CN109012683A - 一种钼酸钴空心微球电催化剂的制备方法 - Google Patents
一种钼酸钴空心微球电催化剂的制备方法 Download PDFInfo
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- KYYSIVCCYWZZLR-UHFFFAOYSA-N cobalt(2+);dioxido(dioxo)molybdenum Chemical compound [Co+2].[O-][Mo]([O-])(=O)=O KYYSIVCCYWZZLR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003054 catalyst Substances 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract 2
- 238000005245 sintering Methods 0.000 claims description 16
- 239000011684 sodium molybdate Substances 0.000 claims description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims 3
- 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 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000004321 preservation Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 239000000376 reactant Substances 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000013019 agitation Methods 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- -1 molybdenum ion Chemical class 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HNIASRFAODUYDL-UHFFFAOYSA-N acetyl acetate;sodium Chemical compound [Na].CC(=O)OC(C)=O HNIASRFAODUYDL-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000002791 soaking Methods 0.000 description 3
- 239000001632 sodium acetate Substances 0.000 description 3
- 235000017281 sodium acetate Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910018864 CoMoO4 Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910004616 Na2MoO4.2H2 O Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical group 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- FDEIWTXVNPKYDL-UHFFFAOYSA-N sodium molybdate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][Mo]([O-])(=O)=O FDEIWTXVNPKYDL-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
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- 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
- B01J23/882—Molybdenum and cobalt
-
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
本发明公开了一种钼酸钴空心微球电催化剂的制备方法,其步骤为:分别称取硝酸钴、钼酸钠、无水醋酸钠,加入去离子水,搅拌至完全溶解,将所得混合溶液进行水热反应,待反应完毕后,清洗后干燥样品;将干燥后的样品在空气气氛下进行高温热处理,即得到钼酸钴空心微球样品。该方法提升了电解水分离效率,并降低了电催化剂的使用成本。
