TY - JOUR

T1 - Emerging metal−organic framework-based materials for photocatalytic and electrocatalytic NH3 synthesis

T2 - Design principles, structure-activity correlation, and mechanistic insights

AU - Li, Ximing

AU - Tian, Lin

AU - Dong, Qibing

AU - Wang, Zhe

AU - Ralphs, Kathryn

AU - Esterhuysen, Catharine

AU - Robertson, Peter K.J.

AU - Bahnemann, Detlef W.

AU - He, Guanjie

AU - Wang, Chuanyi

N1 - Publisher Copyright: © 2025 Elsevier B.V.

PY - 2025/7/1

Y1 - 2025/7/1

N2 - Sustainable ammonia (NH3) synthesis through artificial nitrogen fixation has gained significant attention as a promising alternative to the energy-intensive Haber-Bosch process, offering a greener pathway for NH3 production. In particular, to optimize the economic sustainability pathway of NH3 synthesis technology, it is paramount to engineer novel catalysts. Emerging MOFs are a type of lightweight porous network materials with tunable channels, high surface areas, and designable components, which offer intriguing functionalities in photo- and electro-driven N2 reduction reaction (NRR) by lowering reaction potentials and accelerating reaction rates. Although some progress has been achieved in this area, fundamental issues remain to be addressed to better understand the relationship between the structures, properties, catalytic activity, and potential applications of MOF-based catalysts. Herein, based on the comprehensive design concept, the latest advancements in MOF-based material design principle, structural modulation mechanism, and reaction engineering are systematically summarized to elucidate the structure-activity correlations in NRR. It begins with the MOF-based material design principles, which encompass synthesis strategies, material properties, and the transition from laboratory to large-scale continuous production progress. Following that, in terms of structural modulation mechanism, particular emphasis is placed on the analysis of crystal structure, atomic configuration, and electronic properties, aiming to gain a deeper understanding of the transport and reaction processes of charge carriers. Furthermore, the structure-activity correlations and reaction engineering are elaborated for NRR. Finally, a comprehensive analysis of the prospects and challenges associated with MOF-based catalysts in NRR is presented, along with detailed solutions.

AB - Sustainable ammonia (NH3) synthesis through artificial nitrogen fixation has gained significant attention as a promising alternative to the energy-intensive Haber-Bosch process, offering a greener pathway for NH3 production. In particular, to optimize the economic sustainability pathway of NH3 synthesis technology, it is paramount to engineer novel catalysts. Emerging MOFs are a type of lightweight porous network materials with tunable channels, high surface areas, and designable components, which offer intriguing functionalities in photo- and electro-driven N2 reduction reaction (NRR) by lowering reaction potentials and accelerating reaction rates. Although some progress has been achieved in this area, fundamental issues remain to be addressed to better understand the relationship between the structures, properties, catalytic activity, and potential applications of MOF-based catalysts. Herein, based on the comprehensive design concept, the latest advancements in MOF-based material design principle, structural modulation mechanism, and reaction engineering are systematically summarized to elucidate the structure-activity correlations in NRR. It begins with the MOF-based material design principles, which encompass synthesis strategies, material properties, and the transition from laboratory to large-scale continuous production progress. Following that, in terms of structural modulation mechanism, particular emphasis is placed on the analysis of crystal structure, atomic configuration, and electronic properties, aiming to gain a deeper understanding of the transport and reaction processes of charge carriers. Furthermore, the structure-activity correlations and reaction engineering are elaborated for NRR. Finally, a comprehensive analysis of the prospects and challenges associated with MOF-based catalysts in NRR is presented, along with detailed solutions.

KW - Metal-organic frameworks (MOFs)

KW - N reduction reaction (NRR)

KW - Reaction mechanism

KW - Structure-activity correlations

KW - Sustainable ammonia synthesis

UR - http://www.scopus.com/inward/record.url?scp=85219154444&partnerID=8YFLogxK

U2 - 10.1016/j.ccr.2025.216543

DO - 10.1016/j.ccr.2025.216543

M3 - Review article

AN - SCOPUS:85219154444

VL - 534

JO - Coordination Chemistry Reviews

JF - Coordination Chemistry Reviews

SN - 0010-8545

M1 - 216543

ER -