硫电子桥介导CuInS2/CuS异质结构实现高选择性CO2光还原为C2H4

doi:10.1016/S1872-2067(25)64751-6

催化学报 ›› 2025, Vol. 75: 180-191.DOI: 10.1016/S1872-2067(25)64751-6

硫电子桥介导CuInS₂/CuS异质结构实现高选择性CO₂光还原为C₂H₄

陈鸿境^a, 李月英^c, 陈敏^a^,^*(), 解仲凯^b^,^*(), 施伟东^a^,^b^,^*()

^a江苏大学化学化工学院, 江苏镇江 212013
^b江苏科技大学环境与化学工程学院, 江苏镇江 212003
^c江苏大学医学院, 江苏镇江 212003

收稿日期:2025-03-12 接受日期:2025-05-07 出版日期:2025-08-18 发布日期:2025-07-22
通讯作者: *电子信箱: swd1978@ujs.edu.cn (施伟东), chenmin3226@sina.com (陈敏), xzk0702@sina.com (解仲凯).
基金资助:
国家自然科学基金(22225808);国家自然科学基金(22075111);中德合作小组项目(GZ1579);江苏省创新支持计划国际科技合作项目(BZ2022045);江苏大学应急管理学院专项科研项目(KY-A-02)

Sulfur electron bridge mediating CuInS₂/CuS heterostructure for highly selective CO₂ photoreduction to C₂H₄

Chen Hongjing^a, Li Yueying^c, Chen Min^a^,^*(), Xie Zhongkai^b^,^*(), Shi Weidong^a^,^b^,^*()

^aSchool of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China
^bCollege of Environmental and Chemical Engineering, Jiangsu University of Science and Technology, Zhenjiang 212003, Jiangsu, China
^cSchool of Medicine, Jiangsu University, Zhenjiang 212003, Jiangsu, China

Received:2025-03-12 Accepted:2025-05-07 Online:2025-08-18 Published:2025-07-22
Contact: *E-mail: swd1978@ujs.edu.cn (W. Shi), chenmin3226@sina.com (M. Chen), xzk0702@sina.com (Z. Xie).
Supported by:
National Natural Science Foundation of China(22225808);National Natural Science Foundation of China(22075111);Sino-German Cooperation Group Project(GZ1579);Jiangsu Province Innovation Support Program International Science and Technology Cooperation Project(BZ2022045);Special Scientific Research Project of School of Emergency Management, Jiangsu university(KY-A-02)

摘要/Abstract

摘要：

光催化还原CO₂为高附加值的C₂H₄是实现碳中和的一条重要途径. 然而, 由于CO₂的热力学稳定性和动力学惰性, 传统催化方法难以实现高效、高选择性的CO₂转化,尤其是在多电子还原生成C₂H₄的过程中, 面临C-C偶联能垒高、电子供给不足和副反应竞争等问题. 近年来, 光催化技术因反应条件温和、环境友好及可利用太阳能等优势, 为高效CO₂转化提供了新机遇. 构建异质结光催化剂可优化光生载流子分离和界面电荷转移, 为提升CO₂还原性能提供了有效策略. 本研究旨在设计一种基于CuInS₂/CuS的S型异质结光催化剂, 利用硫电子桥的界面调控作用, 实现CO₂向C₂H₄的高选择性转化, 为碳资源高值化利用和绿色化学发展提供新途径.

本文采用一步溶剂热法合成了具有纳米花状形貌的CuInS₂/CuS异质结光催化剂. 该异质结的形成过程始于CuS核的结晶, 随后In³⁺与CuS表面发生界面反应, 实现CuInS₂的外延生长, 界面处的硫原子形成化学键桥连两相, 确保了强界面结合. 扫描电镜、高分辨透射电镜以及能谱元素映射确认了CuInS₂/CuS的成功合成及In、Cu、S元素在异质结中均匀分布, 表明界面紧密结合. X射线衍射验证了两种晶相共存, X射线光电子能谱(XPS)显示In 3d峰向高结合能方向移动, 表明电子从CuInS₂向CuS的转移及强烈的界面电子相互作用, 进一步证实了异质结的成功构建. 紫外-可见漫反射光谱和Mott-Schottky测试表明, CuInS₂/CuS形成了S型能带结构, 其中CuInS₂和CuS的带隙分别为1.67和1.41 eV, 适合可见光驱动的光催化过程. 原位XPS表征进一步证实了CuInS₂/CuS符合S型的电荷转移路径. 在可见光照射下, CuInS₂/CuS表现出优异的CO₂还原性能, C₂H₄的生成速率达到5.62 µmol·g^-1·h^-1, 其电子选择性高达98.22%, 且在15 h的连续反应中保持稳定. ¹³CO₂同位素标记实验证实了C₂H₄产物源自CO₂. 电化学阻抗谱、瞬态光电流响应、稳态荧光光谱和瞬态荧光光谱测试表明, 异质结的构建有效提高了光生载流子的分离效率, 凸显了S型异质结和硫电子桥在促进光生载流子分离和传输方面的关键作用. 原位红外光谱和密度泛函理论计算揭示了CO₂还原为C₂H₄的反应机理: CO₂首先被还原为COOH, 随后转化为CO中间体, 再经过*COCO和*COCOH等关键中间体, 最终生成C₂H₄. 计算结果表明, CuInS₂/CuS显著降低了C-C偶联关键步骤(CO到COCO)的能垒. 硫电子桥的存在不仅物理连接了CuInS₂和CuS, 更调控了电子相互作用, 创造了有利于CO₂向C₂H₄转化的局部电子环境, 这种独特的界面工程策略为设计高效的光催化剂提供了新思路.

