石墨炔负载的双金属单团簇催化剂用于碱性析氢反应

doi:10.1016/S1872-2067(23)64459-6

催化学报 ›› 2023, Vol. 50: 306-313.DOI: 10.1016/S1872-2067(23)64459-6

石墨炔负载的双金属单团簇催化剂用于碱性析氢反应

陈斌^a, 蒋亚飞^b, 肖海^a^,^*(), 李隽^a^,^b^,^*()

^a清华大学化学系, 稀土新材料教育部工程研究中心, 北京 100084
^b南方科技大学化学系, 广东省催化化学重点实验室, 广东深圳 518055

收稿日期:2023-03-09 接受日期:2023-05-21 出版日期:2023-07-18 发布日期:2023-07-25
通讯作者: *电子信箱: haixiao@tsinghua.edu.cn (肖海), junli@tsinghua.edu.cn (李隽).
基金资助:
国家自然科学基金(92261111);国家自然科学基金(22122304);国家重点研发计划(2022YFA1503000);国家重点研发计划(2022YFA1503900);广东省催化化学重点实验室(2020B121201002);清华大学自主科研计划(20221080065)

Bimetallic single-cluster catalysts anchored on graphdiyne for alkaline hydrogen evolution reaction

Bin Chen^a, Ya-Fei Jiang^b, Hai Xiao^a^,^*(), Jun Li^a^,^b^,^*()

^aDepartment of Chemistry and Engineering Research Center of Advanced Rare-Earth Materials of Ministry of Education, Tsinghua University, Beijing 100084, China
^bDepartment of Chemistry and Guangdong Provincial Key Laboratory of Catalytic Chemistry, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China

Received:2023-03-09 Accepted:2023-05-21 Online:2023-07-18 Published:2023-07-25
Contact: *E-mail: haixiao@tsinghua.edu.cn (H. Xiao), junli@tsinghua.edu.cn (J. Li).
Supported by:
National Natural Science Foundation of China(92261111);National Natural Science Foundation of China(22122304);National Key Research and Development Project(2022YFA1503000);National Key Research and Development Project(2022YFA1503900);Guangdong Provincial Key Laboratory of Catalysis(2020B121201002);Tsinghua University Initiative Scientific Research Program(20221080065)

摘要/Abstract

摘要：

氢气(H₂)可以存储可再生能源并应用于燃料电池, 其中电化学析氢反应(HER)是可持续制备高纯氢气的方法之一. 铂(Pt)是HER最有效的电催化剂之一, 但其在碱性介质中存在较高的水解离能垒, 限制了Pt电催化剂整体的HER活性, 而提高水解离动力学可能会增强H吸附, 不利于制H₂, 这使得进一步优化Pt基碱性HER电催化剂面临类似Sabatier原则的限制.

本文预测, 石墨炔(GDY)负载的具有金字塔结构的双金属M₁A₃ (M为后过渡金属, A为前过渡金属)四原子单团簇催化剂(SCCs)是高性能的碱性HER电催化剂. 通过第一性原理计算发现, Pt₁Ti₃/GDY SCC在工作条件下热力学和动力学稳定, 能够通过Volmer-Heyrovsky机制提供碱性HER的高催化活性. 一方面，Ti金属位点可以协同促进水的解离, 降低水解离能垒，并促进水解离形成的H中间体(*H)向邻近的Pt金属位点转移, 从而加快了碱性HER过程的Volmer决速步; 另一方面, 相邻带负电荷的Pt金属位点的d带中心下移, 从而有利于H的脱附, 提供了更优化的H吸附自由能(ΔG_*H). 因此, Pt₁Ti₃/GDY SCC有希望突破Pt基电催化剂类似Sabatier原则的限制.

通过筛选M₁替代Pt₁, 获得最佳的ΔG_*H和水解离, 进一步预测Ir₁Ti₃/GDY SCC在低*OH覆盖率下是一个更有前景的碱性HER电催化剂. 综上, 本文提出了一种新型的M₁A₃/GDY SCCs, 它具有作为碱性HER高性能电催化剂的巨大潜力, 同时为碱性HER电催化剂的理性设计提供了新见解.

