Exploring nitrogen reduction reaction mechanisms in electrocatalytic ammonia synthesis:A comprehensive review

The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia synthesis.While the process is thermodynamically feasible at ambient temperature and pressure,challenges such as the competing hydrogen evolution reaction,low nitrogen solubility in electrolytes,and the activation of inert dinitrogen(N_(2))gas adversely affect the performance of ammonia production.These hurdles result in low Faradaic efficiency and low ammonia production rate,which pose obstacles to the commercialisation of the process.Researchers have been actively designing and proposing various electrocatalysts to address these issues,but challenges still need to be resolved.A key strategy in electrocatalyst design lies in understanding the underlying mechanisms that govern the success or failure of the electrocatalyst in driving the electrochemical reaction.Through mechanistic studies,we gain valuable insights into the factors affecting the reaction,enabling us to propose optimised designs to overcome the barriers.This review aims to provide a comprehensive understanding of the various mechanisms involved in eNRR on the electrocatalyst surface.It delves into the various mechanisms such as dissociative,associative,Mars-van Krevelen,lithium-mediated nitrogen reduction and surface hydrogenation mechanisms of nitrogen reduction.By unravelling the intricacies of eNRR mechanisms and exploring promising avenues,we can pave the way for more efficient and commercially viable ammonia synthesis through this sustainable electrochemical process by designing an efficient electrocatalyst.

Unveiling the chemistry behind the electrolytic production of hydrogen peroxide by oxygenated carbon

Oxygenated carbon materials exhibit outstanding electrocatalytic performance in the production of hydrogen peroxide(H2O2)through a two-electron oxygen reduction reaction.The nature of the active functional group and underlying reaction mechanism,however,remain unclear.Here,a comprehensive workflow was established to identify the active sites from the numerous possible structures.The common hydroxyl group at the notched edge demonstrates a key role in the two-electron process.The local chemical environment weakens the binding of OOH intermediate to substrate while enhancing interaction with solution,thereby promoting the H_(2)O_(2)production.With increasing pH,the intramolecular hydrogen bond between OOH intermediate and hydroxyl decreases,facilitating OOH desorption.Furthermore,the rise in selectivity with increasing potential stems from the suppression of the four-electron process.The active site was further validated through experiments.Guided by theoretical understanding,optimal performance was achieved with high selectivity(>95%)and current density(2.06 mA/cm^(2))in experiment.

Induced growth of Fe-N_x active sites using carbon templates

Highly active Fe-N_x sites that effectively improve the performance of non-precious metal electrocatalysts for oxygen reduction reactions（ORRs） are desirable. Herein, we propose a strategy for introducing a carbon template into a melamine/Fe-salt mixture to inductively generate highly active Fe-N_x sites for ORR. Using 57 Fe M？sbauer spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction, we studied the structural composition of the Fe and N co-doped carbon catalysts.Interestingly, the results showed that this system not only converted inactive Fe and Fe-carbides into active Fe-N_4 and other Fe-nitrides, but also improved their intrinsic activities.

Cationic surface polarization centers on ionic carbon nitride for efficient solar-driven H_(2)O_(2) production and pollutant abatement

Solar-driven H_(2)O_(2)production and emerging organic pollutants(EOPs)elimination are of great significance from the perspective of environmental sustainability.The efficiency of the photocatalytic reaction system is the key challenge to be addressed.In this work,the strategy of constructing surface ionic local polarization centers to enhance the exciton dissociation of the polymeric photocatalytic is demonstrated.Selected bipyridinium cation(TMAP)is complexed on a K^(+)-incorporated carbon nitride(CNK)framework,and the combination of local polarization centers both on the surface(bipyridinium cation)and bulk(K+cation)contributes to a superior photocatalytic H_(2)O_(2)production performance,affording a remarkable H_(2)O_(2)generation rate of 46.8μmol h^(-1)mg^(-1)and a high apparent quantum yield(AQY)value of 77.5%under irradiation of 405 nm photons.As substantiated experimentally by steady state/transient spectroscopy techniques,the surface local polarization centers increase the population of the long-lived trapped electrons,and thereby promote the interfacial charge transfer process for chemical conversion reaction.The strategy is potentially applicable to the design of a wide range of efficient solar-to-chemical conversion systems.