综上, 本研究通过一步溶剂热法合成了CuInS₂/CuS S型异质结光催化剂, 通过构建高效电荷转移通道和双金属活性位点, 协同优化载流子动力学与反应热力学, 实现了CO₂高选择性光催化还原为C₂H₄, 为设计高选择性CO₂-C₂H₄的催化剂提供了创新策略.

关键词: 光催化二氧化碳还原, 乙烯产物, 硫电子桥, 高效载流子分离, 高选择性

Abstract:

Photocatalytic reduction of CO₂ into high-value C₂H₄ offers a promising pathway toward carbon neutrality. Due to the continuous 12-electron-proton coupled reactions and the mutual repulsion of reaction intermediates, achieving highly selective photocatalytic conversion of CO₂ to C₂H₄ remains challenging. This work synthesized a CuInS₂/CuS heterojunction photocatalyst mediated by a sulfur electron bridge via a one-step solvothermal method, achieving a high selectivity for C₂H₄ conversion (98.22%). The sulfur electron bridge minimized the contact energy barrier between CuInS₂ and CuS to enhance photogenerated carrier separation efficiency, while the asymmetric active sites in CuInS₂ effectively reduced mutual repulsion of reaction intermediates. This work develops a hybrid catalytic system enabling synergistic regulation of reaction kinetics and thermodynamics, offering an innovative strategy for highly selective photocatalytic CO₂-to-C₂H₄ production.

Key words: Photocatalytic CO₂ reduction, C₂H₄ production, Sulfur electron bridge, Efficient charge separation, High selectivity

陈鸿境, 李月英, 陈敏, 解仲凯, 施伟东. 硫电子桥介导CuInS₂/CuS异质结构实现高选择性CO₂光还原为C₂H₄[J]. 催化学报, 2025, 75: 180-191.

Chen Hongjing, Li Yueying, Chen Min, Xie Zhongkai, Shi Weidong. Sulfur electron bridge mediating CuInS₂/CuS heterostructure for highly selective CO₂ photoreduction to C₂H₄[J]. Chinese Journal of Catalysis, 2025, 75: 180-191.

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图/表 6

Fig. 1. (a) Schematic illustration of CuInS2/CuS heterojunction synthesis. (b) The SEM image of CuInS2/CuS. (c) The HRTEM images of CuInS2/CuS. (d) Magnified area in (c). (e) HAADF image and the corresponded EDS elemental mappings of CuInS2/CuS.

Fig. 2. (a) XRD spectrums of CuInS2/CuS, CuS and CuInS2. In 3d (b), S 2p (c), and Cu 2p (d) XPS spectra of the as-prepared sample.

Fig. 3. (a) The photocatalytic CO2 reduction performance of CuInS2/CuS samples under visible light. (b) Comparison for the electron selectivity of C2H4 with previously reported photocatalysts. (c) Yield of CuInS2/CuS reaction within 15 h. (d) GC-MS analysis for photocatalytic 13CO2 reduction over CuInS2/CuS.

Fig. 4. (a) UV-vis DRS spectra. Obtained bandgaps of CuS (b) and CuInS2 (c) estimated by plotting (αhν)2 (Tauc plot). Mott-Schottky plots of CuS (d) and CuInS2 (e). (f) Band structure of CuInS2/CuS composites.

Fig. 5. The EIS (a), TPR (b), TRPL (c), PL (d) tests of as-prepared sample.

Fig. 6. (a) In situ FT-IR spectroscopy of CuInS2/CuS. (b) The charge density difference of *COCO adsorbed on the CuInS2/CuS surface. (c) Gibbs free energy diagrams of CO2 reduction pathways towards C2H4.

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硫电子桥介导CuInS₂/CuS异质结构实现高选择性CO₂光还原为C₂H₄

Sulfur electron bridge mediating CuInS₂/CuS heterostructure for highly selective CO₂ photoreduction to C₂H₄

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