Oxygen‑Coordinated Single Mn Sites for Efficient Electrocatalytic Nitrate Reduction to Ammonia

Electrocatalytic nitrate reduction reaction has attracted increasing attention due to its goal of low carbon emission and environmental protection.Here,we report an efficient NitRR catalyst composed of single Mn sites with atomically dispersed oxygen(O)coordination on bacterial cellulose-converted graphitic carbon(Mn-O-C).Evidence of the atomically dispersed Mn-(O-C_(2))_(4)moieties embedding in the exposed basal plane of carbon surface is confirmed by X-ray absorption spectroscopy.As a result,the as-synthesized Mn-O-C catalyst exhibits superior NitRR activity with an NH_(3)yield rate(RNH_(3))of 1476.9±62.6μg h^(−1)cm^(−2)at−0.7 V(vs.reversible hydrogen electrode,RHE)and a faradaic efficiency(FE)of 89.0±3.8%at−0.5 V(vs.RHE)under ambient conditions.Further,when evaluated with a practical flow cell,Mn-O-C shows a high RNH_(3)of 3706.7±552.0μg h^(−1)cm^(−2)at a current density of 100 mA cm−2,2.5 times of that in the H cell.The in situ FT-IR and Raman spectroscopic studies combined with theoretical calculations indicate that the Mn-(O-C_(2))_(4)sites not only effectively inhibit the competitive hydrogen evolution reaction,but also greatly promote the adsorption and activation of nitrate(NO_(3)^(−)),thus boosting both the FE and selectivity of NH_(3)over Mn-(O-C_(2))_(4)sites.

Progress in electrocatalytic nitrate reduction for green energy:Catalyst engineering,mechanisms,and techno-economic feasibility

Ammonia(NH_(3))is an irreplaceable chemical that has been widely demanded to keep the sustainable development of modern society.However,its industrial production consumes a huge amount of energy and releases extraordinary greenhouse gases(GHGs),leading to various environmental issues.Achieving the green production of ammonia is a great challenge,which has been extensively pursued in the last decade.In this review,the most promising strategy,electrochemical nitrate reduction reaction(e-NO_(3)RR),is comprehensively investigated to give a complete understanding of its development and mechanism and provide guidance for future directions.However,owing to the complex reactions and limited selectivity,a comprehensive understanding of the mechanisms is crucial to further development and commercialization.Moreover,NO_(3)^(-)RR is a promising strategy for simultaneous water treatment and NH_(3)production.A detailed overview of the recent progress in NO_(3)^(-)RR for NH_(3)production with nontransition and transition metal based electrocatalysts is summarized.In addition,critical advanced techniques,future challenges,and prospects are discussed to guide future research on transition metal-based catalysts for commercial NH_(3)synthesis by NO_(3)^(-)reduction.

Electrocatalysts with atomic-level site for nitrate reduction to ammonia

Ammonia(NH_(3))is an important raw material for modern agriculture and industry,being widely demanded to sustain the sustainable development of modern society.Currently,the industrial production methods of NH_(3),such as the traditional Haber-Bosch process,have drawbacks including high energy consumption and significant carbon dioxide emissions.In recent years,the electrocatalytic nitrate reduction reaction(NO_(3)RR)powered by intermittent renewable energy sources has gradually become a multidisciplinary research hotspot,as it allows for the efficient synthesis of NH_(3)under mild conditions.In this review,we focus on the research of electrocatalysts with atomic-level site,which have attracted attention due to their extremely high atomic utilization efficiency and unique structural characteristics in the field of NO_(3)RR.Firstly,we introduce the mechanism of nitrate reduction for ammonia synthesis and discuss the in-situ characterization techniques related to the mechanism study.Secondly,we review the progress of the electrocatalysts with atomic-level site for nitrate reduction and explore the structure-activity relationship to guide the rational design of efficient catalysts.Lastly,the conclusions of this review and the challenges and prospective of this promising field are presented.

