Ir2S3/ZnIn2S4催化下可见光诱导发生的烯烃/炔烃的高效硫氢化反应: Ir2S3的作用

doi:10.1016/S1872-2067(20)63660-9

催化学报 ›› 2021, Vol. 42 ›› Issue (3): 409-416.DOI: 10.1016/S1872-2067(20)63660-9

Ir₂S₃/ZnIn₂S₄催化下可见光诱导发生的烯烃/炔烃的高效硫氢化反应: Ir₂S₃的作用

王星林, 李媛媛, 李朝晖^*()

福州大学化学学院,能源与环境光催化国家重点实验室光催化研究室,福建福州350116

收稿日期:2020-05-19 接受日期:2020-06-25 出版日期:2021-03-18 发布日期:2021-01-23
通讯作者: 李朝晖
基金资助:
国家自然科学基金(21872031);国家自然科学基金(U1705251);闽江学者特聘教授科研启动基金

Efficient visible light initiated hydrothiolations of alkenes/alkynes over Ir₂S₃/ZnIn₂S₄: Role of Ir₂S₃

Xinglin Wang, Yuanyuan Li, Zhaohui Li^*()

Research Institute of Photocatalysis,State Key Laboratory of Photocatalysis on Energy and Environment, College of Chemistry,Fuzhou University, Fuzhou 350116,Fujian,China

Received:2020-05-19 Accepted:2020-06-25 Online:2021-03-18 Published:2021-01-23
Contact: Zhaohui Li
About author:^*Tel/Fax: +86-591-22865855;E-mail:haohuili1969@yahoo.com
Supported by:
National Natural Science Foundation of China (21872031,) and the Award Program for Minjiang Scholar Professorship.(21872031);National Natural Science Foundation of China (21872031,U1705251) and the Award Program for Minjiang Scholar Professorship.(U1705251);Award Program for Minjiang Scholar Professorship

摘要/Abstract

摘要：

C-S键的构建在化学中具有非常重要的意义. 利用硫醇和烯烃/炔烃的硫氢化反应来构建C-S键是一种绿色、可持续和低成本的方法. 本文以ZnCl₂,InCl₃,硫代乙酰胺为前驱体,在微量IrCl₃存在条件下,通过一步溶剂热法制备得到了含有不同Ir摩尔比(0.5 mol%,1 mol%和2 mol%)的Ir₂S₃/ZnIn₂S₄纳米复合材料,并考察了它在可见光下诱导烯烃/炔烃的硫氢化反应中的催化性能. 以苄基硫醇和苯乙炔的硫氢化反应为模型反应,发现在ZnIn₂S₄中引入微量的Ir₂S₃可明显提升其性能,其中以0.5 mol% Ir₂S₃/ZnIn₂S₄为催化剂时反应性能最佳; 反应15 h后苄基硫醇的转化率为97%,苄基苯乙烯基硫醚的产率为95%,明显高于以未修饰的ZnIn₂S₄为催化剂时的转化率和产率. 在反应中加入自由基捕获剂TEMPO之后可淬灭该反应,表明与未修饰的ZnIn₂S₄相同,以Ir₂S₃/ZnIn₂S₄复合材料催化的硫氢化反应同样是由硫醇自由基诱发的反应. 这种微量Ir₂S₃对ZnIn₂S₄上光诱导硫氢化反应的提升作用在所考察的多个系列底物的反应中都有不同程度的体现,尤其对于一些空间体积较大的底物,其提升作用尤为明显,表明微量Ir₂S₃的存在对ZnIn₂S₄上光诱导硫醇和烯烃/炔烃硫氢化反应的提升作用具有普适性. 通过研究负载不同助催化剂(MoS₂,NiS和Pd)的ZnIn₂S₄纳米复合材料在烯烃/炔烃硫氢化反应中的性能及其电化学交流阻抗,我们发现,Ir₂S₃的存在可促进ZnIn₂S₄上光生电子空穴的分离,从而有利于巯基自由基的生成,同时还抑制了副物氢气的产生,因此,烯烃/炔烃的硫氢化反应性能显著提高. 该文提出了一种在可见光下利用半导体光催化来构建C-S键的绿色途径,对于理解和设计新的光催化有机合成反应体系具有一定的指导意义.

关键词: 光催化, 硫化铱/ZnIn₂S₄, 烯烃, 炔烃, 硫氢化反应

Abstract:

Research Institute of Photocatalysis,State Key Laboratory of Photocatalysis on Energy and Environment,College of Chemistry,Fuzhou University,Fuzhou 350116,Fujian,ChinaArticle history:The hydrothiolations of alkynes/alkenes with thiols is an atom-economic and thus attractive method for the constructions of C-S bonds. Here Ir2S3/ZnIn2S4 nanocomposites with varied Ir2S3 loadings were obtained by one-pot solvothermal method from ZnCl2,InCl3 and thioacetamide with IrCl3. The loading of Ir2S3 on the surface of ZnIn2S4 promoted the hydrothiolations of alkenes and alkynes,with an optimum performance observed over 0.5 mol% Ir2S3/ZnIn2S4 nanocomposite. Based on the studies on the performance of several other cocatalysts (MoS2,NiS and Pd) loaded ZnIn2S4 and the EIS analyses,it was proposed that the superior performance over Ir2S3/ZnIn2S4 nanocomposite can be ascribed to an improved efficiency on the photogeneration of the thiyl radicals by loading Ir2S3 as well as its inactivity for photocatalytic hydrogen evolution,a side reaction in the light initiated hydrothiolation reaction over ZnIn2S4. This study not only demonstrates an efficient and green strategy to synthesize thiolated products under visible light based on semiconductor photocatalysis,but also provides some guidances for the design and development of photocatalytic systems for light induced organic syntheses.

