CN108059194A - 球状CoWO4纳米材料的制备方法及其在电催化中的应用 - Google Patents
球状CoWO4纳米材料的制备方法及其在电催化中的应用 Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 7
- 229910019408 CoWO4 Inorganic materials 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 19
- 229910001868 water Inorganic materials 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 10
- 239000001103 potassium chloride Substances 0.000 claims abstract description 9
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 8
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 6
- 229920000557 Nafion® Polymers 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 5
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 5
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 235000021050 feed intake Nutrition 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000005868 electrolysis reaction Methods 0.000 abstract description 2
- 239000000446 fuel Substances 0.000 abstract description 2
- 229910021397 glassy carbon Inorganic materials 0.000 abstract description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 239000007772 electrode material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 244000137852 Petrea volubilis Species 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 238000005516 engineering process 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
- 239000011259 mixed solution Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 cobalt acetates Chemical class 0.000 description 1
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- KSOKAHYVTMZFBJ-UHFFFAOYSA-N iron;methane Chemical group C.[Fe].[Fe].[Fe] KSOKAHYVTMZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
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- 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
- B01J23/888—Tungsten
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Abstract
球状CoWO4纳米材料的制备方法及其在电催化中的应用，涉及电解水、燃料电池和金属‑空气电池等技术领域，将氯化钾水溶液与磷钨酸水溶液混合后常温下搅拌反应，取得K3PW12O40纳米材料后，再将K3PW12O40纳米材料溶于去离子水中，制得钨酸盐溶液，然后再将钨酸盐水溶液与乙酸钴水溶液混合进行水热反应，取得球状CoWO4纳米材料。把该纳米材料溶解在Nafion水溶液中，经修饰玻碳电极，得修饰样品的玻碳电极。可以大大提高在氧析出反应等方面的电催化性能。
Description
技术领域
本发明涉及电解水、燃料电池和金属-空气电池等技术领域，特别是其电极材料的制备技术。
背景技术
近十年来，在全球环境恶化和能源需求日益严重的情况下，能源转换和储存方面的研究逐渐激增。从这个意义上讲，环境友好的水分解制氢取得了巨大的关注。然而，分解水的电化学或光化学的析氧反应的过电位高的（OER）限制。虽然贵金属氧化物（例如RuO2和IrO2）和贵金属（例如Pt）–OER催化剂具有较高的催化活性和稳定性，其实际应用是经济上并不可行，因为他们的高价格和稀缺性。因此，努力研究高性能的替代品，如合金，金属氧化物和金属配合物。钴（Co）已经成为设计和制造坚固的最常见的非贵重元素之一和高效的OER催化剂。
钨酸钴(CoWO4)是一种重要的p型半导体在催化、磁性、传感器和光电领域电化学电池这方面得到了相当大的关注。更重要的是，CoWO4与Co3O4相比，具有优越的电化学活性和更高的电子多价态导电性。因此，预测CoWO4具有增强的电化学性能能源存储设备。
发明内容
针对以上现有技术和缺陷，本发明首先提出一种球状CoWO4纳米材料的制备方法。
本发明包括以下步骤：
1）将氯化钾水溶液与磷钨酸水溶液混合后常温下搅拌反应，取得沉淀物以水和乙醇洗涤后干燥，即得K3PW12O40纳米材料；
KCL+H3PWO40 = K3PW12O40+HCL
2）将K3PW12O40纳米材料溶于去离子水中，制得钨酸盐溶液；
3）将钨酸盐水溶液与乙酸钴水溶液混合进行水热反应，取得沉淀物用水和乙醇洗涤后干燥，即得球状CoWO4纳米材料。
本发明的球状CoWO4电极材料是由简单水热法制备而成，采用的原材料环保、成本低，工艺简单，易于操作控制，适于连续化大规模生产，制备过程绿色环保。
经实验证实，这种CoWO4纳米材料具有球状结构，由于其高的比表面积、优良的电导率等优异性能，可用于电催化。
进一步地，为了取得产物形貌最佳且性能最优，所述步骤1）中氯化钾和磷钨酸的混合体积比为1∶2。
所述步骤3）中乙酸钴为四水乙酸钴（Co(CH3COO)2•4H2O）。经实验证明，由于这几种金属二价盐所带的酸根易脱去，更易得到所需的产物，因此优先采用这种金属盐。
所述钨酸盐和四水乙酸钴的投料摩尔比为1∶10。此比例下CoWO4的形貌和性能较好。
所述水热反应的温度条件为120℃。经反复实验证明，在此水热温度下，能够合成生长良好、纯度较高的球状CoWO4，是最佳的工艺条件。
本发明另一目的还提出采用以上方法制成的球状CoWO4纳米材料在电催化中的应用。
超声条件下，把所述球状CoWO4纳米材料溶解在Nafion水溶液中，然后修饰在玻碳电极上，得到修饰样品的玻碳电极。
该应用的特点及优点：
（1）CoWO4纳米材料虽然其导电性较差，但其特殊的球状的纳米结构，大大提高了在氧析出反应（OER）等方面的电催化性能。
（2）利用电子传递，只需要通过很薄的膜层，电子就可以到达载体电极上。
（3）氧析出反应（OER）被认为是对环境友好和可再生的能源系统。
附图说明
图1为本发明制备的球状K3PW12O40电极材料的扫描电镜图（SEM）。
图2为本发明制备的片球状CoWO4电极材料的扫描电镜图（SEM）。
图3为本发明制备的片球状CoWO4电极材料的透射电镜图（TEM）。
图4为本发明制备的球状CoWO4电极材料的X射线衍射图（XRD）。
图5为本发明制备的球状CoWO4电极材料的OER的循环伏安曲线图。
图6为本发明制备的球状CoWO4电极材料的OER的线性扫描曲线图。
具体实施方式
下面结合附图和具体实施方式用实例对本发明作进一步说明，但不限于此。
一、制备球状CoWO4纳米材料：
1、将氯化钾溶于去离子水中，制得0.20 moL /L氯化钾水溶液。
将磷钨酸溶于去离子水中，制得0.0030 moL/ L磷钨酸水溶液。
再取5 mL氯化钾水溶液逐滴加入10 mL磷钨酸水溶液中，经反应得到沉淀物，将沉淀物以水和乙醇洗涤后干燥，即得粉末状K3PW12O40纳米材料。
对粉末状K3PW12O40纳米材料进行SEM测试：图1为放大10000倍下的扫描电子显微镜照片，其显示典型的球状结晶结构，可以为扩散和储存电解质离子提供大的比表面积。
2、取0.4 g 粉末状K3PW12O40纳米材料溶解在20 mL 去离子水中，得到钨酸盐水溶液。
将0.0249 g Co(CH3COO)2•4H2O溶于20 mL去离子水中，得钴盐水溶液。
将钨酸盐水溶液和钴盐水溶液混合，在120℃条件下水热反应8小时，得到的灰色沉淀物，用去离子水和乙醇分别洗涤3次后干燥，即得到球状CoWO4纳米材料。
二、球状CoWO4纳米材料的特征：
对球状CoWO4纳米材料进行SEM测试：图2为球状CoWO4纳米材料的扫描电镜图，其样品表面为针形的球状结构。
对球状CoWO4纳米材料进行TEM测试：图3为球状CoWO4纳米材料的透射电镜图，样品为实心球并且其表面为针形结构。
对球状CoWO4纳米材料进行XRD测试：图4为球状CoWO4纳米材料的X射线衍射图，其峰可以和标准峰对上，从而表明所合成的样品为所需要的样品。
三、电催化电极的制备：
1、将直径为3 mm的玻碳电极分别用吸附了1 μm氧化铝悬浮液的砂纸和吸附了0.3 μm氧化铝悬浮液的砂纸打磨抛光。
2、将打磨抛光好的玻碳电极依次放在去离子水中超声清洗1分钟后，在0.5M KCl+K3[Fe(CN)6]溶液中扫描循环伏安曲线，以测试电极是否磨好，最后取得洁净的玻碳电极，晾干以待用。
3、取6 mg制备取得的球状CoWO4纳米材料加入由800 mL H2O和200 mL Nafion混合组成的Nafion水溶液中，超声混合，制成混合溶液，随后将5 μL混合溶液采用涂覆的方法修饰在直径为3 mm的洁净的玻碳电极表面，自然晾干后即得球状CoWO4电催化电极。
四、电极的电催化性能试验：
以氢氧化钾作为电解液，其中，氢氧化钾浓度为1 mol/L。
将球状CoWO4电催化电极放置在1 mol/L的KOH溶液中进行测定。
利用电化学工作站，将制备的待测电极在事先通入大约半小时氮气的电解质溶液中，在0.0～0.5 V之间的电位下，扫描速率控制为0.05 V/s，先进行循环伏安扫描，然后在0.0～1.90 V之间的电位下，扫描速率控制为100 mV/s，进行线性伏安扫描，测试样品的电化学性能。
图5显示了样品CoWO4修饰的电极在电位（相对于标准氢电极）为0.90 -1.45 V范围内显示无明显的氧化还原峰。
图6显示了样品CoWO4修饰的电极在电位（相对于标准氢电极）为0.0-1.90 V在1mol/L氢氧化钾电解质溶液中显示出良好的OER电催化性能，在电流密度为10 mA cm-2时对应的电压为1.83 V。
Claims (6)
1.球状CoWO4纳米材料的制备方法，其特征在于包括以下步骤：
1）将氯化钾水溶液与磷钨酸水溶液混合后常温下搅拌反应，取得沉淀物以水和乙醇洗涤后干燥，即得K3PW12O40纳米材料；
2）将K3PW12O40纳米材料溶于去离子水中，制得钨酸盐溶液；
3）将钨酸盐水溶液与乙酸钴水溶液混合进行水热反应，取得沉淀物用水和乙醇洗涤后干燥，即得球状CoWO4纳米材料。
2.根据权利要求1所述的制备方法，其特征在于所述步骤1）中氯化钾和磷钨酸的混合体积比为1∶2。
3.根据权利要求1所述的制备方法，其特征在于所述步骤3）中乙酸钴为四水乙酸钴。
4.根据权利要求3所述的制备方法，其特征在于所述钨酸盐和四水乙酸钴的投料摩尔比为1∶10。
5.根据权利要求1或4所述的制备方法，其特征在于所述水热反应的温度条件为120℃。
6.如权利要求1所述制备方法制得的球状CoWO4纳米材料在电催化中的应用，其特征在于：超声条件下，把所述球状CoWO4纳米材料溶解在Nafion水溶液中，然后修饰在玻碳电极之上，得到修饰样品的玻碳电极。
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