A reduced combustion mechanism of ammonia/diesel optimized with multi-objective genetic algorithm

For the deep understanding on combustion of ammonia/diesel,this study develops a reduced mechanism of ammonia/diesel with 227 species and 937 reactions.The sub-mechanism on ammonia/interactions of N-based and C-based species(N—C)/NOx is optimized using the Non-dominated Sorting Genetic Algorithm II(NSGA-II)with 200 generations.The optimized mechanism(named as 937b)is validated against combustion characteristics of ammonia/methane(which is used to examine the accuracy of N—C interactions)and ammonia/diesel blends.The ignition delay times(IDTs),the laminar flame speeds and most of key intermediate species during the combustion of ammonia/methane blends can be accurately simulated by 937b under a wide range of conditions.As for ammonia/diesel blends with various diesel energy fractions,reasonable predictions on the IDTs under pressures from 1.0 MPa to5.0 MPa as well as the laminar flame speeds are also achieved by 937b.In particular,with regard to the IDT simulations of ammonia/diesel blends,937b makes progress in both aspects of overall accuracy and computational efficiency,compared to a detailed ammonia/diesel mechanism.Further kinetic analysis reveals that the reaction pathway of ammonia during the combustion of ammonia/diesel blend mainly differs in the tendencies of oxygen additions to NH_2 and NH with different equivalence ratios.

Solar hydrogen production from electrochemical ammonia splitting powered by a single perovskite solar cell

For carbon-free electrochemical fuel formation,the electrochemical cell must be powered by renewable energy.Obtaining solar-powered H_(2) fuel from water typically requires multiple photovoltaic cells and/or junctions to drive the water splitting reaction.Because of the lower thermodynamic requirements to oxidize ammonia compared to water,solar cells with smaller open circuit voltages can provide the required potential for ammonia splitting.In this work,a single perovskite solar cell with an open-circuit potential of 1.08 V is coupled to a 2-electrode electrochemical cell employing hybrid electroanodes functionalized with Ru-based molecular catalysts.The device is active for more than 30 min,producing N_(2) and H_(2) in a 1:2.9 ratio with 89%faradaic efficiency with no external applied bias.This work illustrates that hydrogen production from ammonia can be driven by conventional semiconductors.

Morphology and valence state evolution of Cu:Unraveling the impact on nitric oxide electroreduction

Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption and waste gas emissions.To address this,electrocatalytic nitric oxide reduction reaction(NORR)has emerged as a promising strategy to bridge NH3consumption to NH3production,harnessing renewable electricity for a sustainable future.Copper(Cu)stands out as a prominent electrocatalyst for NO reduction,given its exceptional NH3yield and selectivity.However,a crucial aspect that remains insufficiently explored is the effects of morphology and valence states of Cu on the NORR performance.In this investigation,we synthesized CuO nanowires(CuO-NF)and Cu nanocubes(Cu-NF)as cathodes through an in situ growth method.Remarkably,CuO-NF exhibited an impressive NH3yield of 0.50±0.02 mg cm^(-2)h^(-1)at-0.6 V vs.reversible hydrogen electrode(RHE)with faradaic efficiency of29,68%±1,35%,surpassing that of Cu-NF(0.17±0.01 mg cm^(-2)h^(-1),16.18%±1.40%).Throughout the electroreduction process,secondary cubes were generated on the CuO-NF surface,preserving their nanosheet cluster morphology,sustained by an abundant supply of subsurface oxygen(s-O)even after an extended duration of 10 h,until s-O depletion ensued.Conversely,Cu-NF exhibited inadequate s-O content,leading to rapid crystal collapse within the same timeframe.The distinctive current-potential relationship,akin to a volcano-type curve,was attributed to distinct NO hydrogenation mechanisms.Further Tafel analysis revealed the exchange current density(i0)and standard heterogeneous rate constant(k0)for CuO-NF,yielding 3.44×10^(-6)A cm^(-2)and 3.77×10^(-6)cm^(-2)s^(-1)when NORR was driven by overpotentials.These findings revealed the potential of CuO-NF for NO reduction and provided insights into the intricate interplay between crystal morphology,valence states,and electrochemical performance.

Integration of morphology and electronic structure modulation on cobalt phosphide nanosheets to boost photocatalytic hydrogen evolution from ammonia borane hydrolysis

The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.

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.

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.

