Breaking the scaling relations for efficient N-2-to-NH3 conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides

Jiang，Ya Fei1,2; Liu，Jin Cheng1; Xu，Cong Qiao2; Li，Jun1,2; Xiao，Hai1

2022-08-01

10.1016/S1872-2067(22)64129-9

CHINESE JOURNAL OF CATALYSIS   Impact Factor & Quartile

0253-9837

1872-2067

The design of optimal heterogeneous catalysts for N-2-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 N-2-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 N-2 that delivers facile cleavage of N.N bond, while destabilizes the adsorptions of *NHx (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 *NHx 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 N-2-to-NH3 conversion. (c) 2022, Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. All rights reserved.

N-2-to-NH3 conversion Scaling relations Heterogeneous catalyst design First-principles calculations

SCI ; EI

English

Others

National Natural Science Foundation of China["22122304","21903047","22033005","22038002"] ; Guangdong Basic and Applied Basic Research Foundation[2020A1515110282] ; Guangdong Provincial Key Laboratory of Catalysis[2020B121201002]

Chemistry ; Engineering

Chemistry, Applied ; Chemistry, Physical ; Engineering, Chemical

WOS:000826472700004

ELSEVIER

20222612297259

Ammonia ; Catalysis ; Catalyst activity

Chemical Reactions:802.2 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Inorganic Compounds:804.2 ; Mathematics:921

CHEMISTRY

2-s2.0-85132947211

Web of Science

1.Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education,Tsinghua University,Beijing,100084,China
2.Department of Chemistry,Southern University of Science and Technology,Shenzhen,Guangdong,518055,China

Jiang，Ya Fei,Liu，Jin Cheng,Xu，Cong Qiao,et al. Breaking the scaling relations for efficient N-2-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.

Jiang，Ya Fei,Liu，Jin Cheng,Xu，Cong Qiao,Li，Jun,&Xiao，Hai.(2022).Breaking the scaling relations for efficient N-2-to-NH3 conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides.CHINESE JOURNAL OF CATALYSIS,43(8),2183-2192.

Jiang，Ya Fei,et al."Breaking the scaling relations for efficient N-2-to-NH3 conversion by a bowl active site design: Insight from LaRuSi and isostructural electrides".CHINESE JOURNAL OF CATALYSIS 43.8(2022):2183-2192.