CN107199040B - 钼酸盐纳米阵列及其制备方法和应用 - Google Patents
钼酸盐纳米阵列及其制备方法和应用 Download PDFInfo
- Publication number
- CN107199040B CN107199040B CN201710546598.8A CN201710546598A CN107199040B CN 107199040 B CN107199040 B CN 107199040B CN 201710546598 A CN201710546598 A CN 201710546598A CN 107199040 B CN107199040 B CN 107199040B
- Authority
- CN
- China
- Prior art keywords
- molybdate
- nickel
- water catalyst
- salt
- substrate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 22
- 239000001301 oxygen Substances 0.000 claims abstract description 22
- 239000002073 nanorod Substances 0.000 claims abstract description 16
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- 239000000758 substrate Substances 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 80
- 229910052759 nickel Inorganic materials 0.000 claims description 40
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 15
- -1 transition metal salt Chemical class 0.000 claims description 14
- 235000015393 sodium molybdate Nutrition 0.000 claims description 13
- 239000011684 sodium molybdate Substances 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 11
- 229910015667 MoO4 Inorganic materials 0.000 claims description 10
- 238000005868 electrolysis reaction Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004744 fabric Substances 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical class O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 2
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 2
- 239000011609 ammonium molybdate Substances 0.000 claims description 2
- 229940010552 ammonium molybdate Drugs 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 2
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- NMHMDUCCVHOJQI-UHFFFAOYSA-N lithium molybdate Chemical compound [Li+].[Li+].[O-][Mo]([O-])(=O)=O NMHMDUCCVHOJQI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 abstract description 2
- 150000003624 transition metals Chemical class 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000007664 blowing Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 238000001075 voltammogram Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910005809 NiMoO4 Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000003491 array Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Images
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
本申请公开了一种钼酸盐纳米阵列，包括钼酸盐纳米棒和基底；所述钼酸盐纳米棒中的钼酸盐的化学式为AMoO4；其中，A选自过渡金属中的至少一种。其作为电解水产氧的催化剂，在碱性条件下，到达10mA·cm‑2的过电位小于300mV，性能优于商业化的IrO2催化剂。
Description
技术领域
本申请涉及一种钼酸盐纳米阵列及其制备方法和应用，属于催化领域。
