负载无定型钌纳米簇的原子级钴掺杂一维碳纳米笼增强析氢催化性能

doi:10.1016/S1872-2067(21)63921-9

催化学报 ›› 2022, Vol. 43 ›› Issue (1): 110-115.DOI: 10.1016/S1872-2067(21)63921-9

负载无定型钌纳米簇的原子级钴掺杂一维碳纳米笼增强析氢催化性能

杨文秀^a^,^b,†, 张炜钰^a,†, 刘锐^b, 吕帆^a, 晁玉广^a, 王子宸^a, 郭少军^a^,^*()

^a北京大学材料科学与工程学院, 北京100871
^b北京理工大学前沿交叉科学研究院, 前沿技术研究院(济南), 原子分子簇科学教育部重点实验室,化学化工学院, 北京100081

收稿日期:2021-06-03 接受日期:2021-07-08 出版日期:2022-01-18 发布日期:2021-11-15
通讯作者: 郭少军
作者简介:第一联系人：
^†共同第一作者.
基金资助:
国家重点研发计划(2020YFB1506300);国家杰出青年科学基金(52025133);国家自然科学基金(52025025);国家自然科学基金(52072400);国家自然科学基金(22075018);腾讯科学探索奖北京市自然科学基金(JQ18005)

Amorphous Ru nanoclusters onto Co-doped 1D carbon nanocages enables efficient hydrogen evolution catalysis

Wenxiu Yang^a^,^b,†, Weiyu Zhang^a,†, Rui Liu^b, Fan Lv^a, Yuguang Chao^a, Zichen Wang^a, Shaojun Guo^a^,^*()

^aSchool of Materials Science & Engineering, Peking University, Beijing 100871, China
^bAdvanced Research Institute of Multidisciplinary Science, Advanced Technology Research Institute (Jinan), Key Laboratory of Cluster Science, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China

Received:2021-06-03 Accepted:2021-07-08 Online:2022-01-18 Published:2021-11-15
Contact: Shaojun Guo
About author:* E-mail: guosj@pku.edu.cn
First author contact:
^† Contributed equally to this work.
Supported by:
National Key Research and Development Program of China(2020YFB1506300);National Science Fund for Distinguished Young Scholars(52025133);National Natural Science Foundation of China(52025025);National Natural Science Foundation of China(52072400);National Natural Science Foundation of China(22075018);Tencent Foundationthrough the XPLORER Prize, the Beijing Natural Science Foundation(JQ18005)

摘要/Abstract

摘要：

析氢反应是电解水产制氢的关键反应之一. 在碱性条件下, 由于催化剂表面与反应过程中产生的氧物种、氢物种与催化剂的吸附未处于最佳状态, 析氢反应动力学往往比较缓慢, 比在酸性条件下慢2-3个数量级. 目前, 铂基纳米催化剂被认为是最优的析氢催化剂, 但因价格昂贵、稳定性较差, 限制了其在电解水器件上的大规模应用. 因此, 设计一种价格较为低廉、活性高和稳定性好的碱性析氢催化剂尤为必要. 钌作为铂族金属之一, 其价格约为铂的三分之一, 但其与氢的结合能却与铂类似. 因此, 钌基催化剂被认为是有望替代铂作为析氢催化剂.
本文结合模板法、静电纺丝和碳化热解策略构筑了一种负载无定型钌纳米簇的原子级钴掺杂一维碳纳米笼催化剂, 有效提升了碱性条件下析氢反应性能. 该催化剂具有较高的比表面积, 丰富的缺陷结构, 原子级分散的金属Co掺杂以及无定型钌纳米簇结构, 并在碱性条件下催化析氢反应时, 表现出了低起始过电位, 低Tafel斜率(62 mV dec^-1)和高稳定性.
X射线衍射(XRD)结果表明, 该催化剂中钌和钴以无定型形式存在. 选区电子衍射结果表明了无定型结构的存在, 并且钌以纳米簇形式存在, 其平均粒径为1.48 nm. X射线光电子能谱结果表明该催化剂含有较高的氮掺杂, 拉曼光谱证明了其存在碳缺陷结构. 进一步通过X射线近边吸收谱和扩展边精细结构谱研究了钌和钴的配位环境, 结果发现, 钌带轻微正电荷, 并且存在Ru-Ru键; 钴带正电荷, 价态介于0与+2价之间, 其主要与N配位. 在1 mol/L氢氧化钾电解液中, 该杂化催化剂的电催化活性明显高于没有钴掺杂的催化剂以及商业化铂/碳催化剂. 在电流密度为10 mA cm^-2时, 过电位仅为40 mV, 在过电位为100 mV时, 该催化剂的质量催化活性达到了3.77 mA μg_Ru^-1, 远超商业化铂/碳(2.01 mA μg_Ru^-1)和钌/碳(1.66 mA μg_Ru^-1). 该催化剂也表现出了优异的析氢催化稳定性, 5000圈循环后, 10 mA cm^-2下的过电位仅增加了2 mV, 在恒电流测试中, 10 h后电位仅下降了95 mV.

