揭示次表面氢抑制促进炔烃电催化半氢化性能

doi:10.1016/S1872-2067(22)64145-7

催化学报 ›› 2022, Vol. 43 ›› Issue (12): 3095-3100.DOI: 10.1016/S1872-2067(22)64145-7

揭示次表面氢抑制促进炔烃电催化半氢化性能

郝琦^a^,^†, 吴永萌^a^,^*^,^†(), 刘翠波^a, 史艳梅^a, 张兵^a^,^b^,^#()

^a天津大学理学院化学系, 分子+研究院, 天津300072
^b天津大学教育部合成生物前沿科学中心, 天津市分子光电科学重点实验室, 天津300072

收稿日期:2022-03-18 接受日期:2022-05-01 出版日期:2022-12-18 发布日期:2022-10-18
通讯作者: 吴永萌,张兵
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家自然科学基金(21871206);国家自然科学基金(22001192)

Unveiling subsurface hydrogen inhibition for promoting electrochemical transfer semihydrogenation of alkynes with water

Qi Hao^a^,^†, Yongmeng Wu^a^,^*^,^†(), Cuibo Liu^a, Yanmei Shi^a, Bin Zhang^a^,^b^,^#()

^aDepartment of Chemistry, Institute of Molecular Plus, School of Science, Tianjin University, Tianjin 300072, China
^bFrontiers Science Center for Synthetic Biology, Key Laboratory of Systems Bioengineering (Ministry of Education), Tianjin University, Tianjin 300072, China

Received:2022-03-18 Accepted:2022-05-01 Online:2022-12-18 Published:2022-10-18
Contact: Yongmeng Wu, Bin Zhang
About author:First author contact:^†Contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21871206);National Natural Science Foundation of China(22001192)

摘要/Abstract

摘要：

烯烃是生产高附加值精细化工产品和工业聚合级乙烯的基本原料, 炔烃选择性半氢化反应是烯烃合成的重要途径. 近年来, 研究者致力于发展经济、绿色的炔烃半氢化方法. 最近, 以水为氢源的炔烃电催化转移半氢化由于避免了氢气和有机氢化试剂的使用而引起了广泛关注. 该方法中水电解在催化剂表面产生的表面吸附氢(H*_ads)是关键的氢物种, 通过催化剂改性或改变施加电位可以控制H*_ads的数量, 从而调控反应的效率和选择性. 然而, 催化剂的次表面吸收氢(H*_abs)常被忽略, 且热催化中已经证实H*_abs具有比H*_ads更强的氢化能力, 是导致烯烃过度氢化而降低炔烃半氢化选择性的主要原因. 但是, H*_abs在电催化炔烃半氢化中的作用尚不清楚. 因此, 探索催化剂中H*_abs对电催化炔烃半氢化的影响具有重要意义.

钯(Pd)基材料具有良好的C≡C键活化能力和储氢能力, 是均相和非均相炔烃半氢化反应的首选催化剂. 但单质Pd往往难以达到理想的选择性要求, 通常需要对其改性修饰. 本课题组曾以Pd-P为阴极成功实现了以水为氢源的炔烃电催化转移半氢化(Angew. Chem. Int. Ed., 2020, 59, 21170‒21175). 然而, P的引入难以有效地抑制烯烃的过氢化, 烯烃的选择性仍然高度依赖于施加电位. 硫(S)是一种常用的炔烃半氢化催化剂改性剂, S的引入可以减弱金属对烯烃的吸附从而提高烯烃的选择性. 但是S对金属催化剂在电催化半氢化过程中H*_abs的形成的影响以及H*_abs对烯烃选择性的作用仍有待深入研究. 此外, 钯硫化物(Pd-S)的合成通常是以具有毒性和腐蚀性的H₂S、硫醇等为S源在高温条件下进行的, 容易引发环境和安全问题. 而且, 该方法难以控制产物中S含量, 过量的S会占据Pd活性位点, 导致催化活性显著下降. 基于此, 本文发展了一种室温下简单可控的Pd-S电催化剂合成方法, 并揭示了S对Pd中H*_abs的形成和烯烃选择性的影响, 同时实现了非电位依赖的以水为氢源的炔烃电催化转移半氢化.

本文通过固液界面硫化法成功制备了S修饰的Pd纳米线(Pd-S NWs), 并利用扫描电子显微镜、透射电子显微镜、X射线衍射和X射线光电子能谱等方法进行表征. 利用线性循环伏安扫描和电化学原位X射线衍射研究了Pd-S NWs和Pd NWs在电还原过程中H*_ads和H*_abs的含量差异. 结果发现, Pd在电还原条件下产生H*_ads和H*_abs, 而Pd-S只产生H*_ads, 说明S的引入可以有效抑制H*_abs的生成. 当采用Pd-S NWs和Pd NWs分别作为阴极用于电催化炔烃半氢化时, Pd-S NWs表现出更高的烯烃选择性(99%)和法拉第效率(64%), 且其选择性不随反应电位的增大而降低, 证实了抑制H*_abs的生成是提高烯烃选择性的关键. 此外, 该方法还具有良好的底物普适性和易还原官能团兼容性. 通过向反应体系原位添加SCN^-, 可使商业Pd/C阴极在该体系中以99%的选择性和95%的转化率实现烯烃的克级合成, 体现了该方法的应用潜力. 综上, 本文不仅提供了一种通过抑制催化剂次表面氢形成进而提高电催化炔烃半氢化选择性的方法, 也为其他电催化氢化反应的选择性调控提供了借鉴.

关键词: 电催化, 炔烃半氢化, 选择性, 氢吸附, 表面硫化

Abstract:

Highly selective electrocatalytic semihydrogenation of alkynes to alkenes with water as the hydrogen source over palladium-based electrocatalysts is significant but remains a great challenge because of the excessive hydrogenation capacity of palladium. Here, we propose that an ideal palladium catalyst should possess weak alkene adsorption and inhibit subsurface hydrogen formation to stimulate the high selectivity of alkyne semihydrogenation. Therefore, sulfur-modified Pd nanowires (Pd-S NWs) are designedly prepared by a solid-solution interface sulfuration method with KSCN as the sulfur source. The introduction of S weakens the alkene adsorption and prevents the diffusion of active hydrogen (H*) into the Pd lattice to form unfavorable subsurface H*. As a result, electrocatalytic alkyne semihydrogenation is achieved over a Pd-S NWs cathode with wide substrate scopes, potential-independent up to 99% alkene selectivity, good fragile groups compatibility, and easily synthesized deuterated alkenes. An adsorbed hydrogen addition mechanism of this semihydrogenation reaction is proposed. Importantly, an easy modification of commercial Pd/C by in situ addition of SCN^- enabling the gram-scale synthesis of an alkene with 99% selectivity and 95% conversion highlights the promising potential of our method.

Key words: Electrocatalysis, Alkyne semihydrogenation, Selectivity, Hydrogen adsorption, Interface sulfuration

郝琦, 吴永萌, 刘翠波, 史艳梅, 张兵. 揭示次表面氢抑制促进炔烃电催化半氢化性能[J]. 催化学报, 2022, 43(12): 3095-3100.

Qi Hao, Yongmeng Wu, Cuibo Liu, Yanmei Shi, Bin Zhang. Unveiling subsurface hydrogen inhibition for promoting electrochemical transfer semihydrogenation of alkynes with water[J]. Chinese Journal of Catalysis, 2022, 43(12): 3095-3100.

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图/表 5

Fig. 1. (a) TEM, HRTEM, and EDS elemental mapping images of Pd-S NWs. (b) XRD patterns of Pd-S NWs and Pd NWs. XPS spectra of S 2p (c) and Pd 3d (d) of Pd-S NWs.

Fig. 2. Potential-dependent 1a conversion 2a selectivity and 2a FE over Pd-S NWs (a) and Pd NWs (b). Time-dependent (c) and cycle-dependent (d) 1a Conversion and 2a Selectivity over PdS NWs.

Fig. 3. (a) CV curves of Pd NWs and Pd-S NWs in 0.5 mol/L Na2SO4. (b) Electrochemical in situ XRD pattern performed in 1.0 mol/L KOH. (c) Chronoamperometry measurements recorded for Pd NWs and Pd-S NWs at a reductive potential (absorption) and oxidative potential (desorption). (d) Calculated amounts of transformed charge of Pd NWs and Pd-S NWs from chronoamperometry measurements. Inset: quantification of hydrogen absorption in Pd NWs and Pd-S NWs during chronoamperometry measurements.

Table 1 Substrate scopes for electrocatalytic transfer semihydrogenation and semideuterization of alkynes with H2O over a Pd-S cathode.

Fig. 4. (a) Scheme of electrocatalytic gram-scale semihydrogenation over commercial Pd/C with SCN- addition. (b) 1a Conversion and 2a Selectivity over commercial Pd/C with and without SCN- addition. (c) Time-dependent 1a Conversion and 2a Selectivity during gram-scale semihydronation over commercial Pd/C with SCN- addition.

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揭示次表面氢抑制促进炔烃电催化半氢化性能

Unveiling subsurface hydrogen inhibition for promoting electrochemical transfer semihydrogenation of alkynes with water

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