硫锚定策略提升亚3纳米In2S3纳米颗粒电还原CO2至甲酸盐的稳定性

doi:10.1016/S1872-2067(24)60233-0

催化学报 ›› 2025, Vol. 71: 138-145.DOI: 10.1016/S1872-2067(24)60233-0

硫锚定策略提升亚3纳米In₂S₃纳米颗粒电还原CO₂至甲酸盐的稳定性

陈繁荣^a^,^b^,^c, 傅佳驹^b^,^*(), 丁亮^b^,^d, 卢晓英^b, 蒋哲^b^,^d, 张小玲^a^,^*(), 胡劲松^b^,^d^,^*()

^a北京理工大学化学与化工学院, 北京 100081
^b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, 北京分子科学国家研究中心, 北京 100190
^c延安大学化学与化工学院, 陕西省化学反应工程重点实验室, 陕西延安 716000
^d中国科学院大学, 北京 100049

收稿日期:2024-11-13 接受日期:2024-12-17 出版日期:2025-04-18 发布日期:2025-04-13
通讯作者: * 电子信箱: hujs@iccas.ac.cn (胡劲松), zhangxl@bit.edu.cn (张小玲), fujiaju@iccas.ac.cn (傅佳驹).
基金资助:
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);陕西省教育厅重点实验室(20JS157)

Promoting stability of sub-3 nm In₂S₃ nanoparticles via sulfur anchoring for CO₂ electroreduction to formate

Fanrong Chen^a^,^b^,^c, Jiaju Fu^b^,^*(), Liang Ding^b^,^d, Xiaoying Lu^b, Zhe Jiang^b^,^d, Xiaoling Zhang^a^,^*(), Jin-Song Hu^b^,^d^,^*()

^aSchool of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
^bBeijing National Laboratory for Molecular Sciences (BNLMS), Institute of Chemistry, Chinese Academy of Sciences (CAS), Beijing 100190, China
^cShaanxi Key Laboratory of Chemical Reaction Engineering, College of Chemistry & Chemical Engineering, Yan’an University, Yan’an 716000, Shaanxi, China
^dUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-11-13 Accepted:2024-12-17 Online:2025-04-18 Published:2025-04-13
Contact: * E-mail: hujs@iccas.ac.cn (J.-S. Hu), zhangxl@bit.edu.cn (X. Zhang), fujiaju@iccas.ac.cn (J. Fu).
Supported by:
National Natural Science Foundation of China(22025208);National Natural Science Foundation of China(22075300);National Natural Science Foundation of China(22102191);Key Laboratory of Education Department of Shaanxi Province(20JS157)

摘要/Abstract

摘要：

利用可再生电能将CO₂转化为高附加值化学品和燃料是解决能源与环境问题的关键途径之一. p区金属(如In, Sn, Bi, Pb)硫属化物催化剂在电化学CO₂还原(ECR)为甲酸盐中展现出优异活性, 其带正电的活性位点有效抑制析氢反应, 并促进*OCO型吸附, 有利于甲酸盐生成. 然而, 在ECR条件下催化剂的重构和团聚会导致催化活性迅速下降, 严重限制其实际应用. 因此, 开发有效的催化剂稳定策略以提升活性位点的稳定性, 成为CO₂电还原领域一个重要且具有挑战性的研究方向.
催化剂-载体强相互作用的构建被认为是提升电催化剂活性与稳定性的有效方法, 具体可通过强化催化剂与载体之间的电荷传递及电子转移, 进而调控催化活性位点的电子状态, 有利于提高反应物与中间体的吸附和传递, 从而提升催化剂的电催化性能. 强金属硫化物-载体相互作用(MSSI)可以有效抑制纳米颗粒的迁移、团聚和重构. 本文提出一种硫锚定策略, 通过在硫掺杂多孔碳(S-C)基底上原位合成亚3纳米In₂S₃纳米颗粒(i-In₂S₃/S-C), 构建具有强MSSI的催化剂, 促进CO₂电还原至甲酸盐. 该催化剂中In₂S₃纳米颗粒的负载量达到37.9 wt%, 粒径为2.5±0.7 nm. 通过变温X射线衍射、热重、差热、X射线光电子能谱和紫外光电子能谱等系统分析, 证明了硫锚定策略可有效增强In₂S₃与S-C之间的相互作用, 与负载在碳基底上的In₂S₃(i-In₂S₃/C)以及负载在硫掺杂碳上的In₂S₃(l-In₂S₃/S-C)相比, i-In₂S₃/S-C催化剂表现出更强的MSSI, 有效调控了In₂S₃纳米颗粒的电子结构, 并抑制In₂S₃催化剂的团聚和迁移. 此外, i-In₂S₃/S-C催化剂在CO₂到甲酸盐的电催化反应中表现出优异的催化活性, 在-0.95 V (vs. RHE)的条件下, 该催化剂的甲酸盐法拉第效率(FE_formate)高达91%, 甲酸盐的部分电流密度(j_formate)为21 mA cm^-2. 更突出的是, 在相同电位下, 该催化剂在75 h的连续测试后仍保持原有的形貌和结构, 未发生明显的颗粒团聚和重构. 上述研究表明, 通过硫锚定策略构建的强MSSI可显著提高i-In₂S₃/S-C催化剂的电还原CO₂稳定性.
综上所述, 本文通过硫锚定策略合成了具有强MSSI的亚3 nm In₂S₃纳米颗粒催化剂(i-In₂S₃/S-C), 有效调控了In₂S₃的电子结构, 防止催化剂团聚和迁移, 显著提升了电还原CO₂的稳定性. 为开发高效且稳定的CO₂电还原催化剂提供了新的设计思路.

