B原子掺杂调控CuIn纳米合金电子结构以实现电化学CO2还原宽电位活性

doi:10.1016/S1872-2067(23)64443-2

催化学报 ›› 2023, Vol. 49: 132-140.DOI: 10.1016/S1872-2067(23)64443-2

B原子掺杂调控CuIn纳米合金电子结构以实现电化学CO₂还原宽电位活性

王娇, 朱芳芳, 陈必义, 邓爽, 胡博琛, 刘洪, 武猛, 郝金辉(), 李龙华, 施伟东()

江苏大学化学与化工学院, 江苏镇江 212013

收稿日期:2023-03-15 接受日期:2023-04-27 出版日期:2023-06-18 发布日期:2023-06-05
通讯作者: ^*电子信箱: jinhu1_hao@ujs.edu.cn (郝金辉),swd1978@ujs.edu.cn (施伟东).
基金资助:
国家自然科学基金(22225808);中德合作组项目(GZ1579);江苏省国际创新扶持计划科技合作项目(BZ2022045)

B atom dopant-manipulate electronic structure of CuIn nanoalloy delivering wide potential activity over electrochemical CO₂RR

Jiao Wang, Fangfang Zhu, Biyi Chen, Shuang Deng, Bochen Hu, Hong Liu, Meng Wu, Jinhui Hao(), Longhua Li, Weidong Shi()

School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China

Received:2023-03-15 Accepted:2023-04-27 Online:2023-06-18 Published:2023-06-05
Contact: ^*E-mail: jinhu1_hao@ujs.edu.cn (J. Hao), swd1978@ujs.edu.cn (W. Shi).
Supported by:
National Natural Science Foundation of China(22225808);Sino-German Cooperation Group Project(GZ1579);Jiangsu Province Innovation Support Program International Science as well as Technology Cooperation Project(BZ2022045)

摘要/Abstract

摘要：

杂原子掺杂可以调节电子结构以调整中间体吸附并优化反应路径, 是设计高效CO₂还原反应(CO₂RR)催化剂的有应用前景的方法. B原子是常用的掺杂剂, 引入B原子可以有效打破*COOH和OCHO*中间体的吉布斯自由能线性关系, 并且可以通过与CO₂中O原子结合来增强CO₂吸附能力. B掺杂碳材料、单金属和金属氧化物的研究结果表明, B原子掺杂催化剂的CO₂RR活性和/或选择性有明显提高, 然而多数报道的单个活性位点的B掺杂催化剂仅表现出在相对狭窄的电位范围内的CO₂RR高性能, 设计制备CO₂RR的宽电位高选择性催化剂仍是巨大挑战. 研究表明, 合金化是提供多种类的活性位点相互协调和增强催化剂固有活性, 进而改善CO₂RR性能并调节产物分布的可行策略. 引入B原子到合金中以调节电子结构, 最终优化关键中间体吸附的活性位点, 对于寻找具有宽电位窗口的先进催化剂具有重要意义.

本文提出了一种通过B掺杂调节CuIn合金电子结构以实现宽电位高选择性的电子工程策略. 所制得的B掺杂CuIn合金(CuIn(B))在-0.6 V(vs. RHE)时表现出99%的CO法拉第效率(FE_CO), 并在一个宽的阴极电化学窗口(400 mV)内保持了超过90%的较高FE_CO. 同时, 采用X射线光电子能谱(XPS)和CO₂吸附实验等手段研究了CuIn(B)性能提升的原因, 结果表明, B原子与CuIn之间存在强烈的相互作用, 改变了CuIn的电子结构. CO₂吸附结果表明, CuIn(B)比CuIn拥有更强的CO₂吸附能力, 证明它具有潜在的快速CO₂RR反应动力学. 进一步通过密度泛函理论(DFT)模拟研究了催化剂的热力学反应能量学以揭示CO₂RR机制, 结果表明, *COOH更倾向于在CuIn(B)上形成, 且*CO与CuIn(B)催化位点的结合强度最佳, 更利于CO₂还原反应为CO, 而CuIn更利于作为HER的活性位点; 决速步骤是*CO中间体向CO转移,以实现高CO选择性; 热力学限制电位研究表明, CuIn(B)大大提高了CO₂到CO转化的选择性. 随后通过差分电荷密度研究也进一步证明了电荷转移过程是从CuIn位点到B位点. 此外, 根据d带理论, 催化剂中Cu和In原子的投影态密度和d带中心(E_d)研究进一步证明了催化剂结构中的电子价态的变化, 与XPS结果相符; 引入B可以优化催化剂的电子结构, 从而调节催化剂和中间体之间的结合能力, 实现了CO₂RR在宽电位范围内的高活性和选择性. 综上, 本文对于电化学CO₂RR机理的基础理解和其实际应用具有促进作用.

