CN110180574A - 一种氮掺杂三元硫化物电催化剂材料制备及应用 - Google Patents
一种氮掺杂三元硫化物电催化剂材料制备及应用 Download PDFInfo
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 title claims abstract description 16
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 239000005864 Sulphur Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000011733 molybdenum Substances 0.000 claims abstract description 9
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 9
- 150000003624 transition metals Chemical class 0.000 claims abstract description 9
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010937 tungsten Substances 0.000 claims abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000003197 catalytic effect Effects 0.000 claims abstract description 6
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 18
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- 239000006260 foam Substances 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 5
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- 229910052708 sodium Inorganic materials 0.000 claims description 5
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical group [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 4
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
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- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 150000001805 chlorine compounds Chemical group 0.000 claims 1
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- 238000002604 ultrasonography Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
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- 239000011684 sodium molybdate Substances 0.000 description 3
- 235000015393 sodium molybdate Nutrition 0.000 description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- -1 X=Co Chemical class 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 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
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000009790 rate-determining step (RDS) Methods 0.000 description 1
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- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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Abstract
一种氮掺杂三元硫化物电催化剂材料制备及应用,属于催化剂技术领域。包括以下步骤:将金属基底用盐酸、无水乙醇和去离子分别超声去除表面的氧化物及杂质;将过渡金属前驱体盐及钨或钼的可溶性盐加入去离子水,搅拌溶解;将基底竖直放入水热釜中,然后加入上述溶液,进行水热反应;产物水洗,然后放入水热釜中,加入含硫源和氮源的溶液进行硫氮化反应;所得产物用去离子水洗涤、烘干,即得到氮掺杂的三元硫化物电催化剂。制备颗粒则省去基底的引入。在X‑M‑S催化剂的制备过程中进行了原位氮掺杂,提高了作为电解水催化剂的催化性能。
Description
技术领域
本发明提供了一种氮掺杂三元硫化物电催化剂材料的制备技术,属于催化剂技术领域。
背景技术
在传统能源储量日渐减少,污染量与日俱增的同时,新能源的探索和应用成为改善此种情况的关键。氢能具有能量密度高、清洁环保等特点,被认为是优异的化石燃料替代品。电解水由于环境友好、产品纯度高以及无碳排放而成为最具有应用前景的绿色制氢方法之一。铂、铱等贵金属基材料是高效的电解水催化剂,但是储量稀少、价格昂贵,成为限制电解水制氢大规模应用的最重要瓶颈。因此发展廉价、易制备的高效电解水催化剂对于氢能的实际应用十分关键。
目前双金属硫化物X-M-S(X=Co,Ni,Cu等过渡金属,M=W或Mo)电解水催化剂引起了人们的广泛关注。研究表明双金属硫化物中由于两种金属的协同作用改变了单一硫化物催化剂的能带结构,从而产生更多的表面活性位点,有利于催化反应的进行。同时硫化物相对于它们的氧化物来说具有更好的导电性,促进了载流子的传输与分离,同时对氢离子具有更低的吸附能,因而具有较好的电催化活性。但是相对于贵金属催化剂而言,它们的催化性能仍有一定的差距。特别是产氧性能与氧化铱等相差甚远。由于产氧过程是由四个电子参与的复杂的氧化还原过程,是水分解反应过程的决速步骤,因导致整体催化分解水效率的降低。
发明内容
本发明的目的是提供一种制备氮掺杂三元硫化物电催化剂材料的制备方法,既可用于金属基底上生长氮掺杂三元硫化物电催化剂,又可制备氮掺杂三元硫化物电催化剂颗粒,提高作为电解水催化剂的催化性能。该方法工艺简单,过程易控制,环境友好等优点,具有较高的实际应用价值。
为达上述目的,本发明采用如下技术方案:
(1)将金属基底用盐酸、无水乙醇和去离子分别超声处理去除表面的氧化物层及杂质;
(2)将过渡金属前驱体盐及钨或钼的可溶性盐加入去离子水,搅拌溶解;
(3)将步骤(1)基底竖直放入水热釜中,然后加入步骤(2)溶液,优选填充量为70%,然后进行水热反应;
(4)将步骤(3)得到的产物水洗三遍,然后放入水热釜中,加入含硫源和氮源的溶液进行硫氮化反应;
(5)将步骤(4)得到的产物用去离子水洗涤、烘干,即得到氮掺杂的三元硫化物电催化剂。
本发明制备氮掺杂的三元硫化物电催化剂的方法,所述的金属基底可为泡沫镍或泡沫铜。
本发明制备氮掺杂的三元硫化物电催化剂X-M-S的方法,所述的X-M-S(X=Co、Ni、Cu等过渡金属,M=W或Mo)中钨或钼的的可溶性盐为钼酸铵或钼酸铵,钨酸钠或偏钨酸铵。所述的钨或钼的可溶性盐的浓度为2~10mmol/L;过渡金属前驱体盐可为它们的氯化物、硝酸盐、硫酸盐等,过渡金属(X)前驱体盐与钨或钼(M)的可溶性盐的摩尔比为1~4,优选X:M的摩尔浓度比按照X和M形成的对应的合金的化学摩尔计量比进行配置,优选得到的X-M-S催化剂中X和M的摩尔比为现有技术中形成。
本发明制备氮掺杂的三元硫化物电催化剂的方法,步骤(3)所述的水热反应温度为140~220℃,时间为4~24h。
本发明制备氮掺杂的三元硫化物电催化剂的方法,步骤(4)所述的硫源为硫化钠,浓度为5~15mmol/L。氮源为尿素或硫代乙酰胺,浓度为0.2~2mmol/L。
本发明制备氮掺杂的三元硫化物电催化剂的方法,步骤(4)所述的硫氮化温度为100~180℃,时间为4~24h。
本发明制备氮掺杂的三元硫化物电催化剂的方法,如制备颗粒则省去基底的引入,其它步骤相同。本发明在X-M-S催化剂的制备过程中进行了原位氮掺杂,提高了作为电解水催化剂(双催化性能,用于催化产氧和催化产氢)的催化性能。该方法工艺简单,过程易控制,环境友好等优点,具有较高的实际应用价值。
附图说明