Potential-dependent insights into the origin of high ammonia yield rate on copper surface via nitrate reduction:A computational and experimental study

Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.

Cu-based heterojunction catalysts for electrocatalytic nitrate reduction to ammonia

Copper-based catalysts have garnered wide attention in the field of electrocatalytic nitrate reduction for ammonia production due to their low hydrogen precipitation activity and high ammonia selectivity.However,they still face challenges pertaining of poor stability and low activity,which hinder their further application.Herein,we present a Cu_(2)O/Cu heterojunction catalyst supported on nitrogen-doped porous carbon for nitrate reduction.High resolution transmission electron microscopy(HRTEM)and X-ray Diffraction(XRD)results confirm the presence of Cu_(2)O/Cu heterojunctions,which serve as an active phase in catalysis.The nitrogen-doped porous carbon as a carrier not only enhances the catalyst’s stability,but also facilitates the exposure and dispersion of active sites.At-1.29 V(vs.RHE),the maximum production rate of ammonia reaches 8.8 mg/(mg·h)with a Faradaic efficiency of 92.8%.This study also elucidates the effect of Cu_(2)O-to-Cu ratio in the heterojunction on catalytic performance,thereby providing valuable insights for designing efficient nitrate reduction catalysts for ammonia production.

Accelerating Electrocatalytic Nitrate Reduction to Ammonia via Weakening of Intermediate Adsorption on Cu-Based Catalyst

Cu-based materials are commonly used in electrocatalytic nitrate reduction reactions(NO 3 RR).NO 3 RR is a“two birds,one stone”approach,simultaneously removing NO 3−pollutants and producing valuable ammonia(NH 3).However,the strong coordination between the NO 3−intermediate and the catalytic active sites seriously hinders the conversion effi ciency.Here,we determined that,through encapsulation strategies,the carbon layer could weaken the NO 3−intermediate binding to active sites,resulting in higher NH 3 yields.We experimentally fabricated electrocatalysts,i.e.,Cu nanoparticles encapsulating(or loaded on)N-doped carbon nanofi bers(NCNFs)called Cu@NCNFs(Cu-NCNFs),using electrostatic spinning.As a result,Cu@NCNFs can achieve NH 3 yields of 17.08 mg/(h·mg cat)at a voltage of−0.84 V and a Faraday effi ciency of 98.15%.Meanwhile,the electrochemical properties of the Cu nanoparticles on the surface of carbon fi bers(Cu-NCNFs)are lower than those of the Cu@NCNFs.The in situ Raman spectra of Cu@NCNFs and Cu-NCNFs under various reduction potentials during the NO 3 RR process show that catalyst encapsulation within carbon layers can eff ectively reduce the adsorption of N species by the catalyst,thus improving the catalytic performance in the nitrate-to-ammonia catalytic conversion process.

Recent Advances in Transition Metal-Based Catalysts for Electrocatalytic Nitrate Reduction Reaction

The accumulation of excessive nitrate in the atmosphere not only jeopardizes human health but also disrupts the balance of the nitrogen cycle in the ecosystem.Among various nitrate removal technologies,electrocatalytic nitrate reduction reaction(eNO_(3)RR)has been widely studied for its advantages of being eco-friendly,easy to operate,and controllable under environmental conditions with renewable energy as the driving force.Transition metal-based catalysts(TMCs)have been widely used in electrocatalysis due to their abundant reserves,low costs,easy-to-regulate electronic structure and considerable electrochemical activity.In addition,TMCs have been extensively studied in terms of the kinetics of the nitrate reduction reaction,the moderate adsorption energy of nitrogen-containing species and the active hydrogen supply capacity.Based on this,this review firstly discusses the mechanism as well as analyzes the two main reduction products(N_(2)and NH_(3))of eNO_(3)RR,and reveals the basic guidelines for the design of efficient nitrate catalysts from the perspective of the reaction mechanism.Secondly,this review mainly focuses on the recent advances in the direction of eNO_(3RR)with four types of TMCs,Fe,Co,Ni and Cu,and unveils the interfacial modulation strategies of Fe,Co,Ni and Cu catalysts for the activity,reaction pathway and stability.Finally,reasonable suggestions and opportunities are proposed for the challenges and future development of eNO_(3)RR.This review provides far-reaching implications for exploring cost-effective TMCs to replace high-cost noble metal catalysts(NMCs)for eNO_(3)RR.

