非金属掺杂石墨烯异核双原子催化剂氮还原特性研究

doi:10.1016/S1872-2067(23)64500-0

摘要/Abstract

摘要：

氨是化肥、涂料等领域中重要的化工原料, 是产量第二高的商用化学品. 目前, 90%以上的氨均来自Haber-Bosch法, 该工艺需要高温高压, 能耗高, 且依赖化石燃料的使用, 排放大量CO₂, 在倡导节能环保的新时代, 该工艺面临严重的能耗及环保问题. 电催化氮还原合成氨(eNRR)是一种在常温常压条件下, 采用电能作为驱动, 以水和大气中的氮作为原料的新型绿色环保的合成氨方法, 有望替代传统合成氨工艺. 在eNRR过程中, 电催化剂的催化活性和选择性是提高电催化合成氨的关键. 目前, 单原子催化剂(SAC)因其高原子利用率、高选择性等优点, 在氧还原反应(ORR)、二氧化碳还原反应(CO₂RR)等方面得到广泛研究, 但其在eNRR反应中表现不佳, 因为单个金属原子位不能贡献足够多的电荷来活化惰性极强的N≡N键. 据此, 本文利用第一性原理计算, 通过高通量筛选, 系统研究了以非金属掺杂石墨烯为基质, 以异核金属原子为反应位的双原子催化剂的氮还原特性及其微观催化机理.

本文以B, S, P和N四种非金属元素与Fe, Co, Mo, W和Ru五种金属元素随机组成的40种催化剂M₁M₂-X做为催化剂模型, 根据两步筛选, 得到FeMo-S, RuMo-B, RuMo-P, RuMo-S和RuW-S五种双原子催化剂, 表现出优良的氮还原特性. 与现有研究相比, 五种双原子催化剂不但具有高催化活性(过电位为: FeMo-S (-0.18 V), RuMo-B (-0.25 V), RuMo-P (-0.27 V), RuMo-S (-0.29 V)和RuW-S (-0.24 V)), 较高的热力学稳定性, 而且可以有效抑制析氢(HER)反应. 为了进一步与相应的单原子催化剂做比较, 将单个金属原子键合于非金属元素掺杂的石墨烯基质上, 形成17种M-X单原子催化剂. 在同样的筛选机制下, 只有Mo-P催化剂具有好的催化活性, 但与HER的竞争劣势使其无法成为良好的催化剂. 非金属原子调制的异核双原子催化剂对氮还原表现出良好的催化特性有其本质的原因. 对双原子催化剂的电子特性进行研究, 如Bader电荷、态密度、轨道哈密顿布居和电子差分密度等, 结果表明, 双原子催化剂的优良催化特性与下面几个方面有关: (1) 金属双原子作为催化位点, 可以提供更多的d电子, 使其转移到氮气分子的反键轨道, 从而活化N≡N键, 两套d轨道也可以接纳更多的来自氮分子的孤对电子以增强吸附; (2) 双原子的协同作用有效的调整了伴随金属原子的d带中心位置, 中间吸附质的吸附自由能因此得到调节, 从而改善了催化剂的催化性能; (3) 不同种类的非金属元素的引入丰富了金属反应位的配体结构, 使得催化剂对中间吸附质的吸附强度得到调节, 从而降低了初始电位.

综上, 本文不仅分析了异核双原子催化剂性能, 还从电子结构层面分析了NRR催化机理, 为设计高性能催化剂提供一定借鉴. 目前, 电子结构的计算广泛应用于催化剂设计领域, 它从电子结构层面深入理解催化机理, 为催化剂设计, 催化性能调控给出优化趋势. 电催化是一个由多种因素共同影响的复杂化学过程, 希望今后能够通过电子结构计算更加深入理解化学反应细节, 能够对反应过程给出动力学分析, 发现一般规律, 设计出高性能NRR催化剂.

关键词: 电催化, 双原子催化剂, 石墨烯, 氮还原反应, 第一性原理

Abstract:

Electrochemical nitrogen reduction reaction (eNRR) is a promising strategy for sustainable ammonia production. To achieve high yield and energy efficiency, single-atom dispersion on nitrogen-doped graphene nanosheets has been extensively explored as an electrocatalyst for eNRR. However, challenges remain owing to the high overpotentials arising from unitary active sites and unabundant ligands. In this study, heteronuclear dual-metal catalysts with different non-metals doped in a graphene frame were computationally designed. After a two-step scanning based on density functional theory calculations, five candidates, namely FeMo-S, RuMo-B, RuMo-P, RuMo-S, and RuW-S, were identified as promising catalysts with calculated onset potentials of -0.18, -0.25, -0.27, -0.29, and -0.24 V, respectively. These catalysts can also effectively suppress the competitive hydrogen evolution reaction during NRR. Such excellent catalytic performance origins from two synergetic effects: (1) the cooperation of heteronuclear metals contribute to the electron transfer from active sites to the anti-bonding orbitals of N₂ molecules adsorbed on catalysts to effectively activate N≡N bonds; (2) metal-ligands (non-metals) interactions moderate the binding strength of intermediates to slab, which is one of reasons for low NRR onset potential and high NH₃ selectivity. The present study provides a theoretical understanding of the NRR mechanism of dual-metal catalysts, offering useful guidance for the rational design of catalysts with high selectivity and activity for NRR.

Key words: Electrocatalysis, Dual-atom catalyst, Graphene, Nitrogen reduction reaction, First principle theory

张季, 俞爱民, 孙成华. 非金属掺杂石墨烯异核双原子催化剂氮还原特性研究[J]. 催化学报, 2023, 52: 263-270.

Ji Zhang, Aimin Yu, Chenghua Sun. Theoretical insights into heteronuclear dual metals on non-metal doped graphene for nitrogen reduction reaction[J]. Chinese Journal of Catalysis, 2023, 52: 263-270.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64500-0

https://www.cjcatal.com/CN/Y2023/V52/I9/263

图/表 7

Fig. 1. DAC model and reaction process of NRR. (a) Two types of transition metal atoms bounded to the defective graphene matrix along with six nitrogen atoms and another non-metallic atom as its ligands. (b) Schematic representation of NRR mechanisms, including alternating, distal, and enzymatic processes.

Fig. 2. Calculated Gibbs free energy changes for the first and last hydrogenation steps of NRR on M1M2-X catalysts. The dash line represents the value at 0.50 eV. The cyan area encompasses the most promising candidates for NRR.

Fig. 3. NRR and HER selective analysis. NRR is dominant within the bottom right region, while HER is dominant within the top left region.

Fig. 4. Calculated Gibbs free energy changes for the first and last steps of the NRR process on M1M2-X catalysts and their corresponding M-X SACs.

Fig. 5. Free energy profiles for NRR through enzymatic mechanism on FeMo-S (a), RuMo-P (b), RuMo-B (c), RuMo-S (d), and RuW-S (e).

Fig. 6. Study of N2 activation. (a) Optimized configurations of each intermediate adsorbed on the RuMo-B surface for NRR along with the enzymatic pathway under side-on configuration. (b) Diagrams of charge density differences in RuMo-B with N2 adsorption under side-on configuration (the charge density accumulation and depletion areas are displayed in yellow and cyan). (c) projected crystal orbital Hamilton populations (pCOHP) for N-N bonded to Ru-B, Mo-B, and RuMo-B under side-on configuration, respectively; PDOS before (d) and after (e) N2 was adsorbed on Ru-B, Mo-B, and RuMo-B, respectively (the d orbital of the metal atom is represented by the black line, and the N-2p orbital is represented by gray areas).

Fig. 7. Schematic diagram of dual-atom synergistic effect between Ru and Mo atoms, which enhance the NRR activity via moderation of the d-band center of catalysts, shown at the middle of the graph.

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