调节In@InOx核壳纳米颗粒中的表面In‒O提升电催化还原CO2为甲酸盐性能

doi:10.1016/S1872-2067(21)63943-8

催化学报 ›› 2022, Vol. 43 ›› Issue (7): 1674-1679.DOI: 10.1016/S1872-2067(21)63943-8

• 二氧化碳催化转化专栏 • 上一篇下一篇

调节In@InO_x核壳纳米颗粒中的表面In‒O提升电催化还原CO₂为甲酸盐性能

杨艳^a^,^c, 傅佳驹^a, 唐堂^a^,^c, 牛帅^a^,^c, 张礼兵^a^,^c, 张佳楠^b, 胡劲松^a^,^c^,^*()

^a中国科学院化学研究所, 中国科学院分子纳米结构与纳米技术重点实验室, 北京分子科学国家实验室, 北京100190
^b郑州大学材料科学与工程学院, 河南郑州450001
^c中国科学院大学, 北京100049

收稿日期:2021-07-20 接受日期:2021-09-03 出版日期:2022-07-18 发布日期:2022-05-20
通讯作者: 胡劲松
基金资助:
国家重点研发计划(2020YFB1505801);国家自然科学基金(22025208);国家自然科学基金(22075300);国家自然科学基金(22102191);中国博士后创新人才计划(BX2021319)

Regulating surface In-O in In@InO_x core-shell nanoparticles for boosting electrocatalytic CO₂ reduction to formate

Yan Yang^a^,^c, Jia-ju Fu^a, Tang Tang^a^,^c, Shuai Niu^a^,^c, Li-Bing Zhang^a^,^c, Jia-nan Zhang^b, Jin-Song Hu^a^,^c^,^*()

^aBeijing National Laboratory for Molecular Sciences (BNLMS), CAS Key Laboratory of Molecular Nanostructure and Nanotechnology, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
^bCollege of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450001, Henan, China
^cUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2021-07-20 Accepted:2021-09-03 Online:2022-07-18 Published:2022-05-20
Contact: Jin-Song Hu
Supported by:
National Key Research and Development Program of China(2020YFB1505801);National Natural Science Foundation of China(22025208);National Natural Science Foundation of China(22075300);National Natural Science Foundation of China(22102191);China National Postdoctoral Program for Innovative Talents(BX2021319)

摘要/Abstract

摘要：

通过可再生能源驱动的电催化二氧化碳还原反应可以将温室气体转化为燃料或有价值的化学品, 从而缓解因化石燃料过度消耗而导致的能源短缺和温室效应. 在电化学CO₂还原(CO₂RR)反应获得的产物中, 甲酸盐因出色的载氢能力和可在化学工业中用作有机合成原料而被认为是一种具有经济价值和吸引力的产物. 然而, CO₂RR的高动力学势垒和严重的析氢反应限制了其有效生成, 这使构建高效的催化生成甲酸盐的催化剂成为一个巨大挑战. 近期, 研究者设计了基于过渡金属(如In, Bi和Sn)的催化剂, 其对甲酸盐具有较高的选择性. 通过金属氧化物(M-O)结构形成的氧化态p-block金属中心可以加快*OCO^•-的生成, 这通常被认为是生成甲酸盐的关键中间体. 此外, 很多研究已经报道了M-O结构在催化过程中的重要作用, 表面M-O结构可以稳定CO₂中间体并促进反应动力学. 当通过刻蚀或其他特殊预处理破坏M-O结构时, 甲酸盐的形成受到极大阻碍. In具有低毒、高耐腐蚀性和导电性的特点, 在开发用于CO₂RR生成甲酸的催化剂方面具有巨大潜力. Bocarsly课题组曾经报道, In电极上的甲酸盐选择性很大程度上取决于不同的预处理方法. 去除氧化层后的蚀刻电极表现出较低的甲酸盐选择性, 而含有氧化层的阳极氧化电极显著提高了甲酸盐的选择性. 尽管很多研究报道了In-O物种在催化过程中的重要作用, 但关于如何在In基催化剂表面上富集In-O物种的研究很少.

本文采用简便的空气煅烧法调节CNT负载的In₂O₃纳米粒子(NPs)上的In-O含量, 以形成AC-In₂O₃-CNT结构. 在经过原位电化学重构过程后, 形成了表面富集In-O的核壳结构AC-In@InO_x-CNT催化剂, 所得的未经煅烧In@InO_x-CNT与经过煅烧AC-In@InO_x-CNT具有相似的核壳结构. 高分辨透射电子显微镜和X射线能谱(EDS)分析结果表明, In为核, 非晶InO_x为壳. X射线光电子能谱和EDS结果表明, 与未经煅烧的In@InO_x-CNT相比, AC-In@InO_x-CNT中In-O含量更丰富. 与In@InO_x-CNT催化剂相比, 富含In-O的AC-In@InO_x-CNT催化剂表现出显著提高的CO₂RR活性, 其催化生成对甲酸盐的最高法拉第效率(FE)可达到94 ± 1%, 在-1.00 V(相比于RHE)时, 甲酸盐的部分电流密度可达到32.6 mA cm^-2, 而竞争性的析氢反应几乎可以忽略不计(FE小于2%). 经过25 h的稳定性实验, 未观察到反应性能下降及催化剂形貌变化, 表明AC-In@InO_x-CNT催化剂具有较好的稳定性. 综上, 本文通过构建丰富且稳定的表面M-O结构, 为设计高效电催化剂提供新思路.

