CN113416978A - 一种三氧化二铁/氧化亚铜/碳布析氧电催化薄膜的制备方法 - Google Patents
一种三氧化二铁/氧化亚铜/碳布析氧电催化薄膜的制备方法 Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 19
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 15
- 239000004744 fabric Substances 0.000 title claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 title abstract description 8
- 239000001301 oxygen Substances 0.000 title abstract description 8
- 229940112669 cuprous oxide Drugs 0.000 title abstract description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title 1
- 239000002243 precursor Substances 0.000 claims abstract description 36
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000004070 electrodeposition Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 12
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000003792 electrolyte Substances 0.000 claims abstract description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 229910002588 FeOOH Inorganic materials 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 38
- 238000006243 chemical reaction Methods 0.000 claims description 28
- 239000010949 copper Substances 0.000 claims description 28
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000004317 sodium nitrate Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 235000010344 sodium nitrate Nutrition 0.000 claims description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 11
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000004310 lactic acid Substances 0.000 claims description 9
- 235000014655 lactic acid Nutrition 0.000 claims description 9
- 238000000151 deposition Methods 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 150000004677 hydrates Chemical class 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- YHGPYBQVSJBGHH-UHFFFAOYSA-H iron(3+);trisulfate;pentahydrate Chemical compound O.O.O.O.O.[Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YHGPYBQVSJBGHH-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 21
- 239000010408 film Substances 0.000 description 41
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 7
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229940032296 ferric chloride Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052595 hematite Inorganic materials 0.000 description 1
- 239000011019 hematite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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Abstract
本发明公开了一种三氧化二铁/氧化亚铜/碳布析氧电催化薄膜的制备方法。本发明的制备方法包括:1.将碳布基体进行亲水性预处理,备用;2.将步骤1所得基体浸没于Fe3+前驱体溶液中,进行水热反应得FeOOH薄膜,然后在500℃下恒温煅烧得到Fe2O3薄膜;3.以Cu2+的前驱体溶液做电解液,以步骤2所得的Fe2O3/CC作为阴极,进行恒电压电沉积,制得Fe2O3/Cu2O/CC电催化薄膜,制备所得的电催化薄膜的析氧过电位最低可达296mv,塔菲尔斜率最低为66mv/dec。本发明的制备工艺简单,重复性高,制备所得的电催化薄膜具有优异的电催化析氧性能和稳定性。
Description
技术领域
本发明涉及一种三氧化二铁/氧化亚铜/碳布析氧电催化薄膜的制备方法,属于电催化材料技术领域。
背景技术
温室效应和能源短缺是现今人类社会面临的两大问题,寻求高效无害的环境友好的污染治理技术已成为人类亟待解决的课题。氢能由于其高能量密度而被广泛作用于能量载体,分解水被认为是产生清洁和可再生燃料的最有前景的战略之一,水氧化半反应(OER)由于其缓慢的动力学特性而成为整个水分解过程的关键,这会导致过高的电势并降低功率转换效率。因此,设计高效的OER催化剂可以改善反应动力学并降低过电势。迄今为止,含贵金属如RuO2和IrO2的催化剂对水氧化具有很大的催化活性。然而,贵金属的高成本和稀缺性限制了其实际应用和大规模应用。因此开发高效低成本的OER电催化剂,已成为目前该领域研究的重要方向。
氧化铁作为纳米新材料中的一类重要氧化物,在广泛的pH范围内表现出优异的化学稳定性、耐腐蚀性、地壳中的高丰度、无毒性、低加工成本和生物降解性导致高经济可行性,文献中很少有将纯赤铁矿用作OER电催化剂的报道,因为Fe2O3动力学缓慢和导电性差限制了OER效率。通过对Fe2O3催化剂进行掺杂或复合改性来提高Fe2O3的催化活性。
近年来,由于铜的高纯度和低成本以及这些体系的简单性,铜基材料作为潜在的OER催化剂的应用受到了广泛的关注。Du(X.Liu,Z.Sun,S.Cui,P.Du,Cuprous oxide thinfilm directly electrodeposited from a simple copper salt on conductiveelectrode for efficient oxygen evolution reaction,Electrochim.Acta 187(2016)381–388.)团队报道Cu2O薄膜对OER具有良好的催化活性和稳定性,说明Cu2O是一种很有前途的OER催化剂,其析氧过电位最低为296mv,塔菲尔斜率为66mv/dec。
发明内容
本发明所要解决的技术问题是:针对OER催化剂中贵金属的高成本及稀缺性以及Fe2O3动力学和导电性的不足等问题。
为了解决上述技术问题,本发明提供了一种Fe2O3/Cu2O/CC电催化薄膜的制备方法,包括如下步骤:
步骤1:将碳布基体放入硝酸水溶液中,经高压釜反应进行亲水性处理,洗涤,干燥,备用;
步骤2:将经步骤1处理后的碳布基体浸没于Fe3+的前驱体溶液中进行水热反应,反应后经洗涤,干燥得到前驱体FeOOH/CC;
步骤3:将步骤2所得的前驱体进行煅烧,得到Fe2O3/CC。
步骤4:以Cu2+的前驱体溶液做电解液,以步骤3所得Fe2O3/CC作为阴极,Ag/AgCl为参比电极,铂片作为对电极进行恒电压电沉积,水洗,干燥,得到Fe2O3/Cu2O/CC电催化薄膜。
优选地,所述步骤1中的硝酸水溶液的摩尔浓度为4M,所述反应的温度为100℃,时间为4h。
优选地,所述步骤2中的Fe3+的前驱体溶液为铁盐和硝酸钠的酸性水溶液,所述硝酸钠的摩尔浓度为0.8~1.0M;所述铁盐和硝酸钠的摩尔浓度之比为1:8~10。
优选地,所述步骤2中的水热反应的温度为100℃~150℃,时间为6h~12h。
更优选地,所述铁盐为硫酸铁、硝酸铁、氯化铁和其对应的水合物中的至少一种。
优选地,所述酸性水溶液为铁盐和硝酸钠溶于水后,再经1~3M的盐酸溶液调节pH值至1.5~2所得。
优选地,所述步骤3中煅烧的温度为500℃,时间为2~5h。
优选地,所述步骤4中的Cu2+的前驱体溶液为硫酸铜和乳酸的碱性水溶液,其中,硫酸铜的摩尔浓度为0.1~0.2M,硫酸铜和乳酸的摩尔比为0.1:3。
优选地,所述碱性水溶液为硫酸铜和乳酸溶于水后,再通过3~5M NaOH溶液调节pH值至10~12所得。
优选地,所述步骤4中恒电压电沉积的工艺参数为:电沉积温度35℃,工作电压-0.5~-0.7V,沉积时间300~700s。
与现有技术相比,本发明的有益效果在于:
1.本发明利用水热法和电沉积法制备的Fe2O3/Cu2O/CC电催化薄膜,表面均匀、活性物质稳定性好,不宜剥落,薄膜面积易控制,Fe2O3阵列的形貌可以为传质提供足够的空间和大量的活性中心;核-壳异质结构通过电子相互作用为Fe2O3和Cu2O的电子结构调制提供了较大的接触面积,从而实现了有效的电子转移,降低了反应的过电位;
2.本发明的Fe2O3/Cu2O/CC电催化薄膜可循环使用,极大的降低了成本,减少了二次污染,同时解决了粉体催化剂难回收的问题;
3.本发明的制备工艺简单,重复性高,并且经济成本较低;通过对电沉积时间和温度等参数调控,制备氧化亚铜含量不同的Fe2O3/Cu2O/CC电催化薄膜,在10mA·cm-2表现出66mv/dec的低过电势。
附图说明
图1为实施例1~3制备所得的Fe2O3/Cu2O/CC电催化薄膜(分别为CFC-3、CFC-5和CFC-7)与实施例1中步骤1得到的CC薄膜、步骤2制得的Fe2O3/CC(FC)薄膜和FeOOH/CC(FeOOH)的XRD对比图;
图2为实施例1中步骤(2)得到的Fe2O3/CC薄膜表面的SEM图;
图3为实施例1中制备的Fe2O3/Cu2O/CC电催化薄膜表面的SEM图;
图4为实施例1~3制备所得的Fe2O3/Cu2O/CC电催化薄膜(分别为CFC-3、CFC-5和CFC-7)与实施例1中步骤1得到的CC薄膜、步骤2制得的Fe2O3/CC(FC)薄膜的OER极化曲线图。
具体实施方式
为使本发明更明显易懂,兹以优选实施例,并配合附图作详细说明如下。
实施例1
一种Fe2O3/Cu2O/CC电催化薄膜的制备方法,包括以下步骤:
(1)将碳布基体置于4M硝酸水溶液中,100℃反应4h进行亲水性处理,反应结束后,去离子水水洗至中性,干燥备用。
(2)将六水合氯化铁(FeCl3·6H2O)、硝酸钠溶于水配制成六水合氯化铁的浓度为0.1M,硝酸钠的浓度为0.8M的Fe3+的前驱体溶液,2M盐酸调节pH至1.9。将碳布基体浸没于Fe3+的前驱体溶液中,将其置于高压反应釜中进行水热成膜反应,反应温度为120℃,反应时间为6h,反应结束后用去离子水冲洗,干燥后得到FeOOH/CC前驱体,将前驱体放入马弗炉中,在500℃下恒温煅烧2h,即得到Fe2O3/CC薄膜。
(3)配制100mL含有0.1M硫酸铜的3M乳酸溶液,然后取30mL该溶液用4M的氢氧化钠溶液调节pH=10,得到Cu2+的前驱体溶液。以Cu2+的前驱体溶液作为电解液,使用autolab电化学工作站采用三电极体系进行电沉积,即以步骤(2)所得Fe2O3/CC薄膜作为阴极,铂丝为对电极,Ag/AgCl电极作为参比电极,进行电沉积,电沉积的温度为35℃,工作电压为-0.5V,沉积时间为300s。反应结束后,去离子水洗涤,室温干燥后,即制Fe2O3/Cu2O/CC电催化薄膜。
(4)对(3)所得的产品进行电化学性能测试,使用Autolab电化学工作站,在1M的KOH溶液中,采用的是三电极体系对对(3)所得的产品进行电化学性能测试,Hg/HgO为参比电极,箔片为对电极,扫描速率为5mv·s-1。过电位为302mv,塔菲尔斜率为207mv·dec-1。
实施例2
一种Fe2O3/Cu2O/CC电催化薄膜的制备方法,包括以下步骤:
(1)将碳布基体置于4M硝酸水溶液中,100℃反应4h进行亲水性处理,反应结束后,去离子水水洗至中性,干燥备用。
(2)将六水合氯化铁(FeCl3·6H2O)、硝酸钠溶于水配制成六水合氯化铁的浓度为0.1M,硝酸钠的浓度为0.9M的Fe3+的前驱体溶液,2M盐酸调节pH至1.9。,将碳布基体浸没于Fe3+的前驱体溶液中,将其置于高压反应釜中进行水热成膜反应,反应温度为100℃,反应时间为12h,反应结束后用去离子水冲洗,干燥后得到FeOOH/CC前驱体,将前驱体放入马弗炉中,在500℃下恒温煅烧2h,即得到Fe2O3/CC薄膜。
(3)配制100mL含有0.1M硫酸铜的3M乳酸溶液,然后取30mL该溶液用4M的氢氧化钠溶液调节pH=10,得到Cu2+的前驱体溶液。以Cu2+的前驱体溶液作为电解液,使用autolab电化学工作站采用三电极体系进行电沉积,即以步骤(2)所得Fe2O3/CC薄膜作为阴极,铂丝为对电极,Ag/AgCl电极作为参比电极,进行电沉积,电沉积的温度为35℃,工作电压为-0.5V,沉积时间为500s。反应结束后,去离子水洗涤,室温干燥后,即得Fe2O3/Cu2O/CC电催化薄膜。
(4)对(3)所得的产品进行电化学性能测试,使用Autolab电化学工作站,在1M的KOH溶液中,采用的是三电极体系对对(3)所得的产品进行电化学性能测试,Hg/HgO为参比电极,箔片为对电极,扫描速率为5mv·s-1。过电位为296mv,塔菲尔斜率为66mv·dec-1。
实施例3
一种Fe2O3/Cu2O/CC电催化薄膜的制备方法,包括以下步骤:
(1)将碳布基体置于4M硝酸水溶液中,100℃反应4h进行亲水性处理,反应结束后,去离子水水洗至中性,干燥备用。
(2)将六水合氯化铁(FeCl3·6H2O)、硝酸钠溶于水配制成六水合氯化铁的浓度为0.1M,硝酸钠的浓度为1M的Fe3+的前驱体溶液,2M盐酸调节pH至1.9。,将碳布基体浸没于Fe3 +的前驱体溶液中,将其置于高压反应釜中进行水热成膜反应,反应温度为120℃,反应时间为6h,反应结束后用去离子水洗,干燥后得到FeOOH/CC前驱体,将前驱体放入马弗炉中,在500℃下恒温煅烧2h,即得到Fe2O3/CC薄膜。
(3)配制100mL含有0.1M硫酸铜的3M乳酸溶液,然后取30mL该溶液用4M的氢氧化钠溶液调节pH=10,得到Cu2+的前驱体溶液。以Cu2+的前驱体溶液作为电解液,使用autolab电化学工作站采用三电极体系进行电沉积,即以步骤(2)所得的Fe2O3/CC薄膜作为阴极,铂丝为对电极,Ag/AgCl电极作为参比电极,进行电沉积,电沉积的温度为35℃,工作电压为-0.5V,沉积时间为700s。反应结束后,去离子水洗涤,室温干燥后,即制Fe2O3/Cu2O/CC电催化薄膜。
(4)对(3)所得的产品进行电化学性能测试,使用Autolab电化学工作站,在1M的KOH溶液中,采用的是三电极体系对对(3)所得的产品进行电化学性能测试,Hg/HgO为参比电极,箔片为对电极,扫描速率为5mv·s-1。过电位为343mv,塔菲尔斜率为155mv·dec-1。
其中,实施例1~3制备所得的Fe2O3/Cu2O/CC电催化薄膜与实施例1中步骤1得到的CC薄膜、步骤2制得的Fe2O3/CC(FC)薄膜和FeOOH/CC(FeOOH)前驱体的XRD对比图如图1所示,由图1可知,实施例1~3制备所得的Fe2O3/Cu2O/CC电催化薄膜的XRD曲线中含有α-氧化铁晶体和氧化亚铜晶体的特征衍射峰,表明成功合成Fe2O3/Cu2O/CC电催化薄膜材料;实施例1中步骤2制得的Fe2O3/CC(FC)薄膜和最终制备所得的Fe2O3/Cu2O/CC电催化薄膜的电镜扫描图分别如图2和图3所示,由图2和图3可知,Fe2O3晶体呈阵列式均匀分布,经过电化学沉积,Fe2O3/CC薄膜表面均匀沉积Cu2O纳米颗粒;实施例1~3制备所得的Fe2O3/Cu2O/CC电催化薄膜与实施例1中步骤1得到的CC薄膜、步骤2制得的Fe2O3/CC(FC)薄膜的OER极化曲线图如图4所示,由图4可知,沉积时间为500s时,电催化薄膜材料在达到10mA·cm-1时所需要的过电位最低,仅为296mv,当沉积时间为300s和700s时则分别需要302mv和343mv才可以达到10mA·cm-1。
上述实施例仅为本发明的优选实施例,并非对本发明任何形式上和实质上的限制,应当指出,对于本技术领域的普通技术人员,在不脱离本发明的前提下,还将可以做出若干改进和补充,这些改进和补充也应视为本发明的保护范围。
Claims (10)
1.一种Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,包括如下步骤:
步骤1:将碳布基体放入硝酸水溶液中,经高压釜反应进行亲水性处理,洗涤,干燥,备用;
步骤2:将经步骤1处理后的碳布基体浸没于Fe3+的前驱体溶液中进行水热反应,反应后经洗涤,干燥得到前驱体FeOOH/CC;
步骤3:将步骤2所得的前驱体进行煅烧,得到Fe2O3/CC。
步骤4:以Cu2+的前驱体溶液做电解液,以步骤3所得Fe2O3/CC作为阴极,Ag/AgCl为参比电极,铂片作为对电极进行恒电压电沉积,水洗,干燥,得到Fe2O3/Cu2O/CC电催化薄膜。
2.如权利要求1所述的Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,所述步骤1中的硝酸水溶液的摩尔浓度为4M,所述反应的温度为100℃,时间为4h。
3.如权利要求1所述的Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,所述步骤2中的Fe3+的前驱体溶液为铁盐和硝酸钠的酸性水溶液,所述硝酸钠的摩尔浓度为0.8~1.0M;所述铁盐和硝酸钠的摩尔浓度之比为1:8~10。
4.如权利要求1所述的Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,所述步骤2中的水热反应的温度为100℃~150℃,时间为6h~12h。
5.如权利要求3所述的Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,所述铁盐为硫酸铁、硝酸铁、氯化铁和其对应的水合物中的至少一种。
6.如权利要求3所述的Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,所述酸性水溶液为铁盐和硝酸钠溶于水后,再经1~2M的盐酸溶液调节pH值至1.5~2所得。
7.如权利要求1所述的Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,所述步骤3中煅烧的温度为500℃,时间为2~5h。
8.如权利要求1所述的Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,所述步骤4中的Cu2+的前驱体溶液为硫酸铜和乳酸的碱性水溶液,其中,硫酸铜的摩尔浓度为0.1~0.2M,硫酸铜和乳酸的摩尔比为0.1:3。
9.如权利要求8所述的Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,所述碱性水溶液为硫酸铜和乳酸溶于水后,再通过3~5M NaOH溶液调节pH值至10~12所得。
10.如权利要求1所述的Fe2O3/Cu2O/CC电催化薄膜的制备方法,其特征在于,所述步骤4中恒电压电沉积的工艺参数为:电沉积温度35℃,工作电压-0.5~-0.7V,沉积时间300~700s。
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