Mesoporous Carbon Nanofibers Loaded with Ordered PtFe Alloy Nanoparticles for Electrocatalytic Nitrate Reduction to Ammonia

Highly dispersed bimetallic alloy nanoparticle electrocatalysts have been demonstrated to exhibit exceptional performance in driving the nitrate reduction reaction(NO_(3)RR)to generate ammonia(NH_(3)).In this study,we prepared mesoporous carbon nanofibers(mCNFs)functionalized with ordered PtFe alloys(O-PtFe-mCNFs)by a composite micelle interface-induced co-assembly method using poly(ethylene oxide)-block-polystyrene(PEO-b-PS)as a template.When employed as electrocatalysts,O-PtFe-mCNFs exhibited superior electrocatalytic performance for the NO_(3RR)compared to the mCNFs functionalized with disordered PtFe alloys(D-PtFe-mCNFs).Notably,the NH_(3)production performance was particularly outstanding,with a maximum NH_(3)yield of up to 959.6μmol/(h·cm~2).Furthermore,the Faraday efficiency(FE)was even 88.0%at-0.4 V vs.reversible hydrogen electrode(RHE).This finding provides compelling evidence of the potential of ordered PtFe alloy catalysts for the electrocatalytic NO_(3)RR.

Kinetics and corrosion products of aqueous nitrate reduction by iron powder without reaction conditions control

Although considerable research has been conducted on nitrate reduction by zero-valent iron powder （Fe^0）, these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practical application. Without reaction conditions （dissolved oxygen or reaction pH） control, this work aimed at subjecting the kinetics of denitrification by microscale Fe^0 （160-200 mesh） to analysis the factors affecting the denitrification of nitrate and the composition of iron reductive products coating upon the iron surface. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. The reduction rate of nitrate increased with increasing Fe^0 dosage. The reaction can be described as a pseudo-first order reaction with respect to nitrate concentration or Fe^0 dosage. Experimental results also suggested that nitrate reduction by microscale Fe^0 without reaction condition control primarily was an acid-driven surface-mediated process, and the reaction order was 0.65 with respect to hydrogen ion concentration. The analyses of X-ray diffractometry and X-ray photoelectron spectroscopy indicated that a black coating, consisted of Fe2O3, Fe3O4 and FeO（OH）, was formed on the surface of iron grains as an iron corrosion product when the system initial pH was lower than 5. The proportion of FeO（OH） increased as reaction time went on, whereas the proportion of Fe3O4 decreased.

Denitrification and Nitrate Reduction to Ammoniumin Taihu Lake and Yellow Sea Inter-Tidal MarineSediments

Denitrification and nitrate reduction to ammonium in Taihu Lake and Yellow Sea inter-tidal marinesediments were studied. The sediment samples were made into slurry containing 150 g dry matter per liter.Various amounts of glucose and 5 mmol L-1 of potassium nitrate were added in order to achieve differentratios of glucose-C to nitrate-N. Acetylene inhibition technique was applied to measure denitrification in theslumes. All samples were incubated anaerobically under argon atmosphere. Data showed that Taihu Lakesediment produced more N2O than marine sediment. Denitrification potential was higher in Taihu Lakesediment than in marne one. Glucose added increased denitrification activity but not the denitrification po-tential of the sediments. Dissimilatory nitrate reduction to ammonium seemed to occur in marine sediment,but not in freshwater one. When the marine sediment was treated with 25 mmol L-1 glucose, its denitrification poteatial, as indicated by maximum N2O production by acetylene blockage, was lower than that treatedwith no or 2.5 mmol L-l glucose. Acetylene was suspected to have inhibitory effect on dissimilatory nitratereduction to ammonium.

