电化学氮还原反应热力学火山关系的组合描述符

doi:10.1016/S1872-2067(22)64128-7

摘要/Abstract

摘要：

电化学氨合成是一种极具前景的清洁氨合成方法, 但目前受限于较低的催化效率, 难以实现大规模的工业化应用. 因此, 发展高活性的电化学氮还原反应(eNRR)催化剂非常必要, 而理解eNRR机理, 并构建简单的活性预测指标, 能够很好地促进催化剂的发展. 根据催化反应活化能与反应能之间的线性自由能(BEP)关系, 以及各反应中间体的吸附能之间的标度关系, 可以建立催化剂活性与单个反应中间体吸附能(单描述符)之间的火山关系. 这种火山关系为提升催化剂活性指明方向, 从而促进催化剂的合理设计与筛选.

本文对一系列的单原子催化剂(SACs)和单团簇催化剂(SCCs)进行了密度泛函理论(DFT)计算, 确定了其最主要的反应机理, 并计算了机理下的中间体的吸附能. 结果表明, 以文献中常用的N原子吸附能作为单描述符, 其标度关系的线性相关性较差. 相应地, 基于这种单描述符的火山曲线也不能很好地预测催化剂的活性趋势. 还考察了其它中间体的吸附能作为单描述符的情况, 虽然某些单描述符具有较好的线性相关性, 但对不同类型的催化剂, 可以充当单描述符的中间体不同. 比如, 对于SACs, 最好的单描述符为N₂H₂的吸附自由能(ΔG_*NNH2), 而对于SCCs, 最好的单描述符则为ΔG_N2H. 结果表明, 基于单描述符的火山关系曲线并不能很好地预测eNRR催化活性.

基于单描述符的火山关系在eNRR催化剂活性预测中失效的主要原因是其涉及两类吸附构型的中间体. 在N‒N键解离之前, 反应中间体*N₂H_x通过两个氮原子与催化剂的活性中心相互作用; 而N‒N键解离后, 只有一个N原子与催化剂的活性中心相互作用. 这两种吸附模式使得各中间体吸附能之间没有统一的标度关系. 基于此, 本文提出一种组合描述符, 即一个单位点吸附中间体和一个双位点吸附中间体自由能之和作为描述符, 可以较好地描述eNRR活性. 结果表明, 使用组合描述符可以得到较为理想的标度关系, 因而能够显著改善火山关系曲线的预测性. 特别是, 当使用组合描述符ΔG_*NH2+ΔG_*NNH时, 活性火山曲线的顶点对应的描述符的值是固定的, 正好是NH₃的形成自由能, 不随催化剂类型改变. 而利用单描述符或其它组合描述符的火山曲线顶点随催化剂类型改变. 因此, 组合描述符ΔG_*NH2+ΔG_*NNH能够更方便、准确地指导eNRR催化剂的设计与筛选.

关键词: 电催化, 电化学氮还原反应, 单原子催化剂, 单团簇催化剂, 标度关系

Abstract:

Though touted as a potential way to realize clean ammonia synthesis, electrochemical ammonia synthesis is currently limited by its catalytic efficiency. Great effort has been made to find catalysts with improved activity toward electrochemical nitrogen reduction reaction (eNRR). Rational screening of catalysts can be facilitated using the volcano relationship between catalytic activity and adsorption energy of an intermediate, namely, the activity descriptor. In this work, we propose ΔG_*NH2+ΔG_*NNH as a combinatorial descriptor, which shows better predictive power than traditional descriptors using the adsorption free energies of single intermediates. The volcano plots based on the combinatorial descriptor exhibits peak activity fixedly at the descriptor value corresponding to the formation free energy of NH₃, regardless of the catalyst types; while the descriptor values correspond to the top activities for eNRR on volcano plots based on single descriptors usually vary with the types of catalysts.

Key words: Electrocatalysis, Electrochemical nitrogen reduction reaction, Single atom catalyst, Single cluster catalyst, Scaling relationship

蒋子艺, 胡友成, 黄俊, 陈胜利. 电化学氮还原反应热力学火山关系的组合描述符[J]. 催化学报, 2022, 43(11): 2881-2888.

Ziyi Jiang, Youcheng Hu, Jun Huang, ShengLi Chen. A combinatorial descriptor for volcano relationships of electrochemical nitrogen reduction reaction[J]. Chinese Journal of Catalysis, 2022, 43(11): 2881-2888.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64128-7

https://www.cjcatal.com/CN/Y2022/V43/I11/2881

图/表 10

Fig. 1. (a) The top and side view of SCCs. (b) The top view of five types of SACs. Atoms in gray color represent C atoms, those in blue represent N and those in bluish violet represent metal atoms.

Fig. 2. (a) Diagram of three adsorption configurations of N2. (b) Reaction pathway for SCCs. (c) All possible reaction pathway for SACs.

Fig. 3. Scaling relationships between adsorption free energy of N, s-N2, *N-*N (a), s-NNH, s-NHNH (b), s-NHNH2, e-NNH, NH, NH2 (c) and adsorption free energy of N on SCCs. (d) Reaction free energy of each CPET and volcano curve based on single descriptor for SCCs, each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, the solid lines represent the volcano curve.

Fig. 4. Scaling relationships between adsorption free energy of N, NH, NH2 (a), NNH, NHNH, NNH2 (b), NHNH2, NH2NH2 (c) and adsorption free energy of N on SACs. (d) Reaction free energy of each CPET and volcano curve based on single descriptor for SACs, each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, the solid lines represent the volcano curve.

Fig. 5. Scaling relationship between adsorption free energy of N, s-N2, *N-*N (a), s-NNH, s-NHNH, s-NHNH2 (b), e-NNH, NH, NH2 (c) and combinatorial descriptor on SCCs. (d) Reaction free energy of each CPET and volcano curve based on combinatorial descriptor for SCCs, each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, the solid lines represent the volcano curve.

Fig. 6. Scaling relationship between adsorption free energy of N, NH, NH2 (a), NNH, NHNH, NNH2 (b), NHNH2, NH2NH2 (c) and combinatorial descriptor on SACs. (d) Reaction free energy of each CPET and volcano curve based on combinatorial descriptor for SACs, each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, and the solid lines represent the volcano curve.

Table 1 R2 value of scaling relationship between intermediates adsorption energy and single descriptor or combinatorial descriptor in and SCCs.

Descriptor	ΔG_*N	ΔG_*NH	ΔG_*NH2	ΔG_s-N2	ΔG_s-NNH	ΔG_s-NHNH	ΔG_s-NHNH2	ΔG_{N N}	ΔG_e-NNH
ΔG_*N	1	0.889	0.568	0.645	0.855	0.712	0.333	0.924	0.856
ΔG_NH2+ΔG_NNH	0.820	0.885	0.840	0.877	0.975	0.932	0.590	0.898	0.884

Table 2 R2 value of scaling relationship between intermediates adsorption energy and single descriptor or combinatorial descriptor in and SACs.

Descriptor	ΔG_*N	ΔG_*NH	ΔG_*NH2	ΔG_*NNH	ΔG_*NHNH	ΔG_*NNH2	ΔG_*NHNH2	ΔG_*NH2NH2
ΔG_*N	1	0.910	0.795	0.896	0.775	0.905	0.795	0.633
ΔG_NH2+ΔG_NNH	0.871	0.958	0.970	0.968	0.876	0.962	0.965	0.747

Fig. 7. Reaction energy of each CPET and Volcano relationship model based on combinatorial descriptor for side-on (a) and end-on (b) configuration for SACs from Ref. [34]. Each point represents the maximum value of CPET free energy for catalyst, each dotted line represents the scaling relationship between the CPET free energy and the descriptor, the solid lines represent the volcano curve.

Fig. 8. Summary of volcano curves based on combinatorial descriptor. Curves in red, blue represent volcano curves of SCCs and SACs. Curves in green and purple represent volcano curves end-on configuration and side-on configuration from Ref. [34], respectively.

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