关键词: CO₂还原, 宽电位窗口, 高选择性, B原子掺杂, 电子结构

Abstract:

The accuracy and efficiency tuning the local electronic structure of catalyst active sites are pre-requisites for achieving high selectivity CO₂ reduction reaction on a wide potential window, whereas remain a great challenge. Here, a B-doped CuIn alloy catalyst with tunable electronic structure for the highly effective electrochemical conversion of CO₂ to CO has been exploited. The obtained B-doped CuIn alloy performs an optimal CO Faraday efficiency of 99% at -0.6 V (vs. the reversible hydrogen electrode) and particularly keeps outstanding CO Faraday efficiency (> 90%) over a wide cathodic electrochemical window (400 mV). Density functional theory theoretical calculation manifests that the enhanced performance is primarily ascribed to the electron-capturing ability of high valence state B atom, which optimizes the local electronic structure of adjacent metal active sites and adjusts the binding energy between catalyst and intermediates. A foundation of designing advanced electrochemical CO₂ reduction reaction catalysts can be served by the insights gained though this research.

Key words: CO₂ reduction, Wide potential window, High selectivity, B doping, Electronic structure

王娇, 朱芳芳, 陈必义, 邓爽, 胡博琛, 刘洪, 武猛, 郝金辉, 李龙华, 施伟东. B原子掺杂调控CuIn纳米合金电子结构以实现电化学CO₂还原宽电位活性[J]. 催化学报, 2023, 49: 132-140.

Jiao Wang, Fangfang Zhu, Biyi Chen, Shuang Deng, Bochen Hu, Hong Liu, Meng Wu, Jinhui Hao, Longhua Li, Weidong Shi. B atom dopant-manipulate electronic structure of CuIn nanoalloy delivering wide potential activity over electrochemical CO₂RR[J]. Chinese Journal of Catalysis, 2023, 49: 132-140.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64443-2

https://www.cjcatal.com/CN/Y2023/V49/I6/132

图/表 5

Fig. 1. (a) Schematic synthesis process of CuIn(B), Cu(B), In(B) and CuIn catalysts. Morphology and structure characterizations of CuIn(B). (b) FESEM and the average size distribution; TEM (c), HRTEM (d), HAADF-STEM (e) and EDS diagrams of elements (f?i).

Fig. 2. (a) XRD of CuIn(B) and CuIn; (b) XPS spectra of B 1s; (c) Auger Cu LMM; (d) Cu 2p; (e) In 3d.

Fig. 3. Electrocatalytic CO2RR performances of CuIn(B). (a) LSV curves tested in 0.5 mol/L KHCO3 solution with saturated Ar or CO2. (b) FE of gas products of CuIn(B). (c) FECO obtained within the scope of -0.5 V to -1.2 V (vs. RHE). (d) jCO obtained at different applied potential. (e) EECO of diverse catalysts. (f) Long-term durability test of CuIn(B) at -0.8 V (vs. RHE). The standard deviation of three separate measurements of the same sample is represented by the error estimates.

Fig. 4. (a) Differences in current density (Δj/2) displayed against scan rates. (b) The surface roughness factor. (c) Nyquist curves. (d) Tafel curves.

Fig. 5. Theoretical calculations on CuIn(B) and CuIn. (a) Calculated free energy diagrams on the CuIn(B) and CuIn. (b) The distinction in thermodynamic limiting potentials for CO2-to-CO conversion and HER on catalysts. (c) The top and side view of charge density difference in CuIn(B), where charge consumption and accumulation were described by cyan and yellow, respectively. (d) PDOS curves of Cu 3d, In 3d, the Cu site adsorbed with *COOH intermediate on the CuIn(B) and CuIn. The dashed orange line manifests the Fermi level (Ef). Dotted grey lines represent the d-band centers (Ed).

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B原子掺杂调控CuIn纳米合金电子结构以实现电化学CO₂还原宽电位活性

B atom dopant-manipulate electronic structure of CuIn nanoalloy delivering wide potential activity over electrochemical CO₂RR

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