表面硫物种对钯-硫纳米片加氢性能的影响

doi:10.3866/PKU.WHXB202309043

物理化学学报 >> 2024, Vol. 40 >> Issue (11): 2309043.doi: 10.3866/PKU.WHXB202309043

表面硫物种对钯-硫纳米片加氢性能的影响

张伟晗¹^,†, 王梦露¹^,†, 贾安康¹, 邓威², 白树行¹^,*()

¹ 青岛大学化学化工学院可持续能源与资源研究院, 山东青岛 266071
² 江汉大学光电材料与技术学院, 武汉 430056

收稿日期:2023-09-27 修回日期:2023-11-10 录用日期:2023-11-13 发布日期:2024-01-02
通讯作者: Email: shuxbai@qdu.edu.cn; Tel.: +86-15063919273 (白树行)
作者简介:
^†These authors contributed equally to this work.
基金资助:
国家自然科学基金项目(22102078); 山东省自然科学基金(ZR2021QB091); 青岛大学启动资金资助项目

Surface Sulfur Species Influence Hydrogenation Performance of Palladium-Sulfur Nanosheets

Weihan Zhang¹, Menglu Wang¹, Ankang Jia¹, Wei Deng², Shuxing Bai¹^,*()

¹ Institute for Sustainable Energy and Resources, College of Chemistry and Chemical Engineering, Qingdao University, Qingdao 266071, Shandong Province, China
² School of Optoelectronic Materials and Technology, Jianghan University, Wuhan 430056, China

Received:2023-09-27 Revised:2023-11-10 Accepted:2023-11-13 Published:2024-01-02
Contact: Email: shuxbai@qdu.edu.cn; Tel.: +86-15063919273 (Shuxing Bai)
Supported by:
the National Natural Science Foundation of China(22102078); the Natural Science Foundation of Shandong Province, China(ZR2021QB091); the Start-up Supports from Qingdao University

1. WHXB202309043-SI-9p.pdf(5405KB)

摘要/Abstract

摘要：

炔烃制备烯烃在聚合物和精细化工工业中具有至关重要的地位，但在平衡选择性和活性方面仍存在相当大的难题。本文通过使用不同的硫源成功合成了几种钯-硫纳米片(Pd-S NSs)，并研究了表面硫物种对炔烃选择性加氢催化效率的影响。在这些催化剂中，以1,4-苯二硫醇(PT)为硫源的Pd-S-PT NSs/C在苯乙炔加氢2 h后表现出较高的苯乙烯选择性(92.3%–96.7%)。Pd-S-PT NSs的烯烃选择性增强的原因在于Pd到S的电子转移较差，以及表面独立存在的S⁰物种，保持了较高的加氢活性，同时避免了高氧化态的S (S⁴⁺)引起的过度加氢。该研究不仅开发了高效的炔烃加氢催化剂，还推动了对催化表面精确控制的基础研究。

关键词: 钯-硫纳米片, 表面硫物种, 炔烃加氢, 烯烃, 选择性

Abstract:

Olefins play a crucial role as fundamental raw materials in organic synthesis, particularly in the production of polyolefins and synthetic rubber. The conversion of alkynes to olefins is pivotal in both the polymer and fine chemical industries. However, this process faces significant challenges in terms of equilibrium selectivity and activity. The inherent low solubility of hydrogen, coupled with the thermodynamic ease of hydrogenating intermediate olefins compared to alkynes, contributes to a decline in olefin selectivity due to further hydrogenation leading to alkanes. Palladium-based catalysts, widely used for hydrogenation, exhibit robust hydrogen adsorption but lack selectivity. Researchers commonly modify catalyst structures by introducing other metals or non-metals to create intermetallic compounds, aiming to enhance olefin selectivity. This study focuses on synthesizing palladium-sulfur nanosheets (Pd-S NSs) using various sulfur sources to explore the impact of surface S species on the catalytic efficiency of selectively hydrogenating alkynes. Among these, Pd-S-PT NSs/C, utilizing 1,4-benzenedithiol (PT) as the sulfur source, demonstrated high styrene selectivity (92.3%–96.7%) following phenylacetylene hydrogenation for 2 h, showing notable selectivity for different alkynes' end-groups. Contrastingly, Pd-S-TU NSs/C, with thiourea (TU) as the sulfur source, exhibited poor olefin selectivity (72.4%). X-ray photoelectron spectroscopy (XPS) revealed that the improved olefin selectivity in Pd-S-PT NSs/C was attributed to hindered electron transfer from Pd to S, as well as the presence of surface S⁰ species, maintaining high hydrogenation activity while avoiding over-hydrogenation induced by oxidized S species (S⁴⁺). In situ diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) demonstrated weak styrene adsorption on Pd-S-PT NSs, inhibiting further hydrogenation to ethylbenzene. The ease of styrene desorption on Pd-S-PT NSs, indicated by reduced adsorption strength with increasing desorption temperature, highlighted high olefin selectivity. Conversely, stronger styrene adsorption on Pd-S-TU NSs facilitated additional hydrogenation to produce ethylbenzene, suggesting that the presence of additional S⁴⁺ species hindered improved styrene selectivity. This study not only introduces efficient catalysts for olefin hydrogenation but also advances fundamental research on precisely controlling catalytic processes, particularly focusing on the nuanced control of catalytic surfaces.

Key words: Palladium-sulfur nanosheets, Surface sulfur species, Alkyne hydrogenation, Alkene, Selectivity

张伟晗, 王梦露, 贾安康, 邓威, 白树行. 表面硫物种对钯-硫纳米片加氢性能的影响[J]. 物理化学学报, 2024, 40(11), 2309043. doi: 10.3866/PKU.WHXB202309043

Weihan Zhang, Menglu Wang, Ankang Jia, Wei Deng, Shuxing Bai. Surface Sulfur Species Influence Hydrogenation Performance of Palladium-Sulfur Nanosheets[J]. Acta Phys. -Chim. Sin. 2024, 40(11), 2309043. doi: 10.3866/PKU.WHXB202309043

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB202309043

https://www.whxb.pku.edu.cn/CN/Y2024/V40/I11/2309043

图/表 6

参考文献 39

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表面硫物种对钯-硫纳米片加氢性能的影响

Surface Sulfur Species Influence Hydrogenation Performance of Palladium-Sulfur Nanosheets

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