铜掺杂的羟基氧化镍用于高效电催化乙醇氧化

doi:10.1016/S1872-2067(21)63995-5

催化学报 ›› 2022, Vol. 43 ›› Issue (6): 1478-1484.DOI: 10.1016/S1872-2067(21)63995-5

铜掺杂的羟基氧化镍用于高效电催化乙醇氧化

王慧宁^a, 关安翔^a, 张俊波^a, 米玉莹^a, 李思^a, 袁涛涛^b, 静超^b, 张丽娟^a^,^*(), 张林娟^b^,^$(), 郑耿锋^a^,^#()

^a复旦大学先进材料实验室, 化学与材料学院, 化学系, 上海市分子催化和功能材料重点实验室, 上海200438
^b中国科学院上海应用物理研究所, 中国科学院微观界面物理与探测重点实验室, 上海201800

收稿日期:2021-11-13 接受日期:2021-11-13 出版日期:2022-06-18 发布日期:2022-04-14
通讯作者: 张丽娟,张林娟,郑耿锋
基金资助:
国家重点研发计划(2018YFA0209401);国家重点研发计划(2017YFA0206901);国家自然科学基金(22025502);国家自然科学基金(21975051);国家自然科学基金(21773036);上海市科委(21DZ1206800);上海市科委(19XD1420400);上海市教委(2019-01-07-00-07-E00045);中国科学院战略性先导科技专项变革性洁净能源关键技术与示范(XDA2100000);王宽诚教育基金(GJTD-2018-10);中国科学院青年创新促进会(Y201842);中国科学院仪器装备研制项目(YJKYYQ20180066);中国科学院清洁能源实验室协同基金(DNL202008)

Copper-doped nickel oxyhydroxide for efficient electrocatalytic ethanol oxidation

Huining Wang^a, Anxiang Guan^a, Junbo Zhang^a, Yuying Mi^a, Si Li^a, Taotao Yuan^b, Chao Jing^b, Lijuan Zhang^a^,^*(), Linjuan Zhang^b^,^$(), Gengfeng Zheng^a^,^#()

^aLaboratory of Advanced Materials, Department of Chemistry and Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Faculty of Chemistry and Materials Science, Fudan University, Shanghai 200438, China
^bKey Laboratory of Interfacial Physics and Technology, Shanghai Institute of Applied Physics, Chinese Academy of Sciences, Shanghai 201800, China

Received:2021-11-13 Accepted:2021-11-13 Online:2022-06-18 Published:2022-04-14
Contact: Lijuan Zhang, Linjuan Zhang, Gengfeng Zheng
Supported by:
National Key Research and Development Program of China(2018YFA0209401);National Key Research and Development Program of China(2017YFA0206901);National Natural Science Foundation of China(22025502);National Natural Science Foundation of China(21975051);National Natural Science Foundation of China(21773036);Science and Technology Commission of Shanghai Municipality(21DZ1206800);Science and Technology Commission of Shanghai Municipality(19XD1420400);Shanghai Municipal Education Commission(2019-01-07-00-07-E00045);“Transformational Technologies for Clean Energy and Demonstration,” Strategic Priority Research Program of the Chinese Academy of Sciences(XDA2100000);K. C. Wong Education Foundation(GJTD-2018-10);Youth Innovation Promotion Association, Chinese Academy of Science(Y201842);Instrument and Equipment Development Program Chinese Academy of Science(YJKYYQ20180066);DNL Cooperation Fund, CAS(DNL202008)

摘要/Abstract

摘要：

醇的电化学氧化反应是能源和化学转化领域的一个研究热点, 它在燃料电池、生物质利用和精细化学品合成等领域展示出了广阔的应用前景. 其中, 乙醇是绿色、无毒的液体燃料, 与其相关的电催化氧化反应也在直接乙醇燃料电池、电催化乙醇重整制备高附加值的产物(如乙酸盐)等方面得到了广泛的研究. 目前广泛使用的乙醇氧化的电催化剂以铂、钯、铑等贵金属为主, 但其自然界储量较低, 成本高昂, 同时会因电催化乙醇氧化过程中产生的一氧化碳等中间产物而中毒失活. 因此, 研究人员致力于开发具有高活性、高稳定性和高选择性的非贵金属基乙醇氧化电催化剂. 镍基催化剂不仅展示出电催化乙醇氧化的活性, 也可以活化水产生OH_ads用于解决CO中间体引起的催化剂中毒问题. 铜基材料具有优异的本征电导率. 受之前研究的启发, 本文在镍基材料中掺杂铜以形成高价态的镍位点, 如Ni³⁺物种, 从而使镍基材料获得更好的电催化乙醇氧化性能.
通过原位电化学重建策略, 开发了一种以铜镍合金为前驱体的铜均匀掺杂的羟基氧化镍电催化剂. 铜掺杂改善了羟基氧化镍的导电性, 促进高价镍物种的产生, 从而改善了羟基氧化镍在电催化乙醇氧化中的性能. 采用X射线粉末衍射、拉曼光谱、扫描电子显微镜、X射线光电子能谱和透射电子显微镜等技术表征了所制电催化剂的物构性质. 可以发现, 引入铜掺杂物后, 羟基氧化镍中高价态Ni³⁺物种的比例(72%)相较于掺杂前(35%)提高了1倍, 且表现出优异的电催化乙醇氧化制备乙酸盐的性能. 在1.72 V (相对于RHE)下的电流密度可达227 mA·cm^‒2, 具有较高活性, 生产乙酸盐的法拉第效率达到98%以上; 使用32 h后, 催化剂仍然保持了最初活性的73%, 具有较高的稳定性. 通过电化学活性面积、电化学阻抗、塔菲尔斜率等一系列的电化学手段研究, 也证明了铜的引入是羟基氧化镍电催化乙醇氧化性能提高的关键. 此外, 本文使用了电化学原位拉曼光谱实时监测了电催化乙醇到乙酸盐的反应过程, 在所有给定电位下均可以观察到乙醇、乙醛和乙酸盐的特征峰. 结合核磁共振氢谱分析结果, 表明乙酸盐是铜掺杂的羟基氧化镍电催化乙醇氧化过程中的主要产物, 而乙醛可能是该过程中生成的重要中间体. 本工作为设计用于乙醇电化学氧化生产高附加值产品的非贵金属催化剂提供了一条有潜力的途径.

关键词: 乙醇氧化反应, 电催化剂, 铜掺杂, 羟基氧化镍, 乙酸盐

Abstract:

Rational design of low-cost and efficient electrocatalysts for ethanol oxidation reaction (EOR) is imperative for electrocatalytic ethanol fuel cells. In this work, we developed a copper-doped nickel oxyhydroxide (Cu-doped NiOOH) catalyst via in situ electrochemical reconstruction of a NiCu alloy. The introduction of Cu dopants increases the specific surface area and more defect sites, as well as forms high-valence Ni sites. The Cu-doped NiOOH electrocatalyst exhibited an excellent EOR performance with a peak current density of 227 mA·cm ^-2 at 1.72 V versus reversible hydrogen electrode, high Faradic efficiencies for acetate production (> 98%), and excellent electrochemical stability. Our work suggests an attractive route of designing non-noble metal based electrocatalysts for ethanol oxidation.

Key words: Ethanol oxidation reaction, Electrocatalyst, Cu doping, Nickel oxyhydroxide, Acetate

王慧宁, 关安翔, 张俊波, 米玉莹, 李思, 袁涛涛, 静超, 张丽娟, 张林娟, 郑耿锋. 铜掺杂的羟基氧化镍用于高效电催化乙醇氧化[J]. 催化学报, 2022, 43(6): 1478-1484.

Huining Wang, Anxiang Guan, Junbo Zhang, Yuying Mi, Si Li, Taotao Yuan, Chao Jing, Lijuan Zhang, Linjuan Zhang, Gengfeng Zheng. Copper-doped nickel oxyhydroxide for efficient electrocatalytic ethanol oxidation[J]. Chinese Journal of Catalysis, 2022, 43(6): 1478-1484.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)63995-5

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Fig. 1. (a) Schematic illustration for the preparation of Cu-doped NiOOH. (b) Raman spectra of NiCu alloy (black curve) and Cu-doped NiOOH (red curve). SEM (c), TEM (d), and high-resolution TEM (e) images of Cu-doped NiOOH. The panel (e) was zoomed in from the highlighted red box in (d). (f) HRTEM image and corresponding EDS results of Cu-doped NiOOH: Ni (green), Cu (blue), and O (red).

Fig. 2. (a) High-resolution XPS spectra for Ni 2p of NiOOH (upper panel) and Cu-doped NiOOH (lower panel). (b) CV curves of Cu-doped NiOOH in 1 mol/L KOH at increasing potential scan rates of 10, 20, 30, 40, 50, 60, 70, 80, 90, and 100 mV·s-1, respectively. (c) Linear relationship between anodic (Ipa, black curve), cathodic current (Ipc, red curve) densities and the scan rates. (d) Calculations of double layer capacitances for the Cu-doped NiOOH (purple curve) and NiOOH (green curve).

Fig. 3. (a) CV curves of Cu-doped NiOOH, NiOOH, NiCu alloy, Ni and Cu at 100 mV·s-1 in 1 mol/L KOH with 1 mol/L ethanol. (b) Electrocatalytic EOR activity of different catalysts. (c) 1H NMR spectra of liquid products at different potentials on Cu-doped NiOOH. (d) Faradaic efficiency of Cu-doped NiOOH for acetate production at different potentials.

Fig. 4. (a) Photograph of the electrochemical cell setup and the 532-nm laser excitation for in situ electrochemical Raman spectroscopy measurements. (b) Electrochemical Raman spectra of Cu-doped NiOOH before the electrolysis (black curve), under different potentials during EOR, and after the electrolysis (purple curve). (c) Chronopotentiometric curve recorded in a mixture of 1.0 mol/L KOH and 1.0 mol/L ethanol at 1.7 V.

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铜掺杂的羟基氧化镍用于高效电催化乙醇氧化

Copper-doped nickel oxyhydroxide for efficient electrocatalytic ethanol oxidation

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