Computational design of catalysts for ammonia synthesis

Abstract

Ammonia plays a crucial role in agriculture and chemical engineering, and acts as a promising carbon-free transportation fuel. Catalysts design is deemed as a key to solve the restriction of energy-intensive Haber-Bosch process of ammonia production. With the development of computational modeling, computation-aided catalyst design serves as one important driving force for material innovation, saving a lot of experimental efforts based on trial and error. Computational modeling not only provides fundamental mechanistic insights into the reaction with great details regarding adsorbate geometries, electronic structures, and elementary-step energies, but also expedites the material discovery with descriptor-based catalyst design, core of which is the establishment of thermo/kinetic scaling relations. In this review, we present firstly the mechanistic understanding of ammonia synthesis and transition state scaling relations developed on pure transition-metal catalysts. We then summarize catalysts design strategies guided by alloy, size, and magnetic effects with the goal of breaking the limitations set by scaling relations to achieve better catalytic performance. Finally, future opportunities and challenges associated with computation design of optimal catalysts for ammonia synthesis are outlined.

Symmetry-Breaking p-Block Antimony Single Atoms Trigger N-Bridged Titanium Sites for Electrocatalytic Nitrogen Reduction with High Efficiency

“…DFT calculations were performed to investigate the origin of the activity of the Sb SA/N-Ti 3 C 2 T x catalyst toward NRR. − Herein, the Ti 3 C 2 O 2 structure model was constructed as a substitute for Ti 3 C 2 T x . First, the oxygen vacancy formation energies on Ti 3 C 2 O 2 , N-Ti 3 C 2 O 2 , and Sb SA/N-Ti 3 C 2 O 2 were calculated because the abundant oxygen vacancies could promote the exposure of metal active sites.…”

Structural engineering of catalysts for ammonia electrosynthesis from nitrate: recent advances and challenges

“…A well-designed electrocatalyst can boost the activity and selectivity of the NitRR. 139,169 We hope this review helps researchers to develop new catalyst strategies to realize green ammonia electrosynthesis from nitrate under mild conditions. In addition, outstanding electrocatalysts are encouraged to promote the nitrate electroreduction technology from the laboratory to industry, thereby managing nitrate-rich wastewater.…”

Ultrafine AuCu nanowires for electrocatalytic nitrogen fixation

“…[15][16][17] Alloying Au with another transition metal to form a bimetallic structure is a promising strategy, which not only can tailor the adsorption energy of nitrogen species on metals but also can reduce the catalyst cost. [18][19][20][21] Cu has been widely developed as a promising dopant to improve the NRR performance through morphological modification and electronic reconstruction. [22][23][24][25] It has been reported that PdCu nanoparticles anchored to boron nanosheets (PdCu/B) showed superior NRR performance compared to their monometallic counterparts because the introduction of copper can form symmetry-breaking interfacial structures and change the adsorption conformation of N 2 , thus optimizing the NRR performance.…”