图1为本发明实施例1制备的生长在泡沫镍上的NiMoS4电催化剂的扫描电镜照片。
图2为本发明实施例1制备的生长在泡沫镍上的NiMoS4电催化剂的XRD图谱。
图3为本发明实施例1制备的生长在泡沫镍上的NiMoS4电催化剂的XPS图谱。
图4为本发明实施例1制备的生长在泡沫镍上的NiMoS4电催化剂在1M氢氧化钾溶液中的产氢极化曲线。
图5为本发明实施例1制备的生长在泡沫镍上的NiMoS4电催化剂在1M氢氧化钾溶液中的产氧极化曲线。
具体实施方式
下面结合附图及具体实施例,对本发明做进一步的说明:
实施例1
将清洗过的泡沫镍竖直放入水热釜内衬中,然后加入浓度均为6mmol/L的钼酸钠和氯化镍的混合溶液,然后放入不锈钢高压反应釜外套内密封,置于160℃的烘箱中反应10h,反应完成后自然冷却至室温,将镍片分别用蒸馏水和乙醇清洗数次。然后放入硫化钠和硫代乙酰胺的混合溶液,浓度分别为10mmol/L和0.5mmol/L,140℃水热反应24h。反应结束后将镍片取出,用去离子水洗涤3~5遍,80℃烘干。即得到生长在泡沫镍基底上的氮掺杂的NiMoS4电催化剂,从图1可以看出得到线状结构的催化剂。
实施例2
将清洗过的泡沫镍竖直放入水热釜内衬中,然后加入浓度均为4mmol/L的钼酸钠和硝酸钴的混合溶液,然后放入不锈钢高压反应釜外套内密封,置于150℃的烘箱中反应16h,反应完成后自然冷却至室温,将镍片分别用蒸馏水和乙醇清洗数次。然后放入硫化钠和硫脲的混合溶液,浓度分别为6mmol/L和1mmol/L,160℃水热反应12h。反应结束后将镍片取出,用去离子水洗涤3~5遍,80℃烘干。即得到生长在泡沫镍基底上的氮掺杂的CoMoS4电催化剂。
实施例3
将浓度均为8mmol/L的钼酸钠和氯化钴的混合溶液放入不锈钢高压反应釜外套内密封,置于200℃的烘箱中反应24h,反应完成后自然冷却至室温,将得到的产物用蒸馏水和乙醇清洗数次。然后放入硫化钠和硫脲的混合溶液,浓度分别为12mmol/L和1.5mmol/L,180℃水热反应12h。反应结束后将产物收集,用去离子水和无水乙醇洗涤3~5遍,80℃烘干。即得到氮掺杂的CoMoS4电催化剂颗粒。
Claims (10)
1.一种氮掺杂三元硫化物电催化剂材料制备方法,其特征在于,包括以下步骤:
(1)将金属基底用盐酸、无水乙醇和去离子分别超声处理去除表面的氧化物层及杂质;
(2)将过渡金属前驱体盐及钨或钼的可溶性盐加入去离子水,搅拌溶解;
(3)将步骤(1)基底竖直放入水热釜中,然后加入步骤(2)溶液,然后进行水热反应;
(4)将步骤(3)得到的产物水洗,然后放入水热釜中,加入含硫源和氮源的溶液进行硫氮化反应;
(5)将步骤(4)得到的产物用去离子水洗涤、烘干,即得到氮掺杂的三元硫化物电催化剂。
2.按照权利要求1所述的一种氮掺杂三元硫化物电催化剂材料制备方法,其特征在于,步骤(3)中将步骤(2)溶液加入水热釜中的填充量为70%。
3.按照权利要求1所述的一种氮掺杂三元硫化物电催化剂材料制备方法,其特征在于,所述的金属基底为泡沫镍或泡沫铜;或者制备颗粒时省去步骤(1)、步骤(3)基底的引入,其它步骤相同。
4.按照权利要求1所述的一种氮掺杂三元硫化物电催化剂材料制备方法,其特征在于,钨或钼的可溶性盐为钼酸铵或钼酸铵,钨酸钠或偏钨酸铵;过渡金属前驱体盐为氯化物、硝酸盐、硫酸盐的任意一种或几种。
5.按照权利要求1所述的一种氮掺杂三元硫化物电催化剂材料制备方法,其特征在于,所述的钨或钼的可溶性盐的浓度为2~10mmol/L;过渡金属(X)前驱体盐与钨或钼(M)的可溶性盐的摩尔比为1~4,优选X:M的摩尔浓度比按照X和M形成的对应的合金的化学摩尔计量比进行配置,优选得到的X-M-S催化剂中X和M的摩尔比为现有技术中形成。
6.按照权利要求1所述的一种氮掺杂三元硫化物电催化剂材料制备方法,其特征在于,步骤(3)所述的水热反应温度为140~220℃,时间为4~24h。
7.按照权利要求1所述的一种氮掺杂三元硫化物电催化剂材料制备方法,其特征在于,步骤(4)所述的硫源为硫化钠,浓度为5~15mmol/L;氮源为尿素或硫代乙酰胺,浓度为0.2~2mmol/L。
8.按照权利要求1所述的一种氮掺杂三元硫化物电催化剂材料制备方法,其特征在于,步骤(4)所述的硫氮化温度为100~180℃,时间为4~24h。
9.按照权利要求1-8任一项所述的方法制备得到的一种氮掺杂三元硫化物电催化剂材料。
10.按照权利要求1-8任一项所述的方法制备得到的一种氮掺杂三元硫化物电催化剂材料的应用,其特征在于,作为双催化电解水用于催化产氧和催化产氢。
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