Description
技术领域
本发明属于纳米材料合成技术领域,具体涉及一种低成本制备钼酸钴空心微球的方法。
背景技术
鉴于能源危机和环境污染问题的日趋严重,开发可持续发展的清洁能源是迫切需要的。绿色能源氢气的开发有利于缓解当前的能源环境危机,电催化剂裂解水制氢气被认为是产生氢气的有效途径之一。电解水作为氢能源的主要产生方式,通常包括两个半反应,分别是产氢和产氧过程,而电解水的瓶颈主要在于阳极析氧反应(OER)的动力学缓慢,导致电解水制氢的转化效率较低,寻求高催化活性和性能稳定的析氧反应电催化剂成为电解水效率提升的关键。目前活性最高的析氧电催化剂是贵金属氧化物(例如IrO2和RuO2),但是贵金属材料资源稀缺、价格过高,不利于大规模生产。因此,迫切需要研发出高效、稳定的非贵金属催化剂来代替贵金属催化剂。由于过渡金属价格相对低廉而且其具有良好的电催化性能,因此受到广泛的关注。研究表明空心微纳结构的电催化剂具有较高的比表面积、较多的活性位点,较低的密度和热扩散系数,相比于块材或者实心结构具有更加优异的电催化活性。
钼酸钴(CoMoO4)是一种廉价过渡金属氧化物,具有良好的电化学稳定性和较高的电催化活性,截至目前,关于钼酸钴空心球的制备方法报道非常少,例如,(1)利用二氧化硅小球作为模板制备钼酸钴空心球,二氧化硅小球的有效去除增加了反应的复杂性(RSCAdv., 2016, 6, 51710);(2)利用金属有机钼盐作为反应物,有机溶剂作为反应溶剂,经过多步反应制备出钼酸钴空心球,其中金属有机盐和有机溶剂的使用,提高了制备成本,并且有机物的去除使反应过程变得复杂,这将不利于钼酸钴空心球制备的市场化(Chem.Mater. 2016, 28, 2417)。
发明内容
为了解决贵金属析氧电催化剂存在资源稀缺、价格过高等问题,本发明的目的是提供一种钼酸钴(CoMoO4)空心微球电催化剂的制备方法,该方法提升了电解水分离效率,并降低了电催化剂的使用成本。
实现本发明目的的技术解决方案是:一种钼酸钴空心微球结构的电催化剂的制备方法,主要包括以下步骤:
(1)钴离子和钼离子的氧化物空心微球前驱物的制备:分别称取Co(NO3)2.6H2O(硝酸钴)、Na2MoO4.2H2O(钼酸钠)、NaAC(无水醋酸钠),加入去离子水,磁力搅拌至完全溶解,将所得混合溶液加入聚四氟乙烯的反应釜中进行水热反应,待反应完毕后,将反应釜取出并自然冷却到室温,收集反应釜中的固态沉淀物,并分别用去离子水和无水乙醇清洗数次,并干燥样品;
(2)钼酸钴空心微球结构的制备:将烘干的固态样品置于管式烧结炉中,在空气气氛下,在设定的反应温度和反应时间内对样品进行高温热处理,待样品冷却至室温后取出,即得到钼酸钴空心微球样品。
进一步的,步骤(1)中,硝酸钴、钼酸钠和无水醋酸钠的摩尔比为1:1:10,三者在所得混合溶液中的摩尔浓度分别为0.033摩尔/升、0.033摩尔/升和0.33摩尔/升。
进一步的,步骤(1)中,磁力搅拌时间为0.5h-1h。
进一步的,步骤(1)中,水热反应时间为12h-24h,优选为20h, 水热反应温度为160OC-180 OC, 优选为180 OC,反应物溶液体积为反应釜总体积的60%。
进一步的,步骤(1)中,干燥温度为60 OC,干燥时间为24h。
进一步的,步骤(2)中,空气气氛下烧结温度为400 OC -600 OC,优选为500 OC,保温烧结时间为2h,升温速率为10 OC/min。
与现有技术相比,本发明具有如下有益效果:
本发明利用简单有效的方法制备出高效OER电催化活性的钼酸钴空心微球,有利于实现电催化裂解水效率的提升,同时有利于降低电催化剂的使用成本。
附图说明
图1为钼酸钴空心微球样品的XRD图谱分析(烧结温度500℃,烧结时间2h)。
图2为钼酸钴空心微球样品的TEM图(烧结温度500℃,烧结时间2h)。
图3为钼酸钴空心微球样品的SEM图(a: 低倍率,b:高倍率;烧结温度500℃,烧结时间2h)。
图4为反应钼酸钴空心微球样品的电流密度-电压关系的LSV极化曲线图(循环伏安法测试,样品烧结温度分别为400℃, 500℃,600℃)。
具体实施方式
下面结合实施例对本发明作进一步说明,但本发明并不限于以下实施例。
实施例1
第一步分别称量1mmol(290mg)硝酸钴,1mmol(240mg)钼酸钠,4mmol(820mg)无水醋酸钠,各自充分溶解于10ml去离子水中,首先将钼酸钠水溶液缓慢加入到硝酸钴水溶液中,并辅以磁力搅拌,然后将醋酸钠的水溶液缓慢加入到上述钼酸钠和硝酸钴的混合溶液中,并将这三种反应物的混合溶液在室温下磁力搅拌0.5h,最后将反应物的溶液转移到50ml容积的聚四氟乙烯的反应釜中,反应物溶液的体积为反应釜容积的60%,将反应釜于180 OC密闭加热20h,待反应釜自然冷却至室温后,将反应釜中的固态沉淀物取出,并利用去离子水和酒精进行清洗,然后将清洗后的样品在60OC干燥24h, 收集到钼酸钴空心微球的前驱物。
第二步将钼酸钴空心微球的前驱物放置在管式烧结炉中,并于空气气氛中进行热处理,升温速率为10 OC/min,热处理温度为500 OC,保温时间为2h,反应结束后得到黑色的钼酸钴空心微球结构样品。
实施例2
第一步分别称量1mmol(290mg)硝酸钴,1mmol(240mg)钼酸钠,4mmol(820mg)无水醋酸钠,各自充分溶解于10ml去离子水中,首先将钼酸钠水溶液缓慢加入到硝酸钴水溶液中,并辅以磁力搅拌,然后将醋酸钠的水溶液缓慢加入到上述钼酸钠和硝酸钴的混合溶液中,并将这三种反应物的混合溶液在室温下磁力搅拌0.5h,最后将反应物的溶液转移到50ml容积的聚四氟乙烯的反应釜中,反应物溶液的体积为反应釜容积的60%,将反应釜于180 OC密闭加热20h,待反应釜自然冷却至室温后,将反应釜中的固态沉淀物取出,并利用去离子水和酒精进行清洗,然后将清洗后的样品在60OC干燥24h, 收集到钼酸钴空心微球的前驱物。
第二步将钼酸钴空心微球的前驱物放置在管式烧结炉中,并于空气气氛中进行热处理,升温速率为10 OC/min,热处理温度为400 OC,保温时间为2h,反应结束后得到黑色的钼酸钴空心微球结构样品。
实施例3
第一步分别称量1mmol(290mg)硝酸钴,1mmol(240mg)钼酸钠,4mmol(820mg)无水醋酸钠,各自充分溶解于10ml去离子水中,首先将钼酸钠水溶液缓慢加入到硝酸钴水溶液中,并辅以磁力搅拌,然后将醋酸钠的水溶液缓慢加入到上述钼酸钠和硝酸钴的混合溶液中,并将这三种反应物的混合溶液在室温下磁力搅拌0.5h,最后将反应物的溶液转移到50ml容积的聚四氟乙烯的反应釜中,反应物溶液的体积为反应釜容积的60%,将反应釜于180 OC密闭加热20h,待反应釜自然冷却至室温后,将反应釜中的固态沉淀物取出,并利用去离子水和酒精进行清洗,然后将清洗后的样品在60OC干燥24h, 收集到钼酸钴空心微球的前驱物。
第二步将钼酸钴空心微球的前驱物放置在管式烧结炉中,并于空气气氛中进行热处理,升温速率为10 OC/min,热处理温度为600 OC,保温时间为2h,反应结束后得到黑色的钼酸钴空心微球结构样品。
图1为钼酸钴空心微球样品的X射线衍射图谱(XRD),分析表明所得产物为纯的钼酸钴(JCPDS卡片号:21-0868),图2 和图3 为钼酸钴空心微球样品的透射电镜图(TEM)和扫描电镜图(SEM),从图中可以看出钼酸钴样品的形貌为空心微球结构,空心微球的直径尺寸分布约为0.5μm-3.0μm,图4 为不同热处理温度(400 OC, 500 OC,600 OC)下得到的钼酸钴空心微球样品的OER电催化活性测试图,所用电解质为氢氧化钾溶液(浓度为1M/L),利用线性扫描伏安法(LSV)测试三组样品在电流密度为10mA/cm2对应的过电位,500 OC热处理钼酸钴空心微球的过电位为343mV,小于400 OC和600 OC热处理钼酸钴空心微球的过电位,因此,500 OC热处理得到的钼酸钴空心微球展示出最好的OER电催化活性。
Claims (9)
1.一种钼酸钴空心微球电催化剂的制备方法,其特征在于,包括以下步骤:
(1)分别称取硝酸钴、钼酸钠、无水醋酸钠,加入去离子水,搅拌至完全溶解,将所得混合溶液进行水热反应,待反应完毕后,清洗后干燥样品;
(2)将干燥后的样品在空气气氛下进行高温热处理,即得到钼酸钴空心微球样品。
2.如权利要求1所述的制备方法,其特征在于,步骤(1)中,硝酸钴、钼酸钠和无水醋酸钠的摩尔比为1:1:10,三者在所得混合溶液中的摩尔浓度分别为0.033摩尔/升、0.033摩尔/升和0.33摩尔/升。
3.如权利要求1所述的制备方法,其特征在于,步骤(1)中,搅拌时间为0.5h-1h。
4.如权利要求1所述的制备方法,其特征在于,步骤(1)中,水热反应时间为12h-24h,水热反应温度为160OC-180 OC。
5.如权利要求1所述的制备方法,其特征在于,步骤(1)中,水热反应时间为20h,水热反应温度为180 OC。
6. 如权利要求1所述的制备方法,其特征在于,步骤(1)中,干燥温度为60 OC,干燥时间为24h。
7.如权利要求1所述的制备方法,其特征在于,步骤(2)中,空气气氛下烧结温度为400OC -600 OC,保温烧结时间为2h。
8.如权利要求1所述的制备方法,其特征在于,步骤(2)中,空气气氛下烧结温度为500OC。
9.如权利要求1所述的制备方法,其特征在于,步骤(2)中,升温速率为10 OC/min。
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