关键词: CO₂电还原, 强金属硫化物-载体相互作用, In₂S₃纳米颗粒, 稳定性, 甲酸盐

Abstract:

The p-block metal (In, Sn, Bi, etc.)-based electrocatalysts have exhibited excellent activity in the electrocatalytic CO₂ reduction (ECR) to formate. However, the rapid decrease in catalytic activity caused by catalyst reconstruction and agglomeration under ECR conditions significantly restricts their practical applications. Herein, we developed a sulfur anchoring strategy to stabilize the high-density sub-3 nm In₂S₃ nanoparticles on sulfur-doped porous carbon substrates (i-In₂S₃/S-C) for formate production. Systematic characterizations evidenced that the as-prepared catalyst exhibited a strong metal sulfide-support interaction (MSSI), which effectively regulated the electronic states of In₂S₃, achieving a high formate Faradaic efficiency of 91% at −0.95 V vs. RHE. More importantly, the sulfur anchoring effectively immobilized the sub-3 nm In₂S₃ nanoparticles to prevent them from agglomeration. It enabled the catalysts to exhibit much higher durability than the In₂S₃ samples without sulfur anchoring, demonstrating that the strong MSSI and fast charge transfer on the catalytic interface could significantly promote the structural stability of In₂S₃ catalysts. These results provide a viable approach for developing efficient and stable electrocatalysts for CO₂ reduction.

Key words: Electrochemical CO₂ reduction, Strong metal sulfide-support, interaction, In₂S₃ nanoparticles, Stability, Formate

陈繁荣, 傅佳驹, 丁亮, 卢晓英, 蒋哲, 张小玲, 胡劲松. 硫锚定策略提升亚3纳米In₂S₃纳米颗粒电还原CO₂至甲酸盐的稳定性[J]. 催化学报, 2025, 71: 138-145.

Fanrong Chen, Jiaju Fu, Liang Ding, Xiaoying Lu, Zhe Jiang, Xiaoling Zhang, Jin-Song Hu. Promoting stability of sub-3 nm In₂S₃ nanoparticles via sulfur anchoring for CO₂ electroreduction to formate[J]. Chinese Journal of Catalysis, 2025, 71: 138-145.

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图/表 5

Fig. 1. (a) Schematic synthesis process of the i-In2S3/S-C catalyst. (b) TEM image of S-C support. TEM image (c), corresponding size distribution (d), and the HRTEM image (e) of the i-In2S3/S-C catalyst. (f) XRD patterns of i-In2S3/S-C, l-In2S3/S-C, and i-In2S3/C catalysts. (g) EDS elemental mapping of i-In2S3/S-C.

Fig. 2. The In and S atomic contents (a) and high-resolution XPS spectra of In 3d (b) and S 2p (c) in i-In2S3/S-C, l-In2S3/S-C, and i-In2S3/C catalysts. The in-situ temperature-programmed XRD patterns of i-In2S3/S-C (d) and the corresponding temperature-dependent Normalized FWHM with derivatives for In2S3 (311) diffraction peak (e) and the UPS spectra (f) of i-In2S3/S-C, l-In2S3/S-C, i-In2S3/C.

Fig. 3. (a) LSV curves of i-In2S3/S-C, l-In2S3/S-C, i-In2S3/C, and S-C at a scan rate of 10 mV s?1. (b) The potential-dependent product distributions of i-In2S3/S-C catalyst. The potential-dependent FEformate (c), jformate (d), formate formation rates (e), and the Tafel plots (f) of the i-In2S3/S-C l-In2S3/S-C and i-In2S3/C.

Fig. 4. Stability test at ? 0.95 V vs. RHE of i-In2S3/S-C, l-In2S3/S-C and i-In2S3/C.

Fig. 5. (a) XRD patterns of i-In2S3/S-C, l-In2S3/S-C and i-In2S3/C after long time ECR test at ? 0.95 V vs. RHE. (b) EDS mapping image of i- In2S3/S-C after 75 h ECR test at ? 0.95 V vs. RHE. S 2p (c) and In 3d (d) XPS spectra of i-In2S3/S-C before and after long time ECR test at ?0.95 V vs. RHE.

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硫锚定策略提升亚3纳米In₂S₃纳米颗粒电还原CO₂至甲酸盐的稳定性

Promoting stability of sub-3 nm In₂S₃ nanoparticles via sulfur anchoring for CO₂ electroreduction to formate

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