645284B - 一种三相体系三氧化二钒/氮化钒/碳化钼纳米电极材料及其制备方法与应用 - Google Patents
一种三相体系三氧化二钒/氮化钒/碳化钼纳米电极材料及其制备方法与应用 Download PDFInfo
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- 239000007772 electrode material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- SKKMWRVAJNPLFY-UHFFFAOYSA-N azanylidynevanadium Chemical compound [V]#N SKKMWRVAJNPLFY-UHFFFAOYSA-N 0.000 title abstract description 5
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 title abstract description 3
- 229910039444 MoC Inorganic materials 0.000 title abstract description 3
- QUEDYRXQWSDKKG-UHFFFAOYSA-M [O-2].[O-2].[V+5].[OH-] Chemical compound [O-2].[O-2].[V+5].[OH-] QUEDYRXQWSDKKG-UHFFFAOYSA-M 0.000 title abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000001257 hydrogen Substances 0.000 claims abstract description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 22
- 239000002245 particle Substances 0.000 claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 17
- 150000001875 compounds Chemical class 0.000 claims description 32
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 claims description 29
- 229910052720 vanadium Inorganic materials 0.000 claims description 19
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 19
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 15
- 229910052750 molybdenum Inorganic materials 0.000 claims description 15
- 239000011733 molybdenum Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- MFWFDRBPQDXFRC-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;vanadium Chemical compound [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 9
- 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 9
- 238000005303 weighing Methods 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 5
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 claims description 2
- 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 claims description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000012071 phase Substances 0.000 description 26
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000000227 grinding Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 11
- 239000000843 powder Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229910052786 argon Inorganic materials 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013589 supplement Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 239000004570 mortar (masonry) Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052573 porcelain Inorganic materials 0.000 description 7