背景技术
随着社会的发展，环境污染加剧的问题变得日益严重，因此寻找高效的清洁能源也成为了各国关注的焦点。氢气作为一种具有高能量密度，并且属于完全无污染的能源，被认为是最有潜力的清洁能源。但是目前获得氢气的主要途径为石油裂解制氢，而石油是不可再生能源，所以通过其它途径获得高纯度的氢气是很迫切的。
在各种获得氢气的途径中，电解水制氢被认为是最具有潜力的一种方法。目前，制约电解水制氢技术发展的最大因素在于缺少廉价高效的析氧催化剂。虽然目前商业用的IrO2具有很高的析氧反应活性，但是由于铱的稀缺性，使得这类催化剂难以获得大规模的应用，所以寻找廉价高效的析氧反应催化剂已经成为各国科学家关注的重点问题。
发明内容
根据本申请的一个方面，提供了一种钼酸盐纳米阵列，该钼酸盐纳米阵列用于电解水产氧具有高的OER活性。
所述钼酸盐纳米阵列，包括钼酸盐纳米棒和基底；
所述钼酸盐纳米棒中的钼酸盐的化学式为AMoO4；其中，A选自过渡金属元素中的至少一种。
优选地，所述钼酸盐的化学式为BxCyMoO4；其中：x，y均大于0，且x+y＝1；B，C独立地选自过渡金属元素中的一种，且B和C是不同金属元素；优选地，所述x，y独立的选自0.1，0.2，0.3，0.4，0.5，0.6，0.7，0.8，0.9。
优选地，所述钼酸盐的化学式为DpEqFlMoO4；其中：p，q，l均大于0，且p+q+l＝1；D，E，F独立地选自过渡金属元素中的一种，且D，E和F是不同的金属元素；优选地，所述p，q，l独立的选自0.1，0.2，0.3，0.4，0.5，0.6，0.7，0.8，0.9。
所述A包括Fe、Co、Ni中的至少一种；
优选地，B、C中的至少一个选自Fe、Co、Ni中的至少一种；
优选地，D，E，F中的至少一个选自Fe、Co、Ni中的至少一种。
所述钼酸盐纳米棒的横截面上相距最远两点的距离为50nm～400nm；
所述钼酸盐纳米棒的长度为1μm～10μm。
优选地，所述钼酸盐纳米阵列以纳米棒的形态生长于基底上；所述钼酸盐纳米阵列为纳米棒取向排列；优选地，所述钼酸盐纳米阵列为纳米棒均匀取向排列。
优选地，所述基底选自金属网、纤维织物中的至少一种。
优选地，所述基底选自镍网、碳布中的至少一种。
进一步优选地，所述基地选自镍网或者碳布。
本申请的另一个方面，提供了制备所述的钼酸盐纳米阵列的方法，至少包括以下步骤：
将含有过渡金属盐、钼酸盐的原料，与基底接触，在基底上通过水热反应原位生长得到钼酸盐纳米阵列。
所述过渡金属盐与钼酸盐的摩尔比为1：1.2；
其中，过渡金属盐的摩尔数以过渡金属盐中过渡金属元素的总摩尔量计，钼酸盐的摩尔量以钼酸盐中钼元素的摩尔量计。
优选地，制备所述的钼酸盐纳米阵列的方法，至少包括以下步骤：在水溶液中溶解过渡金属盐，然后加入钼酸盐；搅拌后加入基底，转移到反应釜中，进行水热反应。
优选地，所述钼酸盐选自钼酸铵、钼酸的碱金属盐中的至少一种。
优选地，所述钼酸的碱金属盐选自钼酸钠、钼酸钾、钼酸锂中的至少一种。
优选地，所述过渡金属盐包括铁盐、钴盐、镍盐中的至少一种。
优选地，所述过渡金属盐包括硝酸亚铁、硫酸亚铁、氯化亚铁、硫酸亚铁铵、乙酸铁、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍、乙酸镍中的至少一种。
优选地，所述水热反应的温度为100～220℃；优选地，所述水热反应的时间为3～72小时。
优选地，所述水热反应的温度为150～200℃；优选地，所述水热反应的时间为5～12小时。
优选地，所述水热反应的温度为110～180℃；优选地，所述水热反应的时间为20～30小时。
本申请的又一个方面，提供了一种电解水催化剂，所述电解水催化剂包含所述的钼酸盐纳米阵列或/和所述制备方法得到的钼酸盐纳米阵列。即，所述钼酸盐纳米阵列作为电解水催化剂的应用。
优选地，所述电解水催化剂用于碱性条件下电解水产氧。从而促进电解水制氢技术的发展。
本申请能产生的有益效果包括：
1)本申请所提供的钼酸盐纳米阵列，其作为催化剂用于电解水产氧具有高的OER活性；其催化性能在碱性条件下到达10mA·cm-2的过电位为230mV，优于商业用的贵金属，如IrO2。
2)本申请所提供的钼酸盐纳米阵列，反应活性高，制备方法简单。
3)本申请所提供的钼酸盐纳米阵列的制备方法，操作简单，适用于大规模应用。
附图说明
图1为实施例1中样品1#的SEM图。
图2为实施例2中样品2#的SEM图。
图3为实施例1中样品1#在碱性条件下，电解水制氧的线性扫描伏安曲线。
图4为实施例2中样品2#在碱性条件下，电解水制氧的线性扫描伏安曲线。
图5为实施例3中样品3#在碱性条件下，电解水制氧的线性扫描伏安曲线。
图6为实施例4中样品4#在碱性条件下，电解水制氧的线性扫描伏安曲线。
具体实施方式
下面结合实施例详述本申请，但本申请并不局限于这些实施例。
如无特别说明，本申请的实施例中的原料和催化剂均通过商业途径购买。
本申请中采用的镍网购自长沙力元新材料有限公司，碳布购自上海何森电气有限公司。
本申请的实施例中分析方法如下：
利用日本电子公司的JSM-6700F扫描电子显微镜进行SEM形貌分析。
实施例1制备NiMoO4纳米阵列
起始原料为硝酸镍，钼酸钠，水；具体制备方法如下：
称取0.03mol的硝酸镍，0.03mol的钼酸钠溶于30ML水中，搅拌10min使其完全溶解，然后加入3cm×3cm的镍网。然后将溶液和镍网转移到反应釜中，在150℃的条件下反应24小时。反应结束后待其自然冷却，然后取出镍网，放入清水中超声10分钟，重复此步骤三次，以去除未生长在镍网上的钼酸盐；用吹风吹干镍网，得到NiMoO4纳米阵列，记为1#。
实施例2制备Ni0.5Co0.5MoO4纳米阵列
起始原料为硝酸镍，硝酸钴，钼酸钠，水；具体制备方法如下：
称取0.015mol的硝酸镍，0.015mol的硝酸钴，0.03mol的钼酸钠溶于30ML水中，搅拌10min使其完全溶解，然后加入3cm×3cm的镍网。将溶液和镍网转移到反应釜中，在150℃的条件下反应24小时。反应结束后待其自然冷却，然后取出镍网，放入清水中超声10分钟，重复此步骤三次，以去除未生长在镍网上的钼酸盐；用吹风吹干镍网，得到Ni0.5Co0.5MoO4纳米阵列，记为2#。
实施例3制备Ni0.9Fe0.1MoO4纳米阵列
起始原料为硝酸镍，硝酸亚铁，钼酸钠，水；具体制备方法如下：
称取0.027mol的硝酸镍，0.003mol的硝酸亚铁，0.03mol的钼酸钠溶于30mL水中，搅拌10min使其完全溶解，然后加入3cm×3cm的镍网。将溶液和镍网转移到反应釜中，在150℃的条件下反应24小时。反应结束后待其自然冷却后取出镍网，放入清水中超声10分钟，重复此步骤三次，以去除未生长在镍网上的钼酸盐；用吹风吹干镍网，得到Ni0.9Co0.1MoO4纳米阵列，记为3#。
实施例4制备Fe1/3Co1/3Ni1/3MoO4纳米阵列
起始原料为硝酸镍，硝酸钴，硝酸亚铁，钼酸钠，水；具体制备方法如下：
称取0.01mol的硝酸镍，0.01mol的硝酸钴，0.01mol的硝酸亚铁，0.03mol的钼酸钠溶于30ML水中，搅拌10min使其完全溶解，然后加入3cm×3cm的镍网。将溶液和镍网转移到反应釜中，在150℃的条件下反应24小时。反应结束后待其自然冷却后取出镍网，放入清水中超声10分钟，重复此步骤三次，以去除未生长在镍网上的钼酸盐；用吹风吹干镍网，得到Fe1/3Co1/3Ni1/3MoO4纳米阵列，记为4#。
实施例5样品的形貌表征
采用扫描电镜对样品1#～样品4#进行了形貌分析，结果表明，样品1#～样品4#的形貌无明显差别，均为纳米棒状，典型代表如样品1#和样品2#，其扫描电镜照片分别如图1和图2所示。由图可以看出，钼酸盐纳米棒的横向尺寸为50nm～400nm；所述钼酸盐纳米棒的长度为1μm～10μm。
实施例6样品的电解水产氧测试
称取2.805g KOH溶解于50mL去离子水中，配置成1M KOH溶液。向1M KOH溶液中通高纯氧气，半个小时。选取氧化汞电极作为参比电极，石墨电极作为对电极。将样品1#～样品4#剪成1cm×1.5cm大小(已经生长钼酸盐的镍网)作为工作电极；同时保证工作电极浸入溶液的面积为1cm×1cm。电化学工作站选择上海晨华的Chi760e。工作模式选择线性扫描伏安法；电势范围选择0.3-0.7V(vs HgO)。
将样片1#～样品4#经过上述方法进行测试，结果如下：
按照上述电解水产氧测试条件得到的样品1#电解水制氧性能曲线如图3所示，从图中可以看出在1.6V(vs RHE)下的电流密度为99mA·cm-2。
按照上述电解水产氧测试条件得到的样品2#电解水制氧性能曲线如图4所示，从图中可以看出在1.6V(vs RHE)下的电流密度为119mA·cm-2。
按照上述电解水产氧测试条件得到的样品3#电解水制氧性能曲线如图5所示，从图中可以看出在1.6V(vs RHE)下的电流密度为260mA·cm-2。
按照上述电解水产氧测试条件得到的样品4#电解水制氧性能曲线如图6所示，从图中可以看出在1.55V(vs RHE)下的电流密度为237mA·cm-2。
以上所述，仅是本申请的几个实施例，并非对本申请做任何形式的限制，虽然本申请以较佳实施例揭示如上，然而并非用以限制本申请，任何熟悉本专业的技术人员，在不脱离本申请技术方案的范围内，利用上述揭示的技术内容做出些许的变动或修饰均等同于等效实施案例，均属于技术方案范围内。
Claims (11)
1.一种电解水催化剂，其特征在于，所述电解水催化剂包含钼酸盐纳米阵列；所述钼酸盐纳米阵列包括钼酸盐纳米棒和基底；
所述钼酸盐纳米棒中的钼酸盐的化学式为AMoO4；其中，所述A包括Fe、Co、Ni中的至少一种；
所述钼酸盐纳米阵列的制备方法，由以下步骤制备：
将含有过渡金属盐、钼酸盐的原料，与基底接触，在基底上通过水热反应原位生长得到钼酸盐纳米阵列；
所述过渡金属盐包括铁盐、钴盐、镍盐中的至少一种。
2.根据权利要求1所述的电解水催化剂，其特征在于，所述钼酸盐的化学式为BxCyMoO4；其中：x，y均大于0，且x+y=1；B，C独立地选自Fe、Co、Ni中的一种，且B和C是不同金属元素。
3.根据权利要求1所述的电解水催化剂，其特征在于，所述钼酸盐的化学式为DpEqFlMoO4；其中：p，q，l均大于0，且p+q+l=1；D，E，F独立地选自Fe、Co、Ni中的一种，且D，E和F是不同的金属元素。
4.根据权利要求1所述的电解水催化剂，其特征在于，所述钼酸盐纳米棒的横截面上相距最远两点的距离为50nm~400nm；
所述钼酸盐纳米棒的长度为1μm~10μm。
5.根据权利要求1所述的电解水催化剂，其特征在于，所述基底选自金属网、纤维织物中的至少一种。
6.根据权利要求1所述的电解水催化剂，其特征在于，所述基底选自镍网、碳布中的至少一种。
7.根据权利要求1所述的电解水催化剂，其特征在于，所述钼酸盐选自钼酸铵、钼酸的碱金属盐中的至少一种。
8.根据权利要求7所述的电解水催化剂，其特征在于，所述钼酸的碱金属盐选自钼酸钠、钼酸钾、钼酸锂中的至少一种。
9.根据权利要求1所述的电解水催化剂，其特征在于，所述过渡金属盐包括硝酸亚铁、硫酸亚铁、氯化亚铁、硫酸亚铁铵、乙酸铁、氯化钴、硝酸钴、硫酸钴、乙酸钴、氯化镍、硝酸镍、硫酸镍、乙酸镍中的至少一种。
10.根据权利要求1所述的电解水催化剂，其特征在于，所述水热反应的温度为100~220℃，所述水热反应的时间为3~72小时。
11.权利要求1-10任一项所述的电解水催化剂的应用，其特征在于，所述电解水催化剂用于碱性条件下电解水产氧。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710546598.8A CN107199040B (zh) | 2017-07-06 | 2017-07-06 | 钼酸盐纳米阵列及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710546598.8A CN107199040B (zh) | 2017-07-06 | 2017-07-06 | 钼酸盐纳米阵列及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107199040A CN107199040A (zh) | 2017-09-26 |
| CN107199040B true CN107199040B (zh) | 2020-07-31 |
Family
ID=59910597
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710546598.8A Active CN107199040B (zh) | 2017-07-06 | 2017-07-06 | 钼酸盐纳米阵列及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107199040B (zh) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108557887B (zh) * | 2018-06-01 | 2020-02-14 | 中科院合肥技术创新工程院 | 一种含钼酸根溶液的制备方法 |
| CN111020626B (zh) * | 2019-12-09 | 2021-03-16 | 北京工业大学 | 一种3d纳米片-纳米棒混合结构镍钼氧化物的制备方法及应用 |
| CN111575708A (zh) * | 2020-07-03 | 2020-08-25 | 台州学院 | 一种镍钼聚离子化合物混合相纳米棒阵列的制备方法 |
| CN112090436B (zh) * | 2020-09-14 | 2023-07-07 | 江浩 | 一种镍基催化剂、制备方法及应用 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923268A (zh) * | 2015-06-08 | 2015-09-23 | 中国科学院长春应用化学研究所 | 一种自支撑过渡金属硒化物催化剂及其制备方法和应用 |
| CN105600824A (zh) * | 2016-01-20 | 2016-05-25 | 三峡大学 | 一种高性能微纳多级结构MoS2材料、制备方法及应用 |
| CN105720270A (zh) * | 2016-02-02 | 2016-06-29 | 陕西科技大学 | 一种柔性锂离子电池负极材料β-ZnMoO4的制备方法 |
| CN106824198A (zh) * | 2017-03-10 | 2017-06-13 | 中国科学技术大学 | 钴基产氧催化剂及其制备方法以及一种碱性制氢电解槽 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8729798B2 (en) * | 2008-03-21 | 2014-05-20 | Alliance For Sustainable Energy, Llc | Anti-reflective nanoporous silicon for efficient hydrogen production |
-
2017
- 2017-07-06 CN CN201710546598.8A patent/CN107199040B/zh active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923268A (zh) * | 2015-06-08 | 2015-09-23 | 中国科学院长春应用化学研究所 | 一种自支撑过渡金属硒化物催化剂及其制备方法和应用 |
| CN105600824A (zh) * | 2016-01-20 | 2016-05-25 | 三峡大学 | 一种高性能微纳多级结构MoS2材料、制备方法及应用 |
| CN105720270A (zh) * | 2016-02-02 | 2016-06-29 | 陕西科技大学 | 一种柔性锂离子电池负极材料β-ZnMoO4的制备方法 |
| CN106824198A (zh) * | 2017-03-10 | 2017-06-13 | 中国科学技术大学 | 钴基产氧催化剂及其制备方法以及一种碱性制氢电解槽 |
Non-Patent Citations (2)
| Title |
|---|
| An efficient electrode based on one-dimensional CoMoO4 nanorods for oxygen evolution reaction;Xueliang Liu，et al;《Chemical Physics Letters》;20170227;第675卷;第11-14页 * |
| New ternary Fe, Co, and Mo mixed oxide electrocatalysts for oxygen evolution;M. Kumar，et al;《International Journal of Hydrogen Energy》;20110528;第36卷(第15期);第8831-8838页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107199040A (zh) | 2017-09-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wen et al. | Ni-Co-Mo-O nanosheets decorated with NiCo nanoparticles as advanced electrocatalysts for highly efficient hydrogen evolution | |