关键词: In-O含量, 核壳纳米粒子, CO₂还原, 甲酸盐, 电催化

Abstract:

To solve the excessive emission of CO₂ caused by the excessive use of fossil fuels and the corresponding environmental problems, such as the greenhouse effect and climate warming, electrocatalytic CO₂ reduction to liquid fuel with high selectivity is of huge significance for energy conversion and storge. Indium has been considered as a promising and attractive metal for the reduction of CO₂ to formate. However, the current issues, such as low selectivity and current activity, largely limit the industrial application for electrocatalytic CO₂ reduction, the design optimization of the catalyst structure and composition is extremely important. Herein, we develop a facile strategy to regulate surface In-O of In@InO_x core-shell nanoparticles and explore the structure-performance relationship for efficient CO₂-to-formate conversion though air calcination and subsequent in situ electrochemical reconstruction, discovering that the surface In-O is beneficial to stabilize the CO₂ intermediate and generate formate. The optimized AC-In@InO_x-CNT catalyst exhibits a C₁ selectivity up to 98% and a formate selectivity of 94% as well as a high partial formate current density of 32.6 mA cm^-2. Furthermore, the catalyst presents an excellent stability for over 25 h with a limited activity decay, outperforming the previously reported In-based catalysts. These insights may open up opportunities for exploiting new efficient catalysts by manipulating their surface.

Key words: In-O content, Core-shell nanoparticles, CO₂ reduction, Formate, Electrocatalysis

杨艳, 傅佳驹, 唐堂, 牛帅, 张礼兵, 张佳楠, 胡劲松. 调节In@InO_x核壳纳米颗粒中的表面In‒O提升电催化还原CO₂为甲酸盐性能[J]. 催化学报, 2022, 43(7): 1674-1679.

Yan Yang, Jia-ju Fu, Tang Tang, Shuai Niu, Li-Bing Zhang, Jia-nan Zhang, Jin-Song Hu. Regulating surface In-O in In@InO_x core-shell nanoparticles for boosting electrocatalytic CO₂ reduction to formate[J]. Chinese Journal of Catalysis, 2022, 43(7): 1674-1679.

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https://www.cjcatal.com/CN/Y2022/V43/I7/1674

图/表 5

Scheme 1. Schematic diagram of the synthetic route to core-shell structured In@InOx-CNT catalysts supported on CNTs.

Fig. 1. (a) SEM image. (b) HRTEM image and corresponding FFT pattern (inset) of AC-In2O3-CNT before reconstruction. (c) XRD patterns of In2O3-CNT and AC-In2O3-CNT before reconstruction. TEM image, HRTEM image, ADF-STEM image, and corresponding EDS mapping images for AC-In@InOx-CNT (d-f) and In@InOx-CNT (g-i) after reconstruction, respectively. I and II show the FFT patterns of a certain core and shell region in panel (e) and (h), respectively.

Fig. 2. XRD pattern (a) and In 3d XPS spectra (b) of In@InOx-CNT and AC-In@InOx-CNT after reconstruction; O 1s XPS spectra of In2O3-CNT (c) and AC-In2O3-CNT (d) before reconstruction. O 1s XPS spectra of In@InOx-CNT (e) and AC-In@InOx-CNT (f) after reconstruction.

Fig. 3. (a) LSV curves performed in Ar-saturated and CO2-saturated 0.5 mol/L KHCO3 solution on In@InOx-CNT and AC-In@InOx-CNT; Potential-dependent FEs for formate, CO and H2 and partial formate current density on AC-In@InOx-CNT (b) and In@InOx-CNT (c) catalysts. (d) Comparison of formate selectivity between this work and other previously reported In-based catalysts.

Fig. 4. (a) Long-term stability of AC-In@InOx-CNT for CO2RR operated at -1.00 V. The inset is corresponding formate FEs at -1.00 V for 25 h. (b) The comparison of XRD pattern of AC-In@InOx-CNT catalyst before and after long-term stability. (c) HRTEM image and corresponding FFT images in marked regions for AC-In@InOx-CNT catalyst after long-term stability.

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调节In@InO_x核壳纳米颗粒中的表面In‒O提升电催化还原CO₂为甲酸盐性能

Regulating surface In-O in In@InO_x core-shell nanoparticles for boosting electrocatalytic CO₂ reduction to formate

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