Preparation and Electrochemical Properties of the Pd-modified Cu Electrode for Nitrate Reduction in Water

The Pd-modified Cu （Pd/Cu） electrodes for nitrate reduction were prepared using electro-deposition method at different potentials, Compared with other different electrodes so far studied in our work （Cu, Sn/Cu and Pd/Ti electrode） using cyclic voltammetry method, Pd/Cu electrode showed the highest electrocatalytic capacity of nitrate reduction. It was found that at more negative electrode potential the smaller Pd particles formed on the Cu electrode, which was beneficial to the nitrate reduction. With increasing deposition amount of Pd, the capacity of nitrate reduction increased. Too rich Pd, however, has a negative influence on the capacity of nitrate reduction. In our study, the maximum nitrate reduction current was 2.07 mA/cm^2, when electrodeposition potential of Pd was -0.3 V and deposition amount was 0.9 C.

Identification of Dynamic Active Sites Among Cu Species Derived from MOFs@CuPc for Electrocatalytic Nitrate Reduction Reaction to Ammonia

Direct electrochemical nitrate reduction reaction(NITRR)is a promising strategy to alleviate the unbalanced nitrogen cycle while achieving the electrosynthesis of ammonia.However,the restructuration of the high-activity Cu-based electrocatalysts in the NITRR process has hindered the identification of dynamical active sites and in-depth investigation of the catalytic mechanism.Herein,Cu species(single-atom,clusters,and nanoparticles)with tunable loading supported on N-doped TiO_(2)/C are successfully manufactured with MOFs@CuPc precursors via the pre-anchor and post-pyrolysis strategy.Restructuration behavior among Cu species is co-dependent on the Cu loading and reaction potential,as evidenced by the advanced operando X-ray absorption spectroscopy,and there exists an incompletely reversible transformation of the restructured structure to the initial state.Notably,restructured CuN_(4)&Cu_(4) deliver the high NH_(3) yield of 88.2 mmol h^(−1)g_(cata)^(−1) and FE(~94.3%)at−0.75 V,resulting from the optimal adsorption of NO_(3)^(−) as well as the rapid conversion of^(*)NH_(2)OH to^(*)NH_(2) intermediates originated from the modulation of charge distribution and d-band center for Cu site.This work not only uncovers CuN_(4)&Cu_(4) have the promising NITRR but also identifies the dynamic Cu species active sites that play a critical role in the efficient electrocatalytic reduction in nitrate to ammonia.

A core-shell copper oxides-cobalt oxides heterostructure nanowire arrays for nitrate reduction to ammonia with high yield rate

Electrochemical nitrate reduction to ammonia(NRA) can realize the green synthesis of ammonia(NH3) at ambient conditions, and also remove nitrate contamination in water. However, the current catalysts for NRA still face relatively low NH3yield rate and poor stability. We present here a core-shell heterostructure comprising cobalt oxide anchored on copper oxide nanowire arrays(CuO NWAs@Co_(3)O_(4)) for efficient NRA. The CuO NWAs@Co_(3)O_(4)demonstrates significantly enhanced NRA performance in alkaline media in comparison with plain CuO NWAs and Co_(3)O_(4)flocs. Especially, at-0.23 V vs. RHE, NH_(3) yield rate of the CuO NWAs@Co_(3)O_(4)reaches 1.915 mmol h^(-1)cm^(-2),much higher than those of CuO NWAs(1.472 mmol h^(-1)cm^(-2)), Co_(3)O_(4)flocs(1.222 mmol h^(-1)cm^(-2)) and recent reported Cu-based catalysts.It is proposed that the synergetic effects of the heterostructure combing atom hydrogen adsorption and nitrate reduction lead to the enhanced NRA performance.

Nitrate reduction by·CO_(2)^(-) from UV-activated HCOOH

To address the environmental and health hazards of nitrate(NO_(3)^(-))in water,a denitrification advanced reduction process(ARP)using only formic acid(HCOOH)activated by ultraviolet(UV)light was proposed.The efficiency,influencing factors,mechanism,and kinetics of the reduction were investigated through component analysis and radical detection.Results show that,after 90 min of UV illumination,the reduction and gas conversion ratios of 50 mg/L NO_(3)^(-)-N reach 99.9%and 99.8%,respectively,under 9 mM of C_(0)(HCOOH),pH=3.0,and N_(2) aeration.Meanwhile,96.7%of HCOOH is consumed and converted into gas.The NO_(3)^(-)-N conversion process includes the transformation to NO_(2)^(-)-N,followed by a further reduction to gas and a direct conversion into gas,introducing small amounts of nitrite and ammonia.The carbon dioxide anion radical(·CO_(2)^(-))from HCOOH/HCOO^(-)is the principal cause of NO_(3)^(-)-N reduction by UV/HCOOH/N 2 ARP.In contrast,·CO_(2)^(-)production is caused by the hydroxyl radical(·OH).The NO_(3)^(-)-N reduction efficiency is enhanced by the increase in the light intensity,considerably affected by the initial pH,and less affected by inorganic anions,including Cl^(-),H_(2)PO_(4)^(-),and HCO_(3)^(-)/CO_(3)^(2-).The initial HCOOH concentration and light intensity are the main factors that influence the NO_(3)^(-)-N reduction rate.

Unveiling enzyme-mimetic active intermediate of a bioinspired oxo-MoS_(x) electrocatalyst for aqueous nitrate reduction

Excessive nitrate in groundwater has emerged as a serious environmental concern. The elevated nitrate concentration in drinking water causes a serious threat to public health on account of the possible transformation of nitrate to nitrite, which is one of the main predisposing factors of methemoglobinemia [1].

High-throughput mechanistic study of highly selective hydrogen-bonded organic frameworks for electrochemical nitrate reduction to ammonia

Hydrogen-bonded organic frameworks(HOFs),an emerging porous macrocyclic materials linked by hydrogen-bond,hold potential for gas separation and storage,sensors,optical,and electrocatalysts.Here,HOF-based electrocatalysts are rationally developed for nitrates reduction to ammonia,allowing not only to regulate wastewater pollution but also to accomplish carbon-neutral ammonia(NH_(3))synthesis.We preform high-throughput computational screening of thirty-six HOFs with various metals as active sites,denoted as HOF-M1,for nitrate reduction reaction(NO_(3)RR)toward NH_(3).We have implemented a hierarchical four-step screening strategy,and ultimately,HOF-Ti1 was selected based on its exceptional catalytic activity and selectivity in the NO_(3)RR process.Through additional analysis,we discovered that the d band center of the active metal sites serves as an effective parameter for designing and predicting the performance of HOFs in NO_(3)RR.This research not only showcases the immense potential of electrocatalysis in transforming NO_(3)RR into NH_(3)but also provides researchers with a compelling incentive to undertake further experimental investigations.

Zeolite-mediated hybrid Cu^(+)/Cu~0 interface for electrochemical nitrate reduction to ammonia

The electrocatalytic conversion of reactive nitrogen species to ammonia is a promising strategy for efficient NH_(3) synthesis.In this study,we reveal that the hybrid Cu^(+)/Cu~0 interface is catalytically active for electrochemical ammonia synthesis from nitrate reduction.To maintain the hybrid Cu^(+)/Cu~0 state at negative reaction potentials,hydrophilic zeolite is used to modify Cu/Cu_(2)O electrocatalyst,which demonstrates an impressive NH_(3) production rate of 41.65 mg h^(-1) cm^(-2)with ~100% Faradaic efficiency of ammonia synthesis at-0.6 V vs.RHE.In-situ Raman spectroscopy unveil the high activity originates from the zeolite reconstruction at the electrode–electrolyte interface,which protects the valence state of Cu~0/Cu^(+) site under negative potential and promotes electrochemical activity towards NH_(3) synthesis.

Activity and Selectivity of Bimetallic Catalysts Based on SBA-15 for Nitrate Reduction in Water

Nitrate from the application of nitrogen-based fertilizers in intensive agriculture is a notorious waste product, though it lacks cost-effective solutions for its removal from potential drinking water resources. Catalytic reduction appears to be a promising technique for converting nitrates to benign nitrogen gas. Mesoporous silica SBA-15 is a frequently used catalyst support that has large surface areas and highly ordered nanopores. In this work, mesoporous silica SBA-15 bimetallic catalysts for nitrate reduction were investigated. The catalyst was optimized for the selection of promoter metal (Sn and Cu), noble metal (Pd and Pt) and loading ratios of these metals at different temperatures and reduction conditions. The catalysts prepared were characterized by FT-IR, N2 physisorption, XRD, SEM, and ICP. All catalysts showed the presence of cylindrical mesoporous channels and uniform pore structures that remained even after metals loading. In the presence of a CO2 buffer, the catalysts 4Pd-1Cu/SBA-15 and 1Pt-1Cu/SBA-15 reduced at 100?C under H2 and 1Pd-1Cu/SBA-15 reduced at 200°C under H2 demonstrated very high nitrate conversion. Furthermore, the forementioned Pd catalysts had higher N2 selectivity (88% - 87%) compared to Pt catalyst (80%). Nitrate conversion by the 4Pd-1Cu/SBA-15 catalyst was significantly decreased to 81% in the absence of CO2.

Dynamic evolution of Co species and morphological reconstruction on Co-N-C during the nitrate reduction reaction in neutral solution

The electrochemical nitrate reduction reaction(eNO_(3)^(-)RR)is considered an effective approach for converting nitrate-containing wastewater to ammonia.The adsorption and activation of NO_(3)^(-)is the critical step for many materials and the high energy barrier inhibits the continuation of the reduction reaction.The Co nanoparticles encapsulated in the carbon layer we prepared spontaneously react with NO_(3)^(-)and the resulting Co^(2+)is then reduced by electroreduction to Co^(0),which circulates continuously.This resulted in overcoming the energy input required for NO_(3)^(-)adsorption and conversion,thereby increasing the catalytic activity.At the same time,the morphology of the catalyst reconstructed from a dodecahedron to an interwoven nanosheet structure and the increased surface area also gives it better properties.The obtained Co(OH)_(2)@Co-N-C has an excellent eNO_(3)^(-)RR of 2774.7μg·h^(-1)·cm^(-2)with a Faraday efficiency of 81.4%in neutral solution.At the same time,the material-modified electrode can run stably for more than 100 h.Our work provides a new idea for the design of Co-based catalysts for eNO_(3)^(-)RR.

Tandem catalysis in electrocatalytic nitrate reduction:Unlocking efficiency and mechanism

The electrochemical nitrate reduction reaction(NO_(3)RR)holds promise for ecofriendly nitrate removal.However,the challenge of achieving high selectivity and efficiency in electrocatalyst systems still significantly hampers the mechanism understanding and the large-scale application.Tandem catalysts,comprising multiple catalytic components working synergistically,offer promising potential for improving the efficiency and selectivity of the NO3RR.This review highlights recent progress in designing tandem catalysts for electrochemical NO_(3)RR,including the noble metal-related system,transition metal electrocatalysts,and pulsed electrocatalysis strategies.Specifically,the optimization of active sites,interface engineering,synergistic effects between catalyst components,various in situ technologies,and theory simulations are discussed in detail.Challenges and opportunities in the development of tandem catalysts for scaling up electrochemical NO_(3)RR are further discussed,such as stability,durability,and reaction mechanisms.By outlining possible solutions for future tandem catalyst design,this review aims to open avenues for efficient nitrate reduction and comprehensive insights into the mechanisms for energy sustainability and environmental safety.