| CN108816250B (zh) | 一种纳米棒阵列复合材料及其制备方法和应用 | |
| CN107199040B (zh) | 钼酸盐纳米阵列及其制备方法和应用 | |
| CN109954503B (zh) | 一种硒化镍和三元硒化镍铁复合电催化剂及制备方法和应用 | |
| Dong et al. | Ni/Ni 3 C core–shell nanoparticles encapsulated in N-doped bamboo-like carbon nanotubes towards efficient overall water splitting | |
| CN109628951B (zh) | 一种硫化镍析氢电催化剂及其制备方法与应用 | |
| CN110433833B (zh) | 一种基于协同改性的非贵金属析氢电催化剂及其制备方法 | |
| CN110694665B (zh) | 一种锰、氮掺杂八硫九钴电催化剂的制备方法及其应用 | |
| CN109621981B (zh) | 一种金属氧化物-硫化物复合析氧电催化剂及其制备方法和应用 | |
| CN108910962A (zh) | 一种三元CoFeCr水滑石纳米棒及其制备方法与应用 | |
| CN110639534A (zh) | 一种析氧电催化材料及其制备方法和应用 | |
| Guo et al. | Co/Cu-modified NiO film grown on nickel foam as a highly active and stable electrocatalyst for overall water splitting | |
| Qi et al. | Self-supported cobalt–nickel bimetallic telluride as an advanced catalyst for the oxygen evolution reaction | |
| Cao et al. | Carbon skeleton doped with Co, N, S and P as efficient electrocatalyst for oxygen evolution reaction | |
| CN108479791B (zh) | 一种Co/Ni-MoO2复合电解水催化剂的制备方法 | |
| Liu et al. | Industrial stainless steel meshes for efficient electrocatalytic hydrogen evolution | |
| CN110721749B (zh) | 金属有机骨架结构衍生碳复合物包覆的NiCo2S4纳米线阵列状电催化剂及其制备方法 | |
| Yang et al. | Interfaces modulation strategy to synthesize bifunctional electrocatalyst for highly efficient overall water splitting | |
| CN112921351B (zh) | 一种自支撑型催化电极的制备方法和应用 | |
| CN112501652B (zh) | 一种利用形貌及结构调控电催化产氧的钨掺杂硫化镍催化剂及其制备方法与应用 | |
| Wang et al. | Electrochemical fabrication of FeS x films with high catalytic activity for oxygen evolution | |
| Zhang et al. | Self-supported NiFe-LDH nanosheets on NiMo-based nanorods as high-performance bifunctional electrocatalysts for overall water splitting at industrial-level current densities | |
| CN111266121B (zh) | 双功能电解水催化剂及其制备方法和应用 | |
| CN115261915B (zh) | 一种含钴和镍的复合电催化剂及其制备方法和应用 | |
| CN109012673B (zh) | 一种析氧催化剂的制备方法及应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| CB03 | Change of inventor or designer information | ||
| CB03 | Change of inventor or designer information |
Inventor after: Li Guangshe Inventor after: Wang Jianghao Inventor after: Li Liping Inventor after: Liu Yifeng Inventor after: Wang Liping Inventor after: Sun Wengang Inventor after: Li Wenwen Inventor before: Li Guangshe Inventor before: Wang Jianghao Inventor before: Li Liping Inventor before: Liu Yifeng Inventor before: Wang Liping Inventor before: Sun Wengang Inventor before: Li Wenwen |
|
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |