调控Ru的电子态以促进乙烯在酸中高选择性电氧化合成乙二醇

doi:10.1016/S1872-2067(24)60024-0

催化学报 ›› 2024, Vol. 60: 376-385.DOI: 10.1016/S1872-2067(24)60024-0

调控Ru的电子态以促进乙烯在酸中高选择性电氧化合成乙二醇

王杰^a^,^b, 陈怡和^a^,^b, 王宇达^b, 赵浩^b, 叶进裕^c, 程庆庆^b^,^*(), 杨辉^a^,^b^,^*()

^a上海科技大学物质科学与技术学院, 上海 201210
^b中国科学院上海高等研究院, 上海 201210
^c厦门大学化学化工学院, 福建厦门 361005

收稿日期:2024-01-26 接受日期:2024-03-26 出版日期:2024-05-18 发布日期:2024-05-23
通讯作者: *电子邮箱: chengqq@sari.ac.cn (程庆庆), yangh@sari.ac.cn (杨辉).
基金资助:
国家重点研发计划(2021YFB4000200);上海市自然科学基金面上项目(23ZR1471000)

Manipulating the electronic state of ruthenium to boost highly selective electrooxidation of ethylene to ethylene glycol in acid

Jie Wang^a^,^b, Yihe Chen^a^,^b, Yuda Wang^b, Hao Zhao^b, Jinyu Ye^c, Qingqing Cheng^b^,^*(), Hui Yang^a^,^b^,^*()

^aSchool of Physical Science and Technology, Shanghai Tech University, Shanghai 201210, China
^bShanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai 201210, China
^cCollege of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian, China

Received:2024-01-26 Accepted:2024-03-26 Online:2024-05-18 Published:2024-05-23
Contact: *E-mail: chengqq@sari.ac.cn (Q. Cheng), yangh@sari.ac.cn (H. Yang).
Supported by:
National Key R&D Program of China(2021YFB4000200);Shanghai Science and Technology Innovation Action Plan(23ZR1471000)

摘要/Abstract

摘要：

乙二醇(EG)是一种重要的化工产品, 由于在化学品制造行业的广泛应用而备受关注. 然而，目前工业上制备乙二醇主要采用乙烯作为原料, 经过环氧化和水解两步反应, 这一过程不仅需要高温高压, 还需使用成本高的氧化剂(如H₂O₂), 这违背了绿色化学的原则. 因此, 电催化阳极氧化作为一种新兴的合成策略, 正逐渐受到研究者的青睐. 该技术仅通过电子转移并利用水作为氧源, 就能够高效合成高附加值含氧化学品. 特别是, 阳极氧化反应可与阴极还原反应(例如氢析出反应)相耦合, 实现能量的高效利用. 尽管电催化阳极氧化具有诸多优势, 但目前在乙烯电氧化合成乙二醇过程中, 其选择性仍然较低, 这导致后续的纯化过程变得复杂且成本高昂. 因此, 开发高选择性的电氧化合成乙二醇技术, 成为了一项迫切且极具挑战性的任务.

本文提出了一种Ir和Ru合金化策略, 以提高乙烯电氧化制备乙二醇的选择性和耐久性. 研究结果表明, 当Ir和Ru的原子比达到适当的比例(即Ir_0.54Ru_0.46)时, 所制备的IrRu合金表现出近100%的乙二醇选择性, 远远优于Ru NPs对照组样品(43.8%). 此外, 在1.475 V的电压下, Ir_0.54Ru_0.46催化生成乙二醇产率达到了60.62 mmolg_Ru^‒1 h^‒1, 是Ru NPs上最高产率(21.75 mmolg_Ru^‒1 h^‒1)的2.8倍. 在耐久性测试中, Ir_0.54Ru_0.46能够稳定催化生成乙二醇超过12 h, 其生成速率为6 μmol L^‒1 h^‒1. 相比之下, 对照组样品Ru NPs在电解反应3 h后已失去活性. 能量损失谱分析显示, Ir_0.54Ru_0.46在电解2 h后形成了稳定的表面富Ir核壳结构IrRu@Ir, 这是催化剂稳定性提升的关键. 先进光谱研究进一步揭示, Ir的引入导致了电子由Ru位点向Ir流动, 使Ru位点带正电荷, 从而减弱了OH的吸附. OH脱附实验结果表明, 随着Ir/Ru原子比的增加, OH更容易从Ru位点脱附, 这促进了OH与乙烯的偶联反应. 自由基淬灭和氘代同位素标记实验结果表明, 在IrRu催化剂上, 乙烯到乙二醇的转化并非级联反应, 而是直接的表面催化反应, 其中OH的转移是决速步骤. X射线光电子能谱分析显示, 随着合金中Ir比例的增加, 合金d带中心下移, 这有利于关键中间体(*OH等)的转移. 原位红外光谱表明, 乙烯分子在Ru位点上通过Pauling型吸附构型被活化. 值得注意的是, 仅检测到*CH₂CH₂OH中间体, 而未检测到其他氧基团(如羰基), 这表明在反应过程中没有发生过氧化现象. 密度泛函理论计算进一步证实, 与Ir合金化不仅加速了OH的转移, 还优化了反应途径, 使乙二醇的选择性达到100%.

综上, 本文设计了不同Ir/Ru原子比的IrRu合金催化剂, 通过有效调控活性位点Ru的电子结构, 优化了OH的结合能, 使乙烯可以100%选择性高效转化为乙二醇, 这为开发高选择性电催化剂用于乙二醇电合成提供了新思路.

关键词: 乙烯电氧化, 电合成乙二醇, 高选择性, IrRu合金, 电子结构

Abstract:

Electrochemical oxidation of ethylene is a novel approach to manufacture valuable ethylene glycol (EG), which is an important raw material in organic chemical industry. However, the poor EG selectivity and expensive additional purification costs hinder this method from being practically used. In this work, ultrafine iridium-ruthenium (IrRu) alloy nanoparticles are synthesized through the precipitation-reduction method and their electrocatalytic performance towards ethylene oxidation to EG has been comprehensively studied. Near 100% selectivity is achieved with a EG yield of 60.62 mmol g_Ru^-1 h^-1 at 1.475 V on an optimal Ir_0.54Ru_0.46 catalyst. OH-stripping, in-situ electrochemical attenuated total internal reflectance Fourier transform infrared spectra and DFT calculation reveal that the introduction of Ir can modulate the electronic structure and d-band center so as to endow the Ru with the mild binding energy with the key intermediates and small energy barrier for *HOCH₂CH₂OH desorption, thereby enhancing the EG generation. Simultaneously, the high energy barrier for the overoxidation of the *CH₂CH₂OH renders the EG formation thermodynamically favorable, thus realizing the near 100% EG selectivity. This work provides a new understanding for the high-selectivity electrosynthesis of high-value-added oxides.

Key words: Ethylene electrooxidation, Ethylene glycol, High selectivity, IrRu alloy, Electronic structure1. Introduction

王杰, 陈怡和, 王宇达, 赵浩, 叶进裕, 程庆庆, 杨辉. 调控Ru的电子态以促进乙烯在酸中高选择性电氧化合成乙二醇[J]. 催化学报, 2024, 60: 376-385.

Jie Wang, Yihe Chen, Yuda Wang, Hao Zhao, Jinyu Ye, Qingqing Cheng, Hui Yang. Manipulating the electronic state of ruthenium to boost highly selective electrooxidation of ethylene to ethylene glycol in acid[J]. Chinese Journal of Catalysis, 2024, 60: 376-385.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60024-0

https://www.cjcatal.com/CN/Y2024/V60/I5/376

图/表 4

Fig. 1. Synthetic scheme and characterization of Ir-Ru NPs. (a) Schematic illustration of the synthetic process. (b) XRD patterns of Ir0.57Ru0.43, Ir0.54Ru0.46, Ir0.46Ru0.54 and Ru NPs. TEM image (c) and alloy nanoparticle size distribution (d) of Ir0.54Ru0.46 NPs. Aberration STEM image (e), SAED pattern (f) and elemental mapping (g) for Ir0.54Ru0.46 NPs. (h) High-resolution XPS spectra of Ru 3p3/2. Normalized XANES (i) and R-space of the EXAFS spectra (j) of Ir0.57Ru0.43, Ir0.54Ru0.46, Ir0.46Ru0.54, Ir foil, and Ru foil at the Ru K-edge.

Fig. 2. Catalytic performance of IrRu alloy NPs and Ru NPs toward ethylene to EG in 50 mL 0.1 mol L-1 HClO4. CVs (a) and LSVs (b) of Ir0.54Ru0.46 NPs in N2- and ethylene-saturated electrolyte. Yield rates of EG (c), TOF (d) and FEEG (e) at the potentials from 1.400 to 1.475 V. (f) Nyquist plots of different catalysts (The inset is equivalent circuit, where Rs, Rc, Cc, Cdl and Rct represent electrolyte resistance, contact resistance, contact capacitance, Double-layer capacitance and charge transfer resistance, respectively). (g) Selectivity of EG at a potential range from 1.400 to 1.475 V. (h) Durability test for Ir0.54Ru0.46 NPs. (i) EG productivity rate at 1.45 V during the 12 h electrolysis.

Fig. 3. (a) EG yielding and corresponding FEEG in the presence of 100 mmol methanol or 100 mmol p-benzoquinone of Ir0.54Ru0.46 NPs catalysts, respectively. (b) Desorption of OH on Ir0.46Ru0.54 NPs, Ir0.54Ru0.46 NPs, Ir0.57Ru0.43 NPs. CV curves with the scan rate of 50 mV?s?1. (c) VBS of Ir0.57Ru0.43, Ir0.54Ru0.46, Ir0.46Ru0.54, and Ru NPs catalysts measured by XPS. (d) Electrochemical in situ ATR-FTIR spectra of ethylene oxidation on Ir0.54Ru0.46 NPs at different potentials (0.1-1.4 V) in ethylene-saturated 0.1 mol L-1 HClO4 solution. (e) Schematic diagram of electrooxidation of ethylene to EG on IrRu alloy.

Fig. 4. Theoretical calculations for ethylene oxidation. (a) Calculation model for Ru NPs and Ir0.54Ru0.46 NPs. (b) Charge transfer between Ir and Ru atoms in Ir0.54Ru0.46 NPs. (c) P-DOS for Ru NPs and Ir0.54Ru0.46 NPs. (d) Free energy diagram on Ru NPs and Ir0.54Ru0.46 NPs (pathway I: C2H4 → HOCH2CH2OH, pathway II: C2H4 → HOCH2COOH).

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调控Ru的电子态以促进乙烯在酸中高选择性电氧化合成乙二醇

Manipulating the electronic state of ruthenium to boost highly selective electrooxidation of ethylene to ethylene glycol in acid

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