Fundamentals and Advances in Emerging Crystalline Porous Materials for Photocatalytic and Electrocatalytic Nitrogen Fixation

Abstract

Artificial nitrogen fixation, which uses N 2 and H 2 O as raw materials and is powered by renewable energy, is a more environmentally friendly method of permitting NH 3 synthesis under ambient conditions than the industrial Haber−Bosch process. However, only a few catalysts have been reported that can efficiently reduce the nitrogen activation barrier, resulting in low NH 3 production efficiency. Emerging crystalline porous materials (CPMs) are a class of lightweight porous network materials composed of metal and organic linking units through coordinate bonds or organic structural units through covalent bonds, with high surface areas, tunable pores, and designable compositions and structures. CPMs offer intriguing applications as catalysts for photocatalytic and electrocatalytic nitrogen fixation reactions due to their unique structures and characteristics, and significant progress has been made. This Review systematically summarizes the synthetic methods of emerging CPMs (MOFs and COFs), basic principles of photocatalytic and electrocatalytic nitrogen fixation reactions, some representative NH 3 synthesis catalysts and modification strategies, and common reactor types. Finally, prospective development directions of photocatalytic and electrocatalytic nitrogen fixation based on CPMs are proposed, providing a research basis for accelerating the industrialization of artificial nitrogen fixation driven by renewable energy.

Construction of a 2D layered BiVO4/zinc porphyrin (ZnTCPP) S-scheme heterostructure boosting photocatalytic N2oxidation performance

“…14–16 Ammonia and nitrates are important raw materials in modern industry, and compared with the traditional Haber-Bosch and Ostwald processes, the photocatalytic N 2 fixation shows great promise for sustainable environmental nitrogen fixation. 17…”

“…[14][15][16] Ammonia and nitrates are important raw materials in modern industry, and compared with the traditional Haber-Bosch and Ostwald processes, the photocatalytic N 2 xation shows great promise for sustainable environmental nitrogen xation. 17 To date, numerous semiconductor photocatalysts such as g-C 3 N 4 , TiO 2 , CdS, BiVO 4 , Fe 2 O 3 , etc., [18][19][20][21][22] have been developed to boost the efficiency of photocatalytic N 2 xation. However, these traditional semiconductor photocatalysts oen have a limited photoresponse range and poor energy band regulation, which restricts the effective utilization of solar light.…”

Enhancement of the properties of ZnAl-LDHs for photocatalytic nitrogen reduction reaction by controlling anion intercalation

“…The photocatalytic nitrogen reduction (PNR) reaction, based on the characteristics of semiconductor materials to generate photoelectrons under illumination, is considered as a green and renewable nitrogen fixation method instead of the Haber-Bosch process, which has attained widespread attention in recent years. 1,2 Although noble metal catalysts (such as Ag, 3,4 Au, 5,6 Pt, 7 etc.) exhibit excellent catalytic performance, their high price increases the cost of industrial production.…”

Ambient catalyst free nitrogen fixation with water dimer radical cation

“…100 bar and 500°C), severe environmental pollution (>1% of the global carbon emission) and high consumption of fossil fuel (1%-2% of global energy consumption) in the HB process are becoming increasingly crucial for the global sustainable development and urge novel strategies for N2 fixation under mild conditions 4,5 . Extensive research is being done in search of alternative strategies for N2 fixation to NH3, including electrocatalytic 6,7 , photocatalytic 8 , biological 9 , and plasma-based 10 methods, but none of these methods have yet been able to rival the overall performance of HB process with regard to the cost efficiency, scalability and selectivity of NH3 production 6,11,12 .…”