关键词: 碱性析氢反应, 水解离动力学, 单团簇催化, Pt₁Ti₃/Graphdiyne

Abstract:

Pt-based electrocatalysts suffer from high water dissociation barriers that limit their overall hydrogen evolution reaction (HER) activities in alkaline media. Here we predict the bimetallic four-atom single-cluster catalysts (SCCs) M₁A₃ (M as later transition metal and A as early transition metal) with pyramidal structure supported on graphdiyne (GDY) for alkaline HER. Theoretical calculations show that the stable Pt₁Ti₃/GDY SCC delivers high alkaline HER activity via the Volmer-Heyrovsky mechanism. The excellent catalytic performance of Pt₁Ti₃/GDY SCC is attributed to both the low-valent Pt site that renders an optimal hydrogen adsorption free energy (ΔG_*H), and the synergic effect of adjacent Ti sites that leads to a low water dissociation barrier. By screening alternative M₁ in M₁Ti₃/GDY for optimal ΔG_*H and facile water dissociation, we further identify the Ir₁Ti₃/GDY SCC to be a potentially high-performing alkaline HER electrocatalyst at low *OH coverage. Our work provides new insights and guidelines for the rational design of alkaline HER electrocatalysts.

Key words: Alkaline hydrogen evolution reaction, Water dissociation kinetics, Single-cluster catalysis, Pt₁Ti₃/Graphdiyne

陈斌, 蒋亚飞, 肖海, 李隽. 石墨炔负载的双金属单团簇催化剂用于碱性析氢反应[J]. 催化学报, 2023, 50: 306-313.

Bin Chen, Ya-Fei Jiang, Hai Xiao, Jun Li. Bimetallic single-cluster catalysts anchored on graphdiyne for alkaline hydrogen evolution reaction[J]. Chinese Journal of Catalysis, 2023, 50: 306-313.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64459-6

https://www.cjcatal.com/CN/Y2023/V50/I7/306

图/表 5

Fig. 1. Optimized structure of the GDY-supported Pt1Ti3 cluster. (a) Top view. (b) Side view. The grey, blue and brown spheres represent Pt, Ti and C, respectively.

Fig. 2. Calculated reaction barriers and free energies of water dissociation (a), and HER free-energy diagram at U = 0 V (vs. RHE) (b) for different materials. For Pt1Ti3/GDY, Gads(*H) = G(*H) - G(*) - G(H2)/2 where H adsorbs on Pt1 atom of Pt1Ti3/GDY with each Ti atom is coordinated by one OH group.

Fig. 3. Free energy diagrams for alkaline HER at U = 0 V (vs. RHE) on Pt1Ti3/GDY and the corresponding changes of charges of Pt atom in Pt1Ti3/GDY. Every step for water adsorption that enclosed in the black dashed box are shown in Fig. S8. Three of six H2O molecules are chemisorbed on the three Ti sites and involved in the Volmer step, while the other three H2O molecules are from the solution and involved in the Heyrovsky step.

Fig. 4. The optimized structures of Pt1Ti3/GDY with *H and *OH (left), and the corresponding charge density difference maps (right). Yellow and cyan iso-surface represents electron accumulation and electron depletion, respectively. (isosurface level at 0.002|e| Bohr?3). The grey, blue, brown, red and light brown spheres represent Pt, Ti, C, O and H, respectively.

Fig. 5. Relationship between d-band center of M atom in M1Ti3/GDY and calculated free energy of *H (a,c), reaction free energy (b,d) of water dissociation on M1Ti3/GDY at U = 0 V (vs. RHE), with (each Ti atom is coordinated by one OH group) and without *OH coverage, respectively. The gray region denotes |ΔG*H| < 0.2 eV. For M1Ti3/GDY with *OH coverage, Gads(*H) = G(*H-3*OH) - G(3*OH) - G(H2)/2. Gr = G(*H-3*OH) - G(2*OH-H2O*). For M1Ti3/GDY without *OH coverage, Gads(*H) = G(*H) - E(*) - G(H2)/2. Gr = G(*H - *OH) - G(H2O*).

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石墨炔负载的双金属单团簇催化剂用于碱性析氢反应

Bimetallic single-cluster catalysts anchored on graphdiyne for alkaline hydrogen evolution reaction

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