Comprehensive understanding of the thriving electrocatalytic nitrate/nitrite reduction to ammonia under ambient conditions

Ammonia(NH_(3))is a multifunctional compound that is an important feedstock for the agricultural and pharmaceutical industries and attractive energy storage medium.At present,NH_(3)synthesis is highly dependent on the conventional Haber–Bosch process that operates under harsh conditions,which consumes large quantities of fossil fuels and releases a large amount of carbon dioxide.As an alternative,electrosynthesis is a prospective method for producing NH_(3)under normal temperature and pressure conditions.Although electrocatalytic nitrogen reduction to ammonia has attracted considerable attentions,the low solubility of N_(2)and high N≡N cracking energy render the achievements of high NH_(3) yield rate and Faradaic efficiency difficult.Nitrate and nitrite(NO_(x)^(-))are common N-containing pollutants.Due to their high solubilities and low dissociation energy of N=O,NO_(x)^(-)−are ideal raw materials for NH_(3) production.Therefore,electrocatalytic NO_(x)^(-)−reduction to NH_(3)(eNO_(x)RR)is a prospective strategy to simultaneously realise environmental protection and NH_(3) synthesis.This review offers a comprehensive understanding of the thriving eNO_(x)RR under ambient conditions.At first,the popular theory and mechanism of eNO_(x)RR and a summary of the measurement system and evaluation criteria are introduced.Thereafter,various strategies for developing NO_(x)−reduction catalysts are systematically presented and discussed.Finally,the challenges and possible prospects of electrocatalytic NO_(x)^(-1) reduction are outlined to facilitate energy-saving and environmentally friendly large-scale synthesis of NH_(3) in the future.

100 W-class green hydrogen production from ammonia at a dual-layer electrode containing a Pt-Ir catalyst for an alkaline electrolytic process

Ammonia allows storage and transport of hydrogen over long distances and is an attractive potential hydrogen carrier.Electrochemical decomposition has recently been used for the conversion of ammonia to hydrogen and is regarded as a future technology for production of CO_(2)-free pure hydrogen.Herein,a heterostructural Pt-Ir dual-layer electrode is developed and shown to achieve successful long-term operation in an ammonia electrolyzer with an anion exchange membrane(AEM).This electrolyzer consisted of eight membra ne electrode assemblies(MEAs)with a total geometric area of 200 cm~2 on the anode side,which resulted in a hydrogen production rate of 25 L h~(-1).We observed the degradation in MEA performance attributed to changes in the anode catalyst layer during hydrogen production via ammonia electrolysis.Furthermore,we demonstrated the relationship between the ammonia oxidation reaction(AOR)and the oxygen evolution reaction(OER).

Enhancing Green Ammonia Electrosynthesis Through Tuning Sn Vacancies in Sn‑Based MXene/ MAX Hybrids

Renewable energy driven N_(2) electroreduction with air as nitrogen source holds great promise for realizing scalable green ammonia production.However,relevant out-lab research is still in its infancy.Herein,a novel Sn-based MXene/MAX hybrid with abundant Sn vacancies,Sn@Ti_(2)CTX/Ti_(2)SnC–V,was synthesized by controlled etching Sn@Ti_(2)SnC MAX phase and demonstrated as an efficient electrocatalyst for electrocatalytic N2 reduction.Due to the synergistic effect of MXene/MAX heterostructure,the existence of Sn vacancies and the highly dispersed Sn active sites,the obtained Sn@Ti2CTX/Ti_(2)SnC–V exhibits an optimal NH_(3) yield of 28.4μg h^(−1) mg_(cat)^(−1) with an excellent FE of 15.57% at−0.4 V versus reversible hydrogen electrode in 0.1 M Na_(2)SO_(4),as well as an ultra-long durability.Noticeably,this catalyst represents a satisfactory NH3 yield rate of 10.53μg h^(−1) mg^(−1) in the home-made simulation device,where commercial electrochemical photovoltaic cell was employed as power source,air and ultrapure water as feed stock.The as-proposed strategy represents great potential toward ammonia production in terms of financial cost according to the systematic technical economic analysis.This work is of significance for large-scale green ammonia production.

The First Global Map of Atmospheric Ammonia(NH_(3)) as Observed by the HIRAS/FY-3D Satellite

Atmospheric ammonia(NH_(3)) is a chemically active trace gas that plays an important role in the atmospheric environment and climate change. Satellite remote sensing is a powerful technique to monitor NH_(3) concentration based on the absorption lines of NH_(3) in the thermal infrared region. In this study, we establish a retrieval algorithm to derive the NH_(3)column from the Hyperspectral Infrared Atmospheric Sounder(HIRAS) onboard the Chinese Feng Yun(FY)-3D satellite and present the first atmospheric NH_(3) column global map observed by the HIRAS instrument. The HIRAS observations can well capture NH_(3) hotspots around the world, e.g., India, West Africa, and East China, where large NH_(3) emissions exist. The HIRAS NH_(3) columns are also compared to the space-based Infrared Atmospheric Sounding Interferometer(IASI)measurements, and we find that the two instruments observe a consistent NH_(3) global distribution, with correlation coefficient(R) values of 0.28–0.73. Finally, some remaining issues about the HIRAS NH_(3) retrieval are discussed.