Recent advances and trends of single-atom catalysts for proton exchange membrane fuel cell cathodes

Proton exchange membrane fuel cells(PEMFCs),which have the advantages of high-power density,zero emission,and low noise,are considered ideal electrochemical conversion systems for converting hydrogen(H2)and oxy-gen(O_(2))/air into electricity.However,the oxygen reduction reaction(ORR),which is accompanied by multiple electrons,results in voltage loss and low conversion efficiency of PEMFCs.Currently,PEMFCs mainly use high-load precious platinum(Pt)to promote the ORR process;however,the high cost of Pt hinders the widespread commercialization of PEMFCs.Over the past few years,metal-nitrogen-carbon single-atom catalysts(M-N-C SACs)have attracted considerable attention and have been recognized as potential Pt-based catalysts owing to their outstanding ORR activity.This review briefly introduces the components of PEMFCs.Second,we discuss the catalytic mechanisms of the M-N-C SACs for the ORR.Third,the latest advances in noble,non-noble,and heteroatom-doped M-N-C SACs used as ORR and PEMFCs cathode catalysts are systematically reviewed.In sum-mary,we have outlined the current challenges and proposed a future perspective of M-N-C SACs for PEMFCs cathodes.

Novel LaFe_(2)O_(4)spinel structure with a large oxygen reduction response towards protonic ceramic fuel cell cathode

Highly active and stable electrocatalysts are mandatory for developing high-performance and longlasting fuel cells.The current study demonstrates a high oxygen reduction reaction(ORR)electrocatalytic activity of a novel spinel-structured LaFe_(2)O_(4)via a self-doping strategy.The LaFe_(2)O_(4)demonstrates excellent ORR activity in a protonic ceramic fuel cell(PCFC)at temperature range of 350-500℃.The high ORR activity of LaFe_(2)O_(4)is mainly attributed to the facile release of oxide and proton ions,and improved synergistic incorporation abilities associated with interplay of multivalent Fe^(3+)/Fe^(2+)and La^(3+)ions.Using LaFe_(2)O_(4)as cathode over proton conducting BaZr_(0.4)Ce_(0.4)Y_(0.2)O_(3)(BZCY)electrolyte,the fuel cell has delivered a high-power density of 806 mW/cm^(2)operating at 500℃.Different spectroscopic and calculations methods such as UV-visible,Raman,X-ray photoelectron spectroscopy and density functional theory(DFT)calculations were performed to screen the potential application of LaFe_(2)O_(4)as cathode.This study would help in developing functional cobalt-free ORR electrocatalysts for low temperature-PCFCs(LT-PCFCs)and solid oxide fuel cells(SOFCs)applications.

One-step scalable preparation of N-doped nanoporous carbon as a high-performance electrocatalyst for the oxygen reduction reaction

N-doped porous carbon materials have been prepared by a simple one-step pyrolysis of ethylenediaminetetraacetic acid （EDTA） and melamine in the presence of KOH and Co（NO3）2·6H20. The combination of the high specific area （1,485 m2.g-l）, high nitrogen content （10.8%） and suitable graphitic degree results in catalysts exhibiting high activity （with onset and half-wave potentials of 0.88 and 0.79 V vs the reversible hydrogen electrode （RHE）, respectively） and four-electron selectivity for the oxygen reduction reaction （ORR） in alkaline medium---comparable to a commercial Pt/C catalyst, but far exceeding Pt/C in stability and durability. Owing to their superb ORR performance, low cost and facile preparation, the catalysts have great potential applications in fuel cells, metal-air batteries, and ORR-related electrochemical industries.

Advanced non-precious electrocatalyst of the mixed valence CoO_x nanocrystals supported on N-doped carbon nanocages for oxygen reduction

Taking advantage of the nitrogen(N)-participation and large surface area of N-doped carbon nanocages(NCNCs),the Co Ox nanocrystals are conveniently immobilized onto the NCNCs with high dispersion.The Co Ox/NCNCs hybrid exists in the mixed valence with predominant Co O over Co3O4 and demonstrates superb oxygen reduction reaction activity and stability remaining^94%current density even after operation over 100 h.These results suggest a promising strategy to develop advanced electrocatalysts with the novel NCNCs or even beyond.