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Enhancing ammonia production rates from electrochemical nitrogen reduction by engineering three-phase boundary with phosphorus-activated Cu catalysts
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作者 Jeehye Kim Cho Hee Lee +5 位作者 Yong Hyun Moon Min Hee Lee Eun Hyup Kim Sun Hee Choi Youn Jeong Jang Jae Sung Lee 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2023年第9期394-401,共8页
Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to i... Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems. 展开更多
关键词 electrochemical nitrogen reduction reaction Ammonia production Phosphorous modified copper electrodes Gas diffusion electrodes Three-phase boundary PTFE coating
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Bi-Atom Electrocatalyst for Electrochemical Nitrogen Reduction Reactions 被引量:2
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作者 Wenchao Zhang Bin-Wei Zhang 《Nano-Micro Letters》 SCIE EI CAS CSCD 2021年第7期86-90,共5页
The electrochemical nitrogen reduction reaction(NRR)to directly produce NH3 from N_(2) and H_(2)O under ambient conditions has attracted significant attention due to its ecofriendliness.Nevertheless,the electrochemica... The electrochemical nitrogen reduction reaction(NRR)to directly produce NH3 from N_(2) and H_(2)O under ambient conditions has attracted significant attention due to its ecofriendliness.Nevertheless,the electrochemical NRR presents several practical challenges,including sluggish reaction and low selectivity.Here,bi-atom catalysts have been proposed to achieve excellent activity and high selectivity toward the electrochemical NRR by Ma and his co-workers.It could accelerate the kinetics of N_(2)-to-NH_(3) electrochemical conversion and possess better electrochemical NRR selectivity.This work sheds light on the introduction of bi-atom catalysts to enhance the performance of the electrochemical NRR. 展开更多
关键词 electrochemical nitrogen reduction reaction Bi-atom catalysts Excellent activity High selectivity
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Advanced In Situ Characterization Techniques for Direct Observation of Gas-Involved Electrochemical Reactions
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作者 Yanzheng He Sisi Liu +4 位作者 Mengfan Wang Qiyang Cheng Haoqing Ji Tao Qian Chenglin Yan 《Energy & Environmental Materials》 SCIE EI CAS CSCD 2023年第6期73-112,共40页
Gas-involved electrochemical reactions provide feasible solutions to the worldwide energy crisis and environmental pollution.It has been recognized that various elements of the reaction system,including catalysts,inte... Gas-involved electrochemical reactions provide feasible solutions to the worldwide energy crisis and environmental pollution.It has been recognized that various elements of the reaction system,including catalysts,intermediates,and products,will undergo real-time variations during the reaction process,which are of significant meaning to the in-depth understanding of reaction mechanisms,material structure,and active sites.As judicious tools for real-time monitoring of the changes in these complex elements,in situ techniques have been exposed to the spotlight in recent years.This review aims to highlight significant progress of various advanced in situ characterization techniques,such as in situ X-ray based technologies,in situ spectrum technologies,and in situ scanning probe technologies,that enhance our understanding of heterogeneous electrocatalytic carbon dioxide reduction reaction,nitrogen reduction reaction,and hydrogen evolution reaction.We provide a summary of recent advances in the development and applications of these in situ characterization techniques,from the working principle and detection modes to detailed applications in different reactions,along with key questions that need to be addressed.Finally,in view of the unique application and limitation of different in situ characterization techniques,we conclude by putting forward some insights and perspectives on the development direction and emerging combinations in the future. 展开更多
关键词 carbon dioxide reduction reaction gas-involved electrochemical reactions hydrogen evolution reaction in situ characterizations nitrogen reduction reaction
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Effect on electrochemical reduction of nitrogen to ammonia under ambient conditions: Challenges and opportunities for chemical fuels 被引量:2
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作者 Lijuan Niu Li An +1 位作者 Xiayan Wang Zaicheng Sun 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2021年第10期304-318,I0009,共16页
The nitrogen cycle plays an important role in nature,but N-containing products cannot meet human needs.The electrochemical synthesis of ammonia under ambient conditions has attracted the interest of many researchers b... The nitrogen cycle plays an important role in nature,but N-containing products cannot meet human needs.The electrochemical synthesis of ammonia under ambient conditions has attracted the interest of many researchers because it provides a clean and pollution-free synthesis method;however,it has certain difficulties,including a high activation energy,multiple electron transfer,and hydrogenation.Thermodynamic factors limit the selectivity and activity of ammonia synthesis techniques.This review summarizes progress in the electrochemical synthesis of ammonia from theory and experiment.Theoretically,the reduction of nitrogen molecules is analyzed using orbit theory and the thermodynamic reaction pathways.Experimentally,we first discuss the effect of the experimental setup on the nitrogen reduction reaction,and then the four critical of catalysts,including size,electronic,coordination,and orientation effects.These issues must be considered to produce highly-efficient catalysts for electrochemical nitrogen reduction(eNRR).This review provides an overview of the eNRR to enable future researchers to design rational catalysts. 展开更多
关键词 nitrogen reduction reaction nrr ELECTROCATALYST nitrogen-fixing
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Breaking the linear correlations for enhanced electrochemical nitrogen reduction by carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6) 被引量:2
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作者 Lehui Ma Fanfan Xu +5 位作者 Linlin Zhang Zhongfen Nie Kai Xia Mingxia Guo Mingzhu Li Xin Ding 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2022年第8期182-187,I0006,共7页
Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is... Electrochemical nitrogen reduction(NRR)is deemed as a consummate answer for the traditional Haber–Bosch technology.Breaking the linear correlations between adsorption and transition-state energies of intermediates is vital to improve the kinetics of ammonia synthesis and obtain a less energy-intensive process.Herein,carbon-encapsulated mixed-valence Fe_(7)(PO_(4))_(6) was prepared and applied as an electrocatalyst for high-efficiency NRR.A dramatic faradaic efficiency(FE)of 36.93%and an NH_(3) production rate of 13.1μg h^(-1) mg_(cat)^(-1) were obtained at-0.3 V versus RHE,superior to nearly all Fe-based catalysts.Experiments and DFT calculations revealed that the superior performance was ascribed to the synergistic effect of mixed-valence iron pair,which braked the linear correlations to improve the kinetics of ammonia from collaborative hