通过NiMo氧化物-CoMo氧化物混合物衍生催化剂中的界面相互作用促进甲醇到甲酸盐的电催化氧化

doi:10.1016/S1872-2067(23)64565-6

催化学报 ›› 2024, Vol. 56: 139-149.DOI: 10.1016/S1872-2067(23)64565-6

通过NiMo氧化物-CoMo氧化物混合物衍生催化剂中的界面相互作用促进甲醇到甲酸盐的电催化氧化

齐宴宾^a^,^b, 朱以华^b, 江宏亮^a^,^*(), 李春忠^a^,^b^,^*()

^a华东理工大学化工学院, 超细材料制备与应用教育部重点实验室, 上海200237
^b华东理工大学材料科学与工程学院, 上海多级结构纳米材料工程技术研究中心, 上海200237

收稿日期:2023-09-28 接受日期:2023-11-14 出版日期:2024-01-18 发布日期:2024-01-10
通讯作者: *电子信箱: jhlworld@ecust.edu.cn (江宏亮), czli@ecust.edu.cn (李春忠)
基金资助:
国家重点研发计划(2022YFB3808400);国家自然科学基金(22222804);国家自然科学基金(U22B20143);上海市科学技术委员会(22dz1205900);上海市科技重大专项.

Promoting electrocatalytic oxidation of methanol to formate through interfacial interaction in NiMo oxide-CoMo oxide mixture-derived catalysts

Yanbin Qi^a^,^b, Yihua Zhu^b, Hongliang Jiang^a^,^*(), Chunzhong Li^a^,^b^,^*()

^aKey Laboratory for Ultrafine Materials of Ministry of Education, School of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
^bShanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China

Received:2023-09-28 Accepted:2023-11-14 Online:2024-01-18 Published:2024-01-10
Contact: *E-mail: jhlworld@ecust.edu.cn (H. Jiang), czli@ecust.edu.cn (C. Li).
Supported by:
National Key R&D Program(2022YFB3808400);National Natural Science Foundation of China(22222804);National Natural Science Foundation of China(U22B20143);Science and Technology Commission of Shanghai Municipality(22dz1205900);Shanghai Municipal Science and Technology Major Project.

摘要/Abstract

摘要：

为应对气候与环境变化及适应未来工业生产需求, 近年来, H₂O, CO₂以及有机小分子等的电催化还原或氢化反应受到广泛的关注. 但阳极析氧反应(OER)的缓慢动力学过程导致反应能耗高, 限制了其实际应用. 近年来, 研究人员采用热力学上更有利的亲核氧化反应(NOR)代替OER, 并与阴极半反应耦合, 进而降低总体能耗, 同时在阳极获得高附加值产物. 其中, 设计高效、稳定、易放大制备的催化剂是实现NOR工业化应用的关键.

本文采用简便且易于规模化生产的策略制备电催化剂, 并用于甲醇氧化反应(MOR). 首先, 采用沉淀法制备镍钼氧化物水合物和钴钼氧化物水合物; 随后, 将两种水合物按一定比例物理混合得到MOR催化剂. 实验结果表明, 混合物中的镍钴两种组分在含有KOH的碱性电解液中快速脱钼并转变为氢氧化物. 当混合物中NiMo氧化物与CoMo氧化物的质量比为1:1(记为Ni50Co50-m)时, 材料表现出最佳的催化活性. Ni50Co50-m在1 mol L^-1 KOH + 1 mol L^-1甲醇电解液中达到100 mA cm^-2电流密度仅需约1.51 V施加电位, 活性及阳极反应选择性均远远高于单一组分. 相比于化学共沉淀法所制备的NiCoMo氧化物, Ni50Co50-m表现出更好的稳定性. 为明确混合物催化性能比单一组分材料大幅提高的原因, 通过现场原位电化学阻抗谱和工况原位拉曼光谱对单一组分催化剂在服役条件下的反应界面以及催化剂结构演变进行研究. 结果表明, 单一镍组分催化剂在MOR过程中会被部分氧化为NiOOH, 但是由于镍组分导电性很差, 电荷转移微弱, 因此催化性能较差. 单一钴组分催化剂在MOR过程中表面被氧化为CoOOH, OER和MOR均发生在CoOOH表面, 但是钴组分的本征活性并不强且对竞争反应OER的选择性较高. 通过比较真实混合物(Ni50Co50-m)以及镍钴组分间无接触情况下的原位阻抗谱响应, 证明了镍与钴之间存在相互作用. 混合物中镍钴组分接触界面间的相互作用包括以下两个方面: 一方面, 钴组分在一定的外加电压下被氧化为导电良好的CoOOH, 其作为混合物中的电荷传输媒介, 激活更多的镍位点参与到催化剂的电氧化过程中, 增大了Ni²⁺/Ni³⁺氧化还原物种的覆盖度, 为催化活性物种OH*的形成提供了更多位点; 另一方面, 镍钴组分之间的相互作用影响了Ni²⁺的电氧化行为, Ni²⁺的氧化电位明显下降, 钴组分的引入降低了Ni³⁺‒O键的电子云密度, 使得OH^-向Ni³⁺位点的亲核进攻变得更加有利, 进而促进了OH*的产生及其与镍位点的紧密结合, 从而提高了MOR的活性和选择性.

综上, 本文通过混合物中镍与钴组分间的界面相互作用提升了催化剂对MOR的催化活性. 该混合增强策略同样适用于其他NOR(如乙醇氧化反应、乙二醇氧化反应等)以及其他镍基催化剂(如氢氧化镍、硫化镍). 本工作为简便、高效和放大制备NOR催化剂提供了新思路.

关键词: 亲核氧化反应, 电催化, 甲醇电催化氧化, 放大制备, 界面相互作用

Abstract:

Designing efficient, stable, and easily scaled-up catalysts for nucleophile oxidation reactions (NOR) is a key step in promoting the industrial application of NOR. Here, a simple physical mixing strategy is adopted to prepare a mixture of NiMo oxide and CoMo oxide as catalyst for methanol electrocatalytic oxidation reaction (MOR). The mixture exhibits high catalytic activity for MOR and its performance far exceeds that of a single component. The interaction at the contact interface between nickel and cobalt components is clarified through operando electrochemical impedance spectroscopy, in-situ Raman spectroscopy, and a series of electrochemical tests. The interfacial interaction enhances the charge transport and promotes the formation of electrophilic OH* species, which significantly boosts the methanol oxidation reaction. This work provides a new idea for the design of efficient and easily scaled-up catalysts for nucleophile oxidation reactions.

Key words: Nucleophile oxidation reaction, Electrocatalysis, Methanol electrocatalytic oxidation, Large-scale preparation, Interfacial interaction

齐宴宾, 朱以华, 江宏亮, 李春忠. 通过NiMo氧化物-CoMo氧化物混合物衍生催化剂中的界面相互作用促进甲醇到甲酸盐的电催化氧化[J]. 催化学报, 2024, 56: 139-149.

Yanbin Qi, Yihua Zhu, Hongliang Jiang, Chunzhong Li. Promoting electrocatalytic oxidation of methanol to formate through interfacial interaction in NiMo oxide-CoMo oxide mixture-derived catalysts[J]. Chinese Journal of Catalysis, 2024, 56: 139-149.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64565-6

https://www.cjcatal.com/CN/Y2024/V56/I1/139

图/表 5

Fig. 1. (a) TEM image and elemental mapping images of Ni100Co0. (b) High-resolution TEM (HRTEM) image of Ni100Co0. (c) SEM image of Ni0Co100. (d) TEM image and elemental mapping images of Ni0Co100. (e) TEM image of Ni50Co50-m coated on the GCE (fresh). (f) TEM image of Ni50Co50-m coated on the GCE (after immersion in KOH-containing electrolyte).

Fig. 2. (a) Comparison of performance of different samples in electrolytes containing 1 mol L?1 MeOH and different concentrations of KOH at 1.51 V. (b) CV curves of Ni50Co50-m for MOR and OER. (c) SCV curves of different samples for MOR in 1 mol L?1 KOH + 1 mol L?1 MeOH electrolyte. (d) Tafel slopes for MOR. (e) Stability test of different samples at 1.51 V. (f) Arrhenius plots of the current densities at 1.46 V. (g) LSV curves with RRDE for MOR. (h) FE of formate obtained at different potentials on Ni50Co50-m.

Fig. 3. (a,b) 2D-Bode plots of Ni100Co0 for OER and MOR. (c) In-situ Raman spectra of Ni100Co0 for MOR. (d) Possible NOR mechanisms of different nickel-based catalysts. (e,f) 2D-Bode plots of Ni0Co100 for OER and MOR. (g) In-situ Raman spectra of Ni0Co100 for MOR.

Fig. 4. (a) Schematic illustration of the working electrode used to simulate the absence of interaction between nickel and cobalt components and the corresponding equivalent circuit model. (b,c) 2D-Bode plots of Ni50|Co50-m and Ni50Co50-m ( for MOR. (d,e) The equivalent circuit models of Ni50Co50-m for MOR before and after simplification.

Fig. 5. (a) Surface coverage of Ni2+/Ni3+ redox species and proton diffusion coefficients of different samples obtained in 1 mol L?1 KOH. (b) FTACV curves for MOR. (c) Charge transfer resistance of different samples obtained in 1 mol L?1 KOH + 1 mol L?1 MeOH. (d,e) LSV curves with RRDE and the calculated FE of OER and MOR. (f) In-situ Raman spectra of Ni50Co50-m for MOR. (g) Schematic illustration of interfacial interaction.

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通过NiMo氧化物-CoMo氧化物混合物衍生催化剂中的界面相互作用促进甲醇到甲酸盐的电催化氧化

Promoting electrocatalytic oxidation of methanol to formate through interfacial interaction in NiMo oxide-CoMo oxide mixture-derived catalysts

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