Deep decalcification of factory-provided freezing acidolysis solution to achieveα-high-strength gypsum

The freezing acidolysis solution of the nitric acid-phosphate fertilizer process has a high calcium content,which makes it difficult to produce fine phosphate and high water-soluble phosphate fertilizer products.Here,based on the potential crystallization principle of calcium sulfate in NH_(4)NO_(3)-H_(3)PO_(4)-H_(2)O,the deep decalcification(i.e.calcium removal)technology to achieveα-high-strength gypsum originated from freezing acidolysis-solutions has been firstly proposed and investigated.Typically,calcium can be removed from the factory-provided freezing acidolysis-solution by neutralizing it with ammonia,followed by the addition of ammonium sulfate solution.As a result,the formation of calcium sulfate in the reaction system undergoes the nucleation and growth of CaSO_(4)·2H_(2)O(DH),as well as its dissolution and crystallization into short columnarα-CaSO_(4)·0.5H_(2)O(α-HH).Remarkably,with the molar ratio of SO_(4)^(2-)/Ca^(2+)at 1.8,the degree of neutralization(NH_(3)/HNO_(3) molar ratio)at 1.7,the reaction temperature of 94℃,and the reaction time of 300 min,the decalcification rate can reach 86.89%,of which the high-strengthα-CaSO_(4)·0.5H_(2)O(α-HH)will be obtained.Noteworthy,the deep decalcification product meets the standards for the production of fine phosphates and highly water-soluble phosphate fertilizers.Consequently,the 2 h flexural strength ofα-HH is 5.3 MPa and the dry compressive strength is 36.8 MPa,which is up to the standard of commercialα-HH.

Advancements in Catalysts for Electrochemical Nitrate Reduction: A Sustainable Approach for Mitigating Nitrate Pollution: A Review

Nitrate pollution is of great importance in both the environmental and health contexts, necessitating the development of efficient mitigation strategies. This review provides a comprehensive analysis of the many catalysts employed in the electrochemical reduction of nitrate to ammonia, and presents a viable environmentally friendly approach to address the issue of nitrate pollution. Hence, the electrochemical transformation of nitrate to ammonia serves the dual purpose of addressing nitrate pollution in water bodies, and is a useful agricultural resource. This review examines a range of catalyst materials such as noble and non-noble metals, metal oxides, carbon-based materials, nitrogen-doped carbon species, metal complexes, and semiconductor photocatalysts. It evaluates catalytic efficiency, selectivity, stability, and overall process optimization. The performance of catalysts is influenced by various factors, including reaction conditions, catalyst structure, loading techniques, and electrode interfaces. Comparative analysis was performed to evaluate the catalytic activity, selectivity, Faradaic efficiency, current density, stability, and durability of the catalysts. This assessment offers significant perspectives on the structural, compositional, and electrochemical characteristics that affect the efficacy of these catalysts, thus informing future investigations and advancements in this domain. In addition to mitigating nitrate pollution, the electrochemical reduction of nitrate to ammonia is in line with sustainable agricultural methods, resource conservation, and the utilization of renewable energy resources. This study explores the factors that affect the catalytic efficiency, provides new opportunities to address nitrate pollution, and promotes the development of sustainable environmental solutions.

TiO2-PES Fibrous Composite Material for Ammonia Removal Using UV-A Photocatalyst

This study focused on the development and characterization of TiO2-PES composite fibers with varying TiO2 loading amounts using a phase inversion process. The resulting composite fibers exhibited a sponge-like structure with embedded TiO2 nanoparticles within a polymer matrix. Their photocatalytic performance for ammonia removal from aqueous solutions under UV-A light exposure was thoroughly investigated. The findings revealed that PeTi8 composite fibers displayed superior adsorption capacity compared to other samples. Moreover, the study explored the impact of pH, light intensity, and catalyst dosage on the photocatalytic degradation of ammonia. Adsorption equilibrium isotherms closely followed the Langmuir model, with the results indicating a correlation between qm values of 2.49 mg/g and the porous structure of the adsorbents. The research underscored the efficacy of TiO2 composite fibers in the photocatalytic removal of aqueous under UV-A light. Notably, increasing the distance between the photocatalyst and the light source resulted in de-creased hydroxyl radical concentration, influencing photocatalytic efficiency. These findings contribute to our understanding of TiO2 composite fibers as promising photocatalysts for ammonia removal in water treatment applications.

