通过可控硫空位工程调控CdS中的载流子动力学: 飞秒瞬态吸收光谱的见解

doi:10.1016/S1872-2067(26)65278-3

催化学报 ›› 2027, Vol. 92: 274-284.DOI: 10.1016/S1872-2067(26)65278-3

通过可控硫空位工程调控CdS中的载流子动力学: 飞秒瞬态吸收光谱的见解

孟政^a, 艾陈斌^a, 张建军^a, 何博文^a, 张留洋^a,*, 吴珍^b,*, Serguei Filatov ^c, Dmitry Selishchev ^d,*, Jahan B. Ghasemi ^e,*, 余家国^a,*

^a中国地质大学(武汉)材料与化学学院太阳燃料实验室, 湖北武汉 430078, 中国;
^b鄂尔多斯应用技术学院化学工程学院, 内蒙古鄂尔多斯 017000, 中国;
^c白俄罗斯国家科学院热质传递研究所, 明斯克, 白俄罗斯;
^d俄罗斯科学院西伯利亚分院博列斯科夫催化研究所非常规催化过程系, 新西伯利亚, 俄罗斯;
^e伊朗德黑兰大学理学院化学系, 德黑兰, 伊朗

收稿日期:2026-05-09 接受日期:2026-06-25 出版日期:2027-01-18 发布日期:2026-10-30
通讯作者: *zhangliuyang@cug.edu.cn (张留洋), wuzhen@oit.edu.cn (吴珍), selishev@catalysis.ru (D. Selishchev),jahan.ghasemi@ut.ac.ir (J. B. Ghasemi), yujiaguo93@cug.edu.cn (余家国).
基金资助:
国家自然科学基金(52322214, 22278383, 22409181, 22469001, 22361132529); 湖北省自然科学基金(2023AFA088).

Regulating carrier dynamics in CdS via controlled sulfur vacancy engineering: Insights from femtosecond transient absorption spectroscopy

Zheng Meng^a, Chenbin Ai^a, Jianjun Zhang^a, Bowen He^a, Liuyang Zhang^a,*, Zhen Wu^b,*, Serguei Filatov^c, Dmitry Selishchev^d,*, Jahan B. Ghasemi^e,*, Jiaguo Yu^a,*

^aLaboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430078, Hubei, China;
^bDepartment of Chemical Engineering, Ordos Institute of Technology, Ordos 017000, Inner Mongolia, China;
^cHeat and Mass Transfer Institute, National Academy of Sciences of Belarus, P. Brovka, 15, ITMO, Minsk 220072, Belarus;
^dDepartment of Unconventional Catalytic Processes, Boreskov Institute of Catalysis SB RAS, Lavrentieva Ave. 5, Novosibirsk 630090, Russia;
^eFaculty of Chemistry, School of Sciences, University of Tehran, Tehran 1417614335, Iran

Received:2026-05-09 Accepted:2026-06-25 Online:2027-01-18 Published:2026-10-30
Contact: *E-mail: zhangliuyang@cug.edu.cn (L. Zhang), wuzhen@oit.edu.cn (Z. Wu), selishev@catalysis.ru (D. Selishchev), jahan.ghasemi@ut.ac.ir (J. B. Ghasemi), yujiaguo93@cug.edu.cn (J. Yu).
Supported by:
National Natural Science Foundation of China (52322214, 22278383, 22409181, 22469001, 22361132529) and the National Science Foundation of Hubei Province (2023AFA088).

摘要/Abstract

摘要： 光生电子与空穴的严重复合是限制CdS光催化效率的主要瓶颈. 在CdS中引入硫空位(S_v)可调控局域电子结构并影响载流子行为, 但S_v浓度与光生电子捕获、复合及表面反应动力学之间的定量关系尚不明确, 尤其是从超快时间尺度到稳态表面电荷分布的系统研究仍很匮乏. 本文旨在通过精确调控S_v浓度, 揭示其在不同环境(惰性介质与水溶液)中对CdS载流子动力学的双重作用机制, 为缺陷工程优化提供动力学依据.
采用不同温度(300, 500, 700 °C)热处理并结合NaOH刻蚀去除SiO₂模板, 构筑了一系列具有梯度S_v浓度的CdS空心球光催化剂(标记为CdS-300, CdS-500和CdS-700), 并以未煅烧样品(CdS-0)作为对照. 电子顺磁共振(EPR)和X射线光电子能谱等表征证实了S_v的形成, 并表明S_v浓度随热处理温度升高呈先增后减的火山型变化趋势. 紫外-可见(UV-vis)漫反射光谱显示, S_v的引入增强了样品的光吸收能力, 导致了吸收边的红移. 稳态光致发光光谱结果表明, 引入S_v后整体发光强度降低, 证实S_v可作为有效的电子捕获位点, 从而抑制光生载流子的复合. 进一步结合飞秒瞬态吸收光谱和开尔文探针力显微镜等手段, 系统研究了S_v浓度对光生电子捕获、复合及表面电荷分布的影响. 结果表明, 适量S_v (CdS‑300样品)引入浅电子陷阱态, 在乙腈中将光生电子平均寿命延长至1112.0 ps, 同时表面光电压降至77 mV, 表明电子在表面活性位点高效积累; 过量S_v则转变为复合中心, 从而加速载流子衰减. 在水溶液中, CdS‑300的电子寿命为1062.9 ps, 低于CdS‑0的寿命(1077.8 ps), 证实S_v不仅捕获电子, 还作为活性位点直接参与界面还原反应. 除此之外, 加入电子牺牲剂(K₂Cr₂O₇)后CdS-0寿命急剧降低, 而空穴牺牲剂(乳酸)的加入未明显改变其寿命, 这进一步证实了CdS中fs-TA光谱信号是由电子主导.
综上, S_v具有浓度依赖的双重作用: 低浓度时促进电荷分离, 高浓度时演变为复合中心; S_v不仅捕获电子, 还作为活性位点参与界面还原反应. 该工作建立了CdS中结构缺陷与载流子动力学的关联, 为理性设计高效硫化物光催化剂提供了理论指导.

关键词: CdS, 硫空位, 飞秒瞬态吸收光谱, 载流子动力学, 表面光电压

Abstract: Severe electron-hole recombination remains a fundamental bottleneck limiting the efficiency of semiconductor photocatalysts. Engineering defect states, particularly sulfur vacancies (S_v), offers an effective strategy to tailor local electronic structures and regulate charge carrier dynamics. Herein, CdS hollow spheres with tunable S_v concentrations were constructed through thermal treatment, yielding a non-monotonic (volcano-type) dependence of defect density. Ultrafast femtosecond transient absorption spectroscopy reveals that a moderate S_v concentration introduces shallow electron-trapping states, thereby prolonging the lifetime of photogenerated electrons (up to 1112.0 ps in acetonitrile) and suppressing recombination. In contrast, excessive S_v accumulation generates recombination centers, resulting in accelerated carrier decay. Kelvin probe force microscopy further demonstrates that the optimally engineered sample exhibits the lowest surface photovoltage (77 mV), indicative of efficient electron accumulation at surface active sites. More importantly, this work identifies a concentration-dependent dual role of sulfur vacancies—evolving from charge-separation promoters to recombination centers—and elucidates the interplay between defect-mediated carrier trapping and surface reaction kinetics in aqueous environments. These findings establish a refined mechanistic framework for defect engineering and provide strategic guidance for the rational design of high-performance CdS-based photocatalysts.

Key words: CdS, Sulfur vacancy, Femtosecond transient absorption spectroscopy, Carrier dynamics, Surface photovoltage

孟政, 艾陈斌, 张建军, 何博文, 张留洋, 吴珍, Serguei Filatov, Dmitry Selishchev, Jahan B. Ghasemi, 余家国. 通过可控硫空位工程调控CdS中的载流子动力学: 飞秒瞬态吸收光谱的见解[J]. 催化学报, 2027, 92: 274-284.

Zheng Meng, Chenbin Ai, Jianjun Zhang, Bowen He, Liuyang Zhang, Zhen Wu, Serguei Filatov, Dmitry Selishchev, Jahan B. Ghasemi, Jiaguo Yu. Regulating carrier dynamics in CdS via controlled sulfur vacancy engineering: Insights from femtosecond transient absorption spectroscopy[J]. Chinese Journal of Catalysis, 2027, 92: 274-284.

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通过可控硫空位工程调控CdS中的载流子动力学: 飞秒瞬态吸收光谱的见解

Regulating carrier dynamics in CdS via controlled sulfur vacancy engineering: Insights from femtosecond transient absorption spectroscopy

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