双位点协同促进Ru-S-C单原子催化剂上电化学氮还原

doi:10.1016/S1872-2067(22)64136-6

催化学报 ›› 2022, Vol. 43 ›› Issue (12): 3177-3186.DOI: 10.1016/S1872-2067(22)64136-6

双位点协同促进Ru-S-C单原子催化剂上电化学氮还原

杨柳晶^a, 程传祺^a, 张训^a, 唐城^b, 杜坤^a, 杨园园^a, 沈善成^c, 许实龙^c, 尹鹏飞^a^,^*(), 梁海伟^c, 凌涛^a^,^#()

^a天津大学材料科学与工程学院, 新能源研究所, 高级陶瓷与机械加工教育部重点实验室, 天津300072, 中国
^b阿德莱德大学化学工程与高级材料学院, 澳大利亚
^c中国科学技术大学化学系, 安徽合肥230026, 中国

收稿日期:2022-05-19 接受日期:2022-05-27 出版日期:2022-12-18 发布日期:2022-10-18
通讯作者: 尹鹏飞,凌涛
基金资助:
国家自然科学基金(52071231);国家自然科学基金(51722103);国家自然科学基金(52101266);天津市自然科学基金(19JCQJC61900)

Dual-site collaboration boosts electrochemical nitrogen reduction on Ru-S-C single-atom catalyst

Liujing Yang^a, Chuanqi Cheng^a, Xun Zhang^a, Cheng Tang^b, Kun Du^a, Yuanyuan Yang^a, Shan-Cheng Shen^c, Shi-Long Xu^c, Peng-Fei Yin^a^,^*(), Hai-Wei Liang^c, Tao Ling^a^,^#()

^aKey Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Institute of New-Energy, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China
^bSchool of Chemical Engineering and Advanced Materials, The University of Adelaide, Adelaide, SA 5005, Australia
^cDepartment of Chemistry, University of Science and Technology of China, Hefei 230026, Anhui, China

Received:2022-05-19 Accepted:2022-05-27 Online:2022-12-18 Published:2022-10-18
Contact: Peng-Fei Yin, Tao Ling
Supported by:
National Natural Science Foundation of China(52071231);National Natural Science Foundation of China(51722103);National Natural Science Foundation of China(52101266);Natural Science Foundation of Tianjin City(19JCQJC61900)

摘要/Abstract

摘要：

氨是一种非常重要的化学品, 但传统的哈伯-博世制氨法需要消耗大量的化石能源, 并释放二氧化碳. 电催化还原产氨是一种具有前景的绿色制氨方法. 近年来虽取得了较大进展, 但电催化氮还原反应(eNRR)的选择性和活性仍不理想, 理论和实验研究均已表明, eNRR过程中吸附N₂分子的活化以及第一次质子化NNH*中间体的形成通常是反应的决速步骤. 在催化剂中构建多反应位点, 并利用多反应位点间的协同工作效应, 是提升决速步反应的有效策略. 受固氮酶中金属/硫多位点共催化机理的启发, 本文以钌硫碳(Ru-S-C)催化剂为模型, 研究了Ru/S双位点协同催化氮还原产氨的反应过程和机理; 结合理论计算、原位拉曼光谱和动力学同位素效应(KIE)等结果, 证明了Ru/S双位点在eNRR过程中极大地促进了N₂的活化和第一步质子化; 与常规的单位点Ru-N-C催化剂相比, Ru-S-C催化剂表现出更优越的eNRR性能.

本文首先采用理论计算方法研究了Ru-S-C催化剂中Ru/S双位点在eNRR中的催化机制: 当N₂吸附在Ru原子上, Ru原子会将电子推至N₂的反键轨道, 从而实现N≡N键的活化, N₂的活化主要是由Ru对电子的“推”机制完成的; 而当S原子(与Ru原子直接配位)也作为活性位点参与反应并氢化形成S-H*时, N₂的活化将转变为“推-推”机制, 即在Ru位点推动电子向N₂移动的同时, 与S原子结合的表面H*也会诱导电子流向N₂. 在Ru/S双位点协同作用下, 速率决定步骤第一步质子化的热力学和动力学势垒得到大幅降低.

随后, 通过湿浸渍Ru盐加热处理还原的方法将Ru单原子锚定到预合成的硫掺杂的介孔碳上(钴辅助热解方法), 制得Ru-S-C单原子催化剂. X射线衍射、像差校正的高角度环形暗场扫描透射电子显微镜和扩展X射线吸收精细结构等表征结果表明, Ru-S-C材料是单原子结构, 即Ru单原子由4个S原子配位. 将催化剂应用于电催化氮还原产氨反应, 在-0.15 V_RHE电位下, 该催化剂在碱性电解液中的氨产率为13.17 μg h^-1 mg^-1_cat, 法拉第效率为6.16%, 其NRR性能明显高于对比样品Ru-N-C单原子催化剂.