- 239000011734 sodium Substances 0.000 description 6
- 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 5
- 230000002776 aggregation Effects 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000010532 solid phase synthesis reaction Methods 0.000 description 5
- 229910001935 vanadium oxide Inorganic materials 0.000 description 5
- KZEVSDGEBAJOTK-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[5-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]-1,3,4-oxadiazol-2-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CC=1OC(=NN=1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O KZEVSDGEBAJOTK-UHFFFAOYSA-N 0.000 description 4
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 238000005054 agglomeration Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000007580 dry-mixing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000002159 nanocrystal Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 transition metal nitrides Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
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- 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
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- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0637—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron with metals not specified in groups C01B21/0607 - C01B21/0635, other than aluminium, titanium, zirconium or hafnium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
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Abstract
本发明公开一种三相体系三氧化二钒/氮化钒/碳化钼纳米电极材料及其制备方法与应用。所述三相体系V2O3/VN/Mo2C纳米电极材料包括晶格条纹相互交错且均匀分布的V2O3颗粒、VN颗粒和Mo2C颗粒;其中,所述V2O3、VN和Mo2C的质量比为1‑4:10‑40:4‑16。上述三种纳米颗粒相互交织,形成更多的非相干界面面积。非相干界面面积的增加会造成更多的缺陷,进而提供更多活性位点,提高产氢性能。
Description
技术领域
本发明属于催化剂合成与应用技术领域,具体涉及一种三相体系V2O3/VN/Mo2C纳米电极材料及其制备方法与应用。
背景技术
电解水制氢被认为是取代传统化石燃料和对环境污染少的清洁能源。铂基催化材料析氢(HER)性能优越,但是价格昂贵,且铂元素在地球上的存量极少。基于此,电催化制氢领域当前最紧要的任务是探索成本低、稳定性好、性能优异且可持续的非贵金属电催化剂。
Su等人设计一种通过热分解草酸盐制备V2O3纳米粉末的方法,得到高纯度以及分散性良好的V2O3物相([Pinna N,Antonietti M,Niederberger M.A novel nonaqueousroute to V2O3 and Nb2O5 nanocrystals[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,2004,250:211-213.])。过渡金属氮化物中,VN具有优异的导电性、较小的密度和良好的电子传导性,但是其合成温度高,容易团聚甚至会使得部分结构坍塌,这不利于材料活性位点的暴露,导致材料催化活性差([Wang Y,Wang L,Tong M,et al.Co-VN encapsulated in bamboo-like N-doped carbon nanotubes for ultrahigh-stability of oxygen reduction reaction[J].Nanoscale,2018,10:4311-4319.])。过渡金属碳化物中Mo2C具有类Pt的d电子结构,且具备优异的氢吸附性能,但导电性差限制了它的催化活性。
发明内容
本发明的技术目的在于提供一种三相体系V2O3/VN/Mo2C纳米电极材料及其制备方法与应用。所述三相体系V2O3/VN/Mo2C纳米电极材料具有令人满意的催化性能,可以广泛应用于工业中电解水制氢,既经济实用又高效方便。
第一方面,本发明提供一种三相体系V2O3/VN/Mo2C纳米电极材料。所述三相体系V2O3/VN/Mo2C纳米电极材料包括晶格条纹相互交错且均匀分布的V2O3颗粒、VN颗粒和Mo2C颗粒。上述三种纳米颗粒相互交织,形成更多的非相干界面面积(“非相干界面”指的是不同物相的晶相相互交织所形成的区域)。非相干界面面积的增加会造成更多的缺陷,进而提供更多活性位点,提高产氢性能。
其中,所述V2O3、VN和Mo2C的质量比为1-4:10-40:4-16。VN成本低廉,含量丰富,有良好的导电性。Mo2C有令人满意的H+结合能。V-O是促进产氢的活性成分。在三相体系V2O3/VN/Mo2C纳米电极材料中,V2O3和Mo2C修饰VN,增强了协同催化作用,同时极大提高了材料的电化学稳定性。
较佳地,所述V2O3颗粒、VN颗粒和Mo2C颗粒的粒径分别为10-50nm、10-100nm和5-100nm。
较佳地,所述三相体系V2O3/VN/Mo2C纳米电极材料具有异质结结构。三种物相的晶格条纹相互交织,具有明显的三相异质结结构。
本发明的三相体系V2O3/VN/Mo2C纳米电极材料通过设计特殊的纳米结构,既可以揭示更多的催化活性位点,也可以有效解决其导电性弱等问题。其中,VN有良好的导电性,较小的塔菲尔斜率,有利于H2的脱附。V-O作为一种有效的的HER活性成分,促进产氢速率。Mo2C有很好的氢结合能,利于H+的吸附。三者形成复合相,能够平衡H+吸附和H2脱附的动力学,提高催化活性。
第二方面,本发明还提供上述任一项所述的三相体系V2O3 /VN/Mo2C纳米电极材料的制备方法。所述制备方法包括:将包括碳氮同源化合物、钒源、钼源的原料称料并混合后,于惰性气体保护下在600-800℃保温120-180min,获得三相体系V2O3/VN/Mo2C纳米电极材料。
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V2O3/VN/Mo2C纳米电极材料的各组成均匀分散。
较佳地,所述碳氮同源化合物、钒源、钼源的质量比为(30-40):(3-5):(1-3)。
较佳地,所述碳氮同源化合物为尿素、双氰胺、三聚氰胺中的至少一种。所述碳氮同源化合物优选为尿素。
较佳地,所述钼源包括二水合钼酸钠和/或四水合钼酸铵。所述钼源优选为为二水合钼酸钠。
较佳地,所述钒源包括乙酰丙酮钒、偏钒酸铵、偏钒酸钠中的至少一种。所述钒源优选为乙酰丙酮钒。
第三方面,本发明还提供上述任一项所述的三相体系V2O3/VN/Mo2C纳米电极材料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V2O3/VN/Mo2C纳米材料化学组成均一,纯度和结晶度较高,且三种物相相互交错,促进催化效应。
2.本发明V2O3/VN/Mo2C电极材料中同时含有两类导电性物相V2O3和VN,电子传导路径变多,降低电子传导极化。
3.本发明V2O3/VN/Mo2C电极材料导电性好,过电势小,在电解水制氢方面有很大的优势。
附图说明
图1是实施例1制备的V2O3/VN/Mo2C纳米电极材料的XRD图谱;
图2是实施例3制备的V2O3/VN/Mo2C纳米电极材料的TEM图;
图3是实施例4制备的V2O3/VN/Mo2C纳米电极材料的SEM图;
图4是对比例1制备的产物SEM图;
图5是实施例5制备的V2O3/VN/Mo2C纳米电极材料在pH 14条件下的产氢性能图;
图6是实施例6制备的V2O3/VN/Mo2C纳米电极材料在pH 0条件下的产氢性能图;
图7是实施例6制备的V2O3/VN/Mo2C纳米电极材料在pH 7条件下的产氢性能图;
图8是对比例1制备的产物XRD图;
图9是对比例1制备的产物在pH 14条件下的产氢性能图;
图10是实施例5制备的V2O3/VN/Mo2C的时间-电流曲线图。
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。在没有特殊说明的情况下,各百分含量指质量百分含量。
以下示例性说明本发明所述三相体系V2O3/VN/Mo2C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(30-40):(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42:5:3时,纳米颗粒团聚严重,而且引入了杂相V2C。
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,将钒源中的V5+还原成V3+,生成V2O3和VN,还可实现复合结构中V2O3颗粒、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。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V2O3/VN/Mo2C纳米粉体。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20-100sccm,更优选为20-50sccm。