Progress in pathogenesis and treatment of type A hepatic encephalopathy in acute liver failure:a comprehensive review

Hepatic encephalopathy is a serious neuropsychiatric complication caused by liver failure,which is characterized by the development of cognitive and motor disorders into coma.Typically,hepatic encephalopathy can be divided into three types(A,B,and C)according to the etiology.Type A hepatic encephalopathy(AHE)caused by acute liver failure seriously affects the prognosis of patients,ranging from mild neuropsychological changes to coma,brain edema,and even death.So far,the research on the pathogenesis of AHE has focused on the toxic effects of ammonia on the central nervous system,metabolic disorders(glutamine and lactate accumulation),neurotransmission alteration,systemic inflammation,especially neuro-inflammation.All these mechanisms are not independent,but mutually have synergistic effects.In clinic,treatment of AHE based on only one mechanism is often ineffective.To clarify the pathogenesis and the interaction among the mechanisms will be beneficial to the effective treatment of AHE and reduce the mortality.The aim of this review is to provide comprehensive scientific evidence for the clinical treatment of AHE via collecting and analyzing the latest mechanism of AHE,and clarifying the relationship among these mechanisms combing the investigation of the latest research progress of drug treatment of acute liver failure.Consequently,we find that the pathogenesis of AHE is a complex neurocognitive disorder shaped by interactions among hyperammonemia,inflammation,and changes in neurotransmission,the signaling pathways thereby integrating the inflammatory and neurological inputs to impact pathophysiological or neurobehavioral outcomes.

Rational catalyst design and mechanistic evaluation for electrochemical nitrogen reduction at ambient conditions

Ammonia(NH3), a carbon-free hydrogen carrier, is an important commodity for the food supply chain owing to its high energy capacity and ease of storage and transport. The Haber-Bosch process is currently the favored industrial method for large-scale ammonia production but requires energy-intensive and sophisticated infrastructure which hampers its utilization in a sustainable and decentralized system of manufacture.The electrochemical nitrogen reduction reaction(eNRR) at ambient conditions holds great potential for sustainable production of ammonia using electricity generated from renewable energy sources such as solar and wind. However, this approach is limited by a low rate of ammonia production with high overpotential and the competing hydrogen evolution reaction(HER). For a better understanding and utilization of eNRR as a sustainable process, insight into rational catalyst design and mechanistic evaluations by a theoretically-directed experimental approach is imperative. Herein, recent insights into rational catalyst design and mechanisms, based on intrinsic and extrinsic catalytic activity are articulated.Following the elucidation of basic principles and mechanisms, a framework supplied by theoretical studies that lead to the optimal selection and development of eNRR catalysts is presented. Following a discussion of recently developed electrocatalysts for eNRR, we outline various recently-used theoretical and experimental methodologies to improve the intrinsic and extrinsic catalytic activity of advanced electrocatalysts.This review is anticipated to contribute to the development of active, selective, and efficient catalysts for nitrogen reduction.

Nanoengineering Metal–Organic Frameworks and Derivatives for Electrosynthesis of Ammonia

Electrocatalytic synthesis under mild conditions has become increasingly important as one of the practical alternatives for industrial applications,especially for the green ammonia(NH_(3))industry.A properly engineered electrocatalyst plays a vital role in the realization of superior catalytic performance.Among various types of promising nanomaterials,metal–organic frameworks(MOFs)are competitive candidates for developing efficient electrocatalytic NH_(3) synthesis from simple nitrogen-containing molecules or ions,such as N_(2) and NO_(3)^(−).In this review,recent advances in the development of electrocatalysts derived from MOFs for the electrosynthesis of NH_(3) are collected,categorized,and discussed,including their application in the N_(2) reduction reaction(NRR)and the NO_(3)^(−)reduction reaction(NO3RR).Firstly,the fundamental principles are illustrated,such as plausible mechanisms of NH_(3) generation from N_(2) and NO_(3)^(−),the apparatus of corresponding electrocatalysis,parameters for evaluation of reaction efficiency,and detection methods of yielding NH_(3).Then,the electrocatalysts for NRR processes are discussed in detail,including pristine MOFs,MOF-hybrids,MOF-derived N-doped porous carbons,single atomic catalysts from pyrolysis of MOFs,and other MOF-related materials.Subsequently,MOF-related NO3RR processes are also listed and discussed.Finally,the existing challenges and prospects for the rational design and fabrication of electrocatalysts from MOFs for electrochemical NH_(3) synthesis are presented,such as the evolution of investigation methods with artificial intelligence,innovation in synthetic methods of MOF-related catalysts,advancement of characterization techniques,and extended electrocatalytic reactions.

Sustainable Ammonia Synthesis from Nitrogen and Water by One-Step Plasma Catalysis

Sustainable ammonia synthesis at ambient conditions that relies on renewable sources of energy and feedstocks is globally sought to replace the Haber-Bosch process.Here,using nitrogen and water as raw materials,a nonthermal plasma catalysis approach is demonstrated as an effective powerto-chemicals conversion strategy for ammonia production.By sustaining a highly reactive environment,successful plasma-catalytic production of NH_(3) was achieved from the dissociation of N_(2) and H_(2)O under mild conditions.Plasma-induced vibrational excitation is found to decrease the N_(2) and H_(2)O dissociation barriers,with the presence of matched catalysts in the nonthermal plasma discharge reactor contributing significantly to molecular dissociation on the catalyst surface.Density functional theory calculations for the activation energy barrier for the dissociation suggest that ruthenium catalysts supported on magnesium oxide exhibit superior performance over other catalysts in NH_(3) production by lowering the activation energy for the dissociative adsorption of N_(2) down to 1.07 eV.The highest production rate,2.67 mmol gcat.^(-1) h^(-1),was obtained using ruthenium catalyst supported on magnesium oxide.This work highlights the potential of nonthermal plasma catalysis for the activation of renewable sources to serve as a new platform for sustainable ammonia production.

Significant reduction of ammonia emissions while increasing crop yields using the 4R nutrient stewardship in an intensive cropping system

Ammonia (NH_3) emissions should be mitigated to improve environmental quality.Croplands are one of the largest NH_3sources,they must be managed properly to reduce their emissions while achieving the target yields.Herein,we report the NH_3 emissions,crop yield and changes in soil fertility in a long-term trial with various fertilization regimes,to explore whether NH_3 emissions can be significantly reduced using the 4R nutrient stewardship (4Rs),and its interaction with the organic amendments (i.e.,manure and straw) in a wheat–maize rotation.Implementing the 4Rs significantly reduced NH_3 emissions to 6 kg N ha~(–1) yr~(–1) and the emission factor to 1.72%,without compromising grain yield (12.37 Mg ha~(–1) yr~(–1))and soil fertility (soil organic carbon of 7.58 g kg~(–1)) compared to the conventional chemical N management.When using the 4R plus manure,NH_3 emissions (7 kg N ha~(–1) yr~(–1)) and the emission factor (1.74%) were as low as 4Rs,and grain yield and soil organic carbon increased to 14.79 Mg ha~(–1) yr~(–1) and 10.09 g kg~(–1),respectively.Partial manure substitution not only significantly reduced NH_3 emissions but also increased crop yields and improved soil fertility,compared to conventional chemical N management.Straw return exerted a minor effect on NH_3 emissions.These results highlight that 4R plus manure,which couples nitrogen and carbon management can help achieve both high yields and low environmental costs.

Efficient electrocatalytic conversion of N_(2) to NH_(3) using oxygen-rich vacancy lithium niobate cubes

Instead of the energy-intensive Haber-Bosch process,the researchers proposed a way to produce ammonia using water and nitrogen as feedstock,powered by electricity,without polluting the environment.Nevertheless,how to design efficient electrocatalyst for electrocatalytic nitrogen reduction reaction(NRR)is still urgent and challenging.Herein,a strategy is proposed to adjust the morphology and surface electronic structure of electrocatalyst by optimizing material synthesis method.LiNbO3(lithium niobate,LN)cubes with oxygen-rich vacancy and regular morphology were synthesized by hydrothermal synthesis and followed molten salt calcination process,which were used for electrocatalytic NRR under mild conditions.Compared with LN nanoparticles synthesized by solid phase reaction,LN cubes exhibit better NRR performance,with the highest ammonia yield rate(13.74μg.h^(-1).mg^(-1))at the best potential of-0.45V(vs.reversible hydrogen electrode,RHE)and the best Faradaic efficiency(85.43%)at-0.4 V.Moreover,LN cubes electrocatalyst also demonstrates high stability in 7 cycles and 18 h current-time tests.Further investigation of the reaction mechanism confirmed that the structure of oxygen vacancy could adjust the electronic structure of the electrocatalyst,which was conducive to the adsorption and activation of N_(2) molecule and also increased the ECSA of electrocatalyst,thus providing more active sites for the NRR process.

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.