关键词: 无定型钌纳米簇, 单原子, 富缺陷碳, 析氢反应, 电催化

Abstract:

The development of high-performance electrocatalysts for hydrogen evolution reaction (HER) is of great significance for green, sustainable, and renewable energy conversion. Herein, we report the synthesis of amorphous Ru clusters on Co-doped defect-rich hollow carbon nanocage (a-Ru@Co-DHC) as an efficient electrocatalyst for HER in the basic media. Due to the advantages such as high surface area, rich edge defect, atomic Co doping and amorphous Ru clusters, the as-made a-Ru@Co-DHC displays an efficient HER performance with a near-zero onset overpotential, a low Tafel slope (62 mV dec^-1), a low overpotential of 40 mV at 10 mA cm^-2 and high stability, outperforming the commercial Ru nanocrystal/C, commercial Pt/C, and other reported Ru-based catalysts. This work provides a new insight into designing new metal doped carbon nanocages catalysts supported by amorphous nanoclusters for achieving the enhanced electrocatalysis.

Key words: Amorphous Ru cluster, Single atom, Defect-rich carbon, Hydrogen evolution reaction, Electrocatalysis

杨文秀, 张炜钰, 刘锐, 吕帆, 晁玉广, 王子宸, 郭少军. 负载无定型钌纳米簇的原子级钴掺杂一维碳纳米笼增强析氢催化性能[J]. 催化学报, 2022, 43(1): 110-115.

Wenxiu Yang, Weiyu Zhang, Rui Liu, Fan Lv, Yuguang Chao, Zichen Wang, Shaojun Guo. Amorphous Ru nanoclusters onto Co-doped 1D carbon nanocages enables efficient hydrogen evolution catalysis[J]. Chinese Journal of Catalysis, 2022, 43(1): 110-115.

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https://www.cjcatal.com/CN/Y2022/V43/I1/110

图/表 5

Scheme 1. Schematic illustration of the preparation procedure of the a-Ru@Co-DHC material.

Fig. 1. Characterization of the a-Ru@Co-DHC material. XRD (a), SEM (b), TEM (c,d) images of a-Ru@Co-DHC. The inset of Fig. 1(d) is the SAED pattern of a-Ru@Co-DHC. HRTEM (e) and HAADF-STEM (f) images of a-Ru@Co-DHC; (g) HAADF-STEM images and the corresponding EDS mapping of a-Ru@Co-DHC (C green, O purple, N blue, Co yellow, and Ru orange).

Fig. 2. Compositional and structural information of the a-Ru@Co-DHC material. (a) XPS spectrum; (b) high-resolution C 1s and Ru 3d; (c) high-resolution N 1s; (d) Raman; (e) nitrogen adsorption-desorption isotherms; (f) its pore distribution.

Fig. 3. Ru K-edge XANES spectra (a) and the K3-weighted FT-EXAFS spectra (b) of Ru foil, RuO2 and a-Ru@Co-DHC. Co K-edge XANES spectra (c) and the K3-weighted FT-EXAFS (d) of Co foil, CoPc and a-Ru@Co-DHC.

Fig. 4. Electrocatalytic activities of different materials in 1.0 M KOH solution. HER polarization curves (a), corresponding Tafel plots (b), overpotentials at a current density of 10 mA cm-2 (c), and mass activities (d) for the a-Ru@DHC, a-Ru@Co-DHC, commercial Ru/C and commercial Pt/C catalysts; (e) Polarization curves of a-Ru@Co-DHC recorded before and after 5000 cycles; (f) Chronopotentiometry measurements of the a-Ru@Co-DHC catalyst at current density of 10 mA cm-2; (g) Comparison of HER catalytic performance for a-Ru@Co-DHC with other reported Ru-based catalysts in alkaline media (1.0 M KOH) [39-47].

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负载无定型钌纳米簇的原子级钴掺杂一维碳纳米笼增强析氢催化性能

Amorphous Ru nanoclusters onto Co-doped 1D carbon nanocages enables efficient hydrogen evolution catalysis

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