固相合成过程中,固相合成温度可为600-800℃,固相合成时间可为120-180min。
一些实施方式中,将碳氮同源化合物、钒源和钼源混合并研磨15-25min,置于瓷舟中并放入管式炉,并在管两端各放两个炉塞。连接好装置后,先检查气密性,继而进行3-6次抽气补气,排尽管内空气,最后一次补气后不再抽气。以20-50sccm的流速通入氩气,以5-10℃/min加热至600-800℃,在600-800℃保温120-180min。氩气流速较大时,产率有所下降,超过50sccm,产率下降明显。待冷却到室温后将得到的样品在研钵中研磨20-30min,得到V2O3/VN/Mo2C纳米粉体。
Mo2C的合成温度略高于V2O3和VN。在上述制备过程中,逐渐形成V2O3和VN的的同时,伴随着Mo2C的生成,最终产物中三种物相相互交错,有利于促进协同反应。V-O是一种有效的HER活性成分,并且氧化钒的存在增强了催化剂在恒电位极化下(时间-电流曲线)的稳定性,稳定工作超过200h。
在上述原料体系中,钒元素能够以氮化钒、氧化钒、碳化钒这几种形式存在。经过实验,在不改变钒源量和煅烧温度的情况下,当碳氮同源化合物的用量低于技术方案比例(碳氮同源化合物、钒源、钼源的质量比为(30-40):(3-5):(1-3))时,钒主要以氧化钒存在。这是由于碳氮同源化合物的质量较少时,热解过程中产生的还原性气体较少,优先还原生成氧化钒。当碳氮同源化合物的用量为技术方案比例(碳氮同源化合物、钒源、钼源的质量比(30-40):(3-5):(1-3))时,倾向于同时生成生成氧化钒和氮化钒。当碳氮同源化合物的用量高于于技术方案比例时,主要生成碳化钒(参见对比例1)。
本发明的制备方法无需大型设备和苛刻的反应条件,原料廉价易得,成本低,产率高,无需后期处理,对环境友好,安全性高,适合工业化生产。一些实施方式中,本发明制备的三相体系V2O3/VN/Mo2C纳米粉体在电流密度10mA/cm2时,于碱性、酸性和中性中的过电势分别为124mV、180mV和320mV。
通过CHI660E B17060电化学工作站(上海辰华仪器有限公司),采用典型的三电极体系测试系统进行电催化析氢测试,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。工作电极的制备方法如下:用(i)将10mg粉末样品加入到异丙醇溶液(200μL)中,使之形成均匀的混合溶液;(ii)将2μL混合物溶液滴到玻碳电极上,担载量约为1.4mg cm-2;(iii)等催化剂自然风干后,需要将2μl的1%Nafion滴在催化剂表面,防止在测试过程中催化剂的脱落。我们对所制备的样品在酸性(0.5M H2SO4)、碱性(1M KOH)和中性(1M PBS)中进行电化学测试:(a)进行线性扫描伏安曲线(LSV)测试时,扫速设置为以3mV s-1;(b)绘制的电流随时间变化曲线(I-t),在一个恒定的电压下进行。
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30:3:1称取尿素(CH4N2O)、乙酰丙酮钒(C15H21O6V)、二水合钼酸钠(Na2MoO4·2H2O);
(2)将上述原料混合并研磨15min,置于瓷舟中放入管式炉,并在管两端各放两个炉塞;
(3)连接好装置后,检查气密性,继而进行3次抽气补气,排尽管内空气,最后一次补气后不再抽气。以20sccm的流速通入氩气,以5℃/min加热至600℃,在600℃保温120min;
(4)待冷却到室温后将得到的样品在研钵中研磨15min,得到V2O3/VN/Mo2C纳米粉体。
图1是实施例1制备的V2O3/VN/Mo2C纳米电极材料的XRD图谱,可以看出V2O3、VN和Mo2C的衍射峰与标准卡片匹配较好,且强度高,说明制备得到的V2O3/VN/Mo2C结晶性很好。
实施例2
(1)按照质量比35:4:2称取尿素(CH4N2O)、乙酰丙酮钒(C15H21O6V)、二水合钼酸钠(Na2MoO4·2H2O);
(2)将上述原料混合并研磨20min,置于瓷舟中放入管式炉,并在管两端各放两个炉塞;
(3)连接好装置后,检查气密性,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30sccm的流速通入氩气,以10℃/min加热至700℃,在700℃保温180min;
(4)待冷却到室温后将得到的样品在研钵中研磨20min,得到V2O3/VN/Mo2C纳米粉体。
实施例3
(1)按照质量比40:5:3称取尿素(CH4N2O)、乙酰丙酮钒(C15H21O6V)、二水合钼酸钠(Na2MoO4·2H2O);
(2)将上述原料混合并研磨25min,置于瓷舟中放入管式炉,并在管两端各放两个炉塞;
(3)连接好装置后,检查气密性,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40sccm的流速通入氩气,以5℃/min加热至800℃,在800℃保温120min;
(4)待冷却到室温后将得到的样品在研钵中研磨25min,得到V2O3/VN/Mo2C纳米粉体。
图2是实施例3制备的V2O3/VN/Mo2C纳米电极材料的TEM图,可以看出V2O3、VN和Mo2C的颗粒尺寸较小,晶格条纹明显且相互交错,促进了它们之间的协同催化效应。
实施例4