原位拉曼光谱以及KIE的测试进一步从实验上证实了在Ru-S-C单原子催化剂中S-H*的存在及其对eNRR第一步加氢的促进作用. 原位拉曼测试谱结果表明, 施加电位后, 2531 cm^-1处有明显的S-H*键伸缩振动峰, 证明了S-H*的存在, 此外, 该峰的强度还随着电位的增加呈先增大后减小的趋势, 并在-0.15 V_RHE达到峰值, 这与其NH₃产率随电位的变化趋势一致, 说明S-H*参与了N₂的还原过程. 此外, Ru-S-C表现出较高的KIE值, 说明H键的断裂参与了eNRR的决速步NNH*的形成. 综上, 本文所提出的双位点协同催化机制将为推进可持续NH₃生产开辟新途径, 提供新机遇.

关键词: Ru/S双位点催化机制, 电子“推-推”效应, 电催化氮还原反应

Abstract:

Electrocatalytic reduction of nitrogen into ammonia (NH₃) is a highly attractive but challenging route for NH₃ production. We propose to realize a synergetic work of multi reaction sites to overcome the limitation of sustainable NH₃ production. Herein, using ruthenium-sulfur-carbon (Ru-S-C) catalyst as a prototype, we show that the Ru/S dual-site cooperates to catalyse eletrocatalytic nitrogen reduction reaction (eNRR) at ambient conditions. With the combination of theoretical calculations, in situ Raman spectroscopy, and experimental observation, we demonstrate that such Ru/S dual-site cooperation greatly facilitates the activation and first protonation of N₂ in the rate-determining step of eNRR. As a result, Ru-S-C catalyst exhibits significantly enhanced eNRR performance compared with the routine Ru-N-C catalyst via a single-site catalytic mechanism. We anticipate that our specifically designed dual-site collaborative catalytic mechanism will open up a new way to offers new opportunities for advancing sustainable NH₃ production.

Key words: Ru/S dual-site mechanism, Electronic ‘push-push’, mechanism, Electrocatalytic nitrogen reduction, reaction

杨柳晶, 程传祺, 张训, 唐城, 杜坤, 杨园园, 沈善成, 许实龙, 尹鹏飞, 梁海伟, 凌涛. 双位点协同促进Ru-S-C单原子催化剂上电化学氮还原[J]. 催化学报, 2022, 43(12): 3177-3186.

Liujing Yang, Chuanqi Cheng, Xun Zhang, Cheng Tang, Kun Du, Yuanyuan Yang, Shan-Cheng Shen, Shi-Long Xu, Peng-Fei Yin, Hai-Wei Liang, Tao Ling. Dual-site collaboration boosts electrochemical nitrogen reduction on Ru-S-C single-atom catalyst[J]. Chinese Journal of Catalysis, 2022, 43(12): 3177-3186.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64136-6

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图/表 4

Fig. 1. Theoretical investigation on activation and first protonation of N2 over Ru-S-C catalyst. (a,b) Schematic diagrams of N2 activation without and with S-H*, respectively. The grey, light red, light blue, yellow, and red coloured balls represent C, Ru, N, S, and H atoms, respectively. (c) Projected density of states of N 2s, 2p, and Ru 3d of N2 adsorbed Ru-S-C catalyst without and with S-H*. (d) Schematic diagram of the formation of NNH* on Ru-S-C catalyst with S-H*. (e) DFT calculated free energy diagram of the NNH* formation on Ru-S-C catalyst with the S-H* (upper) and without S-H* (lower).

Fig. 2. Structural characterisation of the Ru-S-C catalyst. (a) HAADF-STEM image and EDS elemental mappings of Ru, C, and S. (b) XRD patterns of Ru-S-C catalyst and S-C framework. (c) HAADF-STEM image of the Ru-S-C catalyst, showing atomically dispersed Ru atoms (marked by yellow circles) on the S-C matrix. (d) Normalized XANES spectra of Ru-S-C, Ru foil, RuCl3, and RuO2 at the Ru K-edge, with the inset showing the enlarged spectra in a range from 22113 to 22134 eV. (e) Corresponding EXAFS spectra of Ru-S-C, Ru foil, RuCl3, and RuO2 at R space. (f) EXAFS fitting for Ru-S-C catalyst, with the inset showing the schematic diagram of a Ru-S4 moiety embedded in Ru-S-C catalyst.

Fig. 3. Electrochemical eNRR performances of Ru-S-C and Ru-N-C catalysts. (a) 1H NMR spectra (500 MHz) of the collected electrolyte after the eNRR process using 14N2 and 15N2 as the feeding N2 source. The 1H NMR spectra of the standard solutions containing 14NH4+ and 15NH4+ are also shown as the references. Faradaic efficiencies (b), NH3 yields (c), and TOFs (d) measured by ammonia sensitive electrode. The error bars represent variations in the three experimental samples. The inset in (c) shows the partial current density of eNRR based on geometric area.

Fig. 4. Experimental verification of the Ru/S dual-site mechanism of Ru-S-C catalyst. In situ Raman spectra tested in N2- (a) and Ar- (b) saturated 0.10 mol L-1 KOH at various applied potentials. (c) KIE of H/D of the Ru-S-C catalyst tested in N2-saturated 0.10 mol L-1 KOH at -0.15 VRHE. (d) Schematic diagram of the Ru/S dual-site collaborative catalytic mechanism.

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双位点协同促进Ru-S-C单原子催化剂上电化学氮还原

Dual-site collaboration boosts electrochemical nitrogen reduction on Ru-S-C single-atom catalyst

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