Key words: Photocatalysis, Ir2S3/ZnIn2S4, Alkenes, Alkynes, Hydrothiolation

王星林, 李媛媛, 李朝晖. Ir₂S₃/ZnIn₂S₄催化下可见光诱导发生的烯烃/炔烃的高效硫氢化反应: Ir₂S₃的作用[J]. 催化学报, 2021, 42(3): 409-416.

Xinglin Wang, Yuanyuan Li, Zhaohui Li. Efficient visible light initiated hydrothiolations of alkenes/alkynes over Ir₂S₃/ZnIn₂S₄: Role of Ir₂S₃[J]. Chinese Journal of Catalysis, 2021, 42(3): 409-416.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(20)63660-9

https://www.cjcatal.com/CN/Y2021/V42/I3/409

图/表 9

Fig.1. XRD patterns of different samples. (a) ZnIn2S4; (b) 0.5 mol% Ir2S3/ZnIn2S4; (c) 1 mol% Ir2S3/ZnIn2S4; (d) 2 mol% Ir2S3/ZnIn2S4.

Fig.2. XPS spectra of 0.5?mol% Ir2S3/ZnIn2S4 nanocomposite. (a) Ir 4f ; (b) S 2p; (c) Zn 2p; (d) In 3d.

Fig. 3. SEM (a),TEM (b) and HRTEM (c) image 0.5?mol% Ir2S3/ZnIn2S4 nanocomposite.

Fig. 4. UV‐visible diffuse reflectance spectra of ZnIn2S4,0.5 mol%Ir2S3/ZnIn2S4,1 mol% Ir2S3/ZnIn2S4,2 mol% Ir2S3/ZnIn2S4.

Table 1 Light initiated hydrothiolation between benzyl mercaptane and phenylacetylene over Ir2S3/ZnIn2S4 under different conditions.

Entry	Catalyst	Conv ^a (%)	Yield of 3a^b (%)
1	1 mol% Ir₂S₃/ZnIn₂S₄	99	94
2	2 mol% Ir₂S₃/ZnIn₂S₄	91	85
3	0.5 mol% Ir₂S₃/ZnIn₂S₄	97	95
4	ZnIn₂S₄	94	90
5^c	—	0	0
6^d	0.5 mol% Ir₂S₃/ZnIn₂S₄	trace	trace
7^f	0.5 mol% Ir₂S₃/ZnIn₂S₄	5	5

Table 2 Investigations of the substrate scope of visible‐light‐initiated hydrothiolations of alkynes and alkenes over 0.5 mol% Ir2S3/ZnIn2S4.

Fig.5. (a) Cycling of the hydrothiolation reaction between phenylacetylene and benzyl mercaptane over Ir2S3/ZnIn2S4 under visible light irradiation; (b) XRD patterns of (a) used Ir2S3/ZnIn2S4 after three cycling reactions (1) and fresh Ir2S3/ZnIn2S4 (2).

Fig.6. Nyquist plots of experimental impedance data for bare ZnIn2S4,Ir2S3/ZnIn2S4,MoS2/ZnIn2S4,NiS/ZnIn2S4 and Pd/ZnIn2S4 in the frequency range of 0.1-1.0×105 Hz using an ac bias of 0 V vs Ag/AgCl without visible light irradiations in an aqueous solution containing K3[Fe(CN)6] (1 mmol/L),K4[Fe(CN)6] (1 mmol/L) and KCl (0.1 mol/L).

Table 3 Light initiated hydrothiolation between phenylacetylene and 1-dodecanethiol over Ir2S3/ZnIn2S4,MoS2/ZnIn2S4,Pd/ZnIn2S4,NiS/ZnIn2S4 and bare ZnIn2S4.

Entry	Catalyst	Conversion ^a (%)	Yield ^b (%)	H₂ (μmol)
1	0.5 mol% Ir₂S₃/ZnIn₂S₄	79	76	0.7
2	0.5 mol% MoS₂/ZnIn₂S₄	55	54	13.2
3	0.5 mol% Pd/ZnIn₂S₄	60	59	1.9
4	0.5 mol% NiS/ZnIn₂S₄	41	39	3.9
5	ZnIn₂S₄	58	56	—

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Ir₂S₃/ZnIn₂S₄催化下可见光诱导发生的烯烃/炔烃的高效硫氢化反应: Ir₂S₃的作用

Efficient visible light initiated hydrothiolations of alkenes/alkynes over Ir₂S₃/ZnIn₂S₄: Role of Ir₂S₃

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