(1)按照质量比38:4:2称取将尿素(CH4N2O)、乙酰丙酮钒(C15H21O6V)、二水合钼酸钠(Na2MoO4·2H2O);
(2)将上述原料混合并研磨20min,置于瓷舟中放入管式炉,并在管两端各放两个炉塞;
(3)连接好装置后,先检查气密性,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20sccm的流速通入氩气,以10℃/min加热至700℃,在700℃保温120min;
(4)待冷却到室温后将得到的样品在研钵中研磨20min,得到V2O3/VN/Mo2C纳米粉体。
图3是实施例4制备的V2O3/VN/Mo2C纳米电极材料的SEM图,可以看出样品形貌分散均匀,暴露了较多的活性位点。
实施例5
(1)按照质量比39:5:3称取尿素(CH4N2O)、乙酰丙酮钒(C15H21O6V)、二水合钼酸钠(Na2MoO4·2H2O);
(2)将上述原料混合并研磨25min,置于瓷舟中放入管式炉,并在管两端各放两个炉塞;
(3)连接好装置后,先检查气密性,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40sccm的流速通入氩气,以5℃/min加热至800℃,在800℃保温180min;
(4)待冷却到室温后将得到的样品在研钵中研磨25min,得到V2O3/VN/Mo2C纳米粉体。
图5是实施例5制备的V2O3/VN/Mo2C纳米电极材料的产氢性能图,表示在碱性测试条件下,当电流密度为10mA/cm2,扫描速率为3mV/s时,该样品过电势为124mV,说明具有优异的催化性能。图10是实施例5制备的V2O3/VN/Mo2C的时间-电流曲线图,可以看出在碱性条件中,样品在10mA/cm2下可以稳定工作200h,表明样品具有非常优异的稳定性。
实施例6
(1)按照质量比40:4:2称取尿素(CH4N2O)、乙酰丙酮钒(C15H21O6V)、二水合钼酸钠(Na2MoO4·2H2O);
(2)将上述原料混合并研磨20min,置于瓷舟中放入管式炉,并在管两端各放两个炉塞;
(3)连接好装置后,先检查气密性,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30sccm的流速通入氩气,以10℃/min加热至700℃,在700℃保温120min;
(4)待冷却到室温后将得到的样品在研钵中研磨20min,得到V2O3/VN/Mo2C纳米粉体。
图6是实施例6制备的V2O3/VN/Mo2C纳米电极材料的产氢性能图,表示在酸性测试条件下,当电流密度为10mA/cm2,扫描速率为3mV/s时,该样品过电势为180mV,说明具有良好的催化活性。
图7是实施例6制备的V2O3/VN/Mo2C纳米电极材料的产氢性能图,表示在中性测试条件下,当电流密度为10mA/cm2,扫描速率为3mV/s时,该样品过电势为320mV,说明具有令人满意的催化性能。
对比例1
与实施例1基本相同,区别仅在于:所述碳氮同源化合物、钒源、钼源的质量比为42:5:3。
图4是对比例1产物的SEM图,可以看出纳米颗粒团聚严重,分散不均匀。这是由于碳氮同源化合物使用量的增加,热解产生的还原性气体NH3较多时,还原生成的V2C较多,聚集严重(因为V2C比VN的表面能还高,形成的晶核较多,容易发生团聚)。图8是对比例1产物的XRD图,随着碳氮同源化合物添加量的增加,生成的杂相V2C较多,同时导致VN的结晶性变差。图9是对比例1产物的LSV图,表示在碱性测试条件下,当电流密度为10mA/cm2,扫描速率为3mV/s时,该样品过电势为260mV,产物性能变差。这是由于碳氮同源化合物量增加,产物形貌出现团聚,且引入杂相V2C,导致活性位点数量暴露较少,产氢性能变差。
Claims (7)
1.一种三相体系V2O3/VN/Mo2C纳米电极材料,其特征在于,所述三相体系V2O3/VN/Mo2C纳米电极材料包括晶格条纹相互交错且均匀分布的V2O3颗粒、VN颗粒和Mo2C颗粒;其中,所述V2O3、VN和Mo2C的质量比为1-4:10-40:4-16。
2. 根据权利要求1所述的纳米电极材料,其特征在于,所述V2O3颗粒、VN颗粒和Mo2C颗粒的粒径分别为10-50 nm、10-100 nm和5-100 nm。
3.根据权利要求1或2所述的纳米电极材料,其特征在于,所述三相体系V2O3/VN/Mo2C纳米电极材料具有异质结结构。
4. 根据权利要求1至3中任一项所述的三相体系V2O3/VN/Mo2C纳米电极材料的制备方法,其特征在于,所述制备方法包括:将包括碳氮同源化合物、钒源、钼源的原料称料并混合后,于惰性气体保护下在600-800℃保温120-180 min,获得三相体系V2O3/VN/Mo2C纳米电极材料;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V2O3/VN/Mo2C纳米电极材料的各组成均匀分散;所述碳氮同源化合物为尿素、双氰胺、三聚氰胺中的至少一种;所述碳氮同源化合物、钒源、钼源的质量比为(30-40):(3-5):(1-3)。
5.根据权利要求4所述的制备方法,其特征在于,所述钼源包括二水合钼酸钠和/或四水合钼酸铵。
6.根据权利要求4或5所述的制备方法法,其特征在于,所述钒源包括乙酰丙酮钒、偏钒酸铵、偏钒酸钠中的至少一种。
7.权利要求1至3中任一项所述的三相体系V2O3/VN/Mo2C纳米电极材料在电解水制氢方面的应用。
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