打破合成氨反应中线性标度关系的碗型活性位点设计: 来自LaRuSi及其同构电子化物的启示

doi:10.1016/S1872-2067(22)64129-9

催化学报 ›› 2022, Vol. 43 ›› Issue (8): 2183-2192.DOI: 10.1016/S1872-2067(22)64129-9

打破合成氨反应中线性标度关系的碗型活性位点设计: 来自LaRuSi及其同构电子化物的启示

蒋亚飞^a^,^b, 刘锦程^a, 许聪俏^b, 李隽^a^,^b, 肖海^a^,^*()

^a清华大学化学系, 有机光电与分子工程教育部重点实验室, 北京100084
^b南方科技大学化学系, 广东深圳518055

收稿日期:2022-02-01 接受日期:2022-04-12 出版日期:2022-08-18 发布日期:2022-06-20
通讯作者: 肖海
基金资助:
国家自然科学基金(22122304);国家自然科学基金(21903047);国家自然科学基金(22033005);国家自然科学基金(22038002);广东省基础与应用基础研究基金联合基金(2020A1515110282);广东省催化化学重点实验室(2020B121201002)

Breaking the scaling relations for efficient N₂-to-NH₃ conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides

Ya-Fei Jiang^a^,^b, Jin-Cheng Liu^a, Cong-Qiao Xu^b, Jun Li^a^,^b, Hai Xiao^a^,^*()

^aDepartment of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China
^bDepartment of Chemistry, Southern University of Science and Technology, Shenzhen 518055, Guangdong, China

Received:2022-02-01 Accepted:2022-04-12 Online:2022-08-18 Published:2022-06-20
Contact: Hai Xiao
About author:Hai Xiao obtained his B.Sc. and M.Sc. in Chemistry both from Tsinghua University. He later earned his Ph.D. from California Institute of Technology (Caltech), and continued to work at Caltech as a post-doc and research scientist. He joined Tsinghua University in 2017 and is currently an associate professor. His research area lies in computational chemistry, and his current research interests focus on the design of heterogenous catalytic systems and understanding of catalysis at electrochemical interfaces. He served as a young member of the Editorial Board of Chin. J. Catal. since 2020.
Supported by:
National Natural Science Foundation of China(22122304);National Natural Science Foundation of China(21903047);National Natural Science Foundation of China(22033005);National Natural Science Foundation of China(22038002);Guangdong Basic and Applied Basic Research Foundation(2020A1515110282);Guangdong Provincial Key Laboratory of Catalysis(2020B121201002)

摘要/Abstract

摘要：

合成氨反应是现代工业和农业中提供所需氮源的关键基础化学过程, 但在温和条件下实现低能耗、高效率合成氨反应的多相催化剂设计依然是一个挑战. 其中, 一个普适的限制起源于线性标度关系, 即合成氨反应中的一系列含氮物种在催化剂表面的吸附能构成正相关的线性关系, 这使得同时提高催化剂活化N₂与释放NH₃的能力形成矛盾, 最终导致最优的催化剂设计需要采用折衷办法, 即:最优催化剂对含氮物种的吸附既不能太强也不能太弱, 这正是Sabatier原则. 因此, 线性标度关系导致了催化剂设计中的火山型曲线, 其顶点限制了最优催化剂的性能. 如果想进一步优化催化剂性能, 超越该限制, 需要设计能打破合成氨反应中线性标度关系的多相催化剂活性位点.

基于电子化物LaRuSi催化合成氨反应机理的理论研究, 本文揭示了一种能打破合成氨反应中线性标度关系的碗型活性中心设计. 采用第一性原理计算, 首先确认了LaRuSi催化剂最稳定的(001)-La表面可高效催化合成氨反应, 其最优反应路径为解离机理. 通过理论分析发现, (001)-La表面上的碗型活性位点在高效催化中起到了关键作用. 该碗型活性位点由四个带正电的表面La离子和一个在催化过程中可变正负电荷的亚表面Si原子组成, 其既可通过有利的静电吸引和共价作用, 促进N₂的活化以及裂解; 又可通过静电排斥作用减弱NH_x物种的吸附, 促进NH₃的脱附释放. 因此, 该碗型活性位点在概念上打破了合成氨反应中的线性标度关系.

为了进一步定量确定被打破的线性标度关系, 对比了一系列与LaRuSi同构的电子化物以及一系列过渡金属表面, 确认碗型活性位点打破了NH_x物种与N物种吸附能的正相关线性关系.

本文还讨论了几种可能的包含类似碗型活性位点设计的合成氨催化体系, 包括: 覆盖了碱金属离子的过渡金属表面, 稀土金属和后过渡金属组成的合金体系(比如YRu₂), 以及过渡金属氢化物与碱金属组成的三元复合物(比如Li₄H₆Ru). 综上, 碗型活性位点展示了一种新的高效合成氨催化剂设计概念, 可打破合成氨反应中的线性标度关系, 超越火山型曲线顶点对催化性能的限制, 这为合成氨反应以及其它受线性标度关系所限制的催化反应的高效多相催化剂的理性设计提供了新的启示.

关键词: 合成氨反应, 线性标度关系, 多相催化剂设计, 第一性原理计算

Abstract:

The design of optimal heterogeneous catalysts for N₂-to-NH₃ conversion is often dictated by the scaling relations, which result in a volcano curve that poses a limit on the catalytic performance. Herein, we reveal a bowl active site that can break the scaling relations, through investigating the catalytic mechanisms of N₂-to-NH₃ conversion on the lanthanide intermetallic electride catalyst LaRuSi by first-principles modeling. This bowl active site, composed of four surface La cations and one subsurface Si atom rich in electrons, plays the key role in enabling efficient catalysis. With adaptive electrostatic and orbital interactions, the bowl active site promotes the adsorption and activation of N₂ that delivers facile cleavage of N‒N bond, while destabilizes the adsorptions of *NH_x (x = 1, 2, 3) species, which facilitates the release of the final NH₃ product. By comparison with other electride catalysts isostructural to LaRuSi, we confirm the breaking of scaling relations between the adsorptions of *NH_x species and that of *N on the bowl active site. Thus, this bowl active site presents a design concept that breaks the scaling relations for highly efficient heterogeneous catalysis of N₂-to-NH₃ conversion.

Key words: N2-to-NH3 conversion, Scaling relations, Heterogeneous catalyst design, First-principles calculations

蒋亚飞, 刘锦程, 许聪俏, 李隽, 肖海. 打破合成氨反应中线性标度关系的碗型活性位点设计: 来自LaRuSi及其同构电子化物的启示[J]. 催化学报, 2022, 43(8): 2183-2192.

Ya-Fei Jiang, Jin-Cheng Liu, Cong-Qiao Xu, Jun Li, Hai Xiao. Breaking the scaling relations for efficient N₂-to-NH₃ conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides[J]. Chinese Journal of Catalysis, 2022, 43(8): 2183-2192.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(22)64129-9

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Fig. 1. Electronic structure analyses of the most stable conformation of N2 adsorbed on the LaRuSi(001)-La surface. (a) Charge density difference upon N2 adsorption. (b) The bowl active site with selected bond lengths shown in the unit of ?. (c) Partial electron density in the energy range between Ef and Ef ? 1.0 eV on the (110) plane. (d) Projected densities of states (pDOS) of selected atoms on the LaRuSi(001)-La surface (i) before and (ii) after N2 adsorption. (iii) Crystal orbital Hamilton population (COHP) between the adsorbed N2 and LaRuSi(001)-La surface.

Fig. 2. The Gibbs free energy profiles for catalytic mechanisms of N2-to-NH3 conversion on the LaRuSi(001)-La surface, including all viable branches for both the dissociative and associative mechanisms. The superscripts b and t denote the bridge and top sites, respectively. Structures of intermediates and transition states (TS) along all the pathways are shown in Fig. S6.

Fig. 3 (a) Evolution of Si charge and distance between Si and N atoms for selected species along the N2-to-NH3 conversion. (b) Schematic electrostatic interactions between adsorbates and the bowl active site that break the scaling relations conceptually. (b) schematically depicts the charge distributions of the bowl active site with *N2 and *NH2 that regulate the electrostatic interactions. The initial activation of N2 to *N23? is well stabilized by favorable electrostatics, while the *NH2 and the final *NH3 are driven by repulsion to adsorb weakly on the bridge and top sites of La atoms, respectively. The final *NH3 thus is easily released from the (001)-La surface, recovering the active site for the next catalytic cycle. Conceptually, this breaks the scaling relations between the adsorption energies of *N and *NHx, and this is explicitly confirmed by comparison with other isostructural electride catalysts in the following section.

Fig. 4. The general structure of RTX(001)-R surface (R = Ca, La, Ce; T = Ru, Co, X = Si) with N2 adsorption. (b) The N?N bond lengths and adsorption energies of N2 on the RTX(001)-R surfaces. (c) The correlations of adsorption energies of *N2, *NH and *NH2 with the *N adsorption energy on the RTX(001)-R surfaces and 6 transition metal surfaces. Note that the data for the transition metal surfaces are taken from Ref. [2]. For clarity, the data for the Pd case are not shown here, but are included in Fig. S13.

Fig. 5. Other heterogeneous catalysts that may present the bowl active site design, including the Ru metal surface covered with K cations (a), the (001)-Y terminated surface of YRu2 alloy (b), and the ternay Ru complex hydride with Li cations (c).

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打破合成氨反应中线性标度关系的碗型活性位点设计: 来自LaRuSi及其同构电子化物的启示

Breaking the scaling relations for efficient N₂-to-NH₃ conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides

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打破合成氨反应中线性标度关系的碗型活性位点设计: 来自LaRuSi及其同构电子化物的启示

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Breaking the scaling relations for efficient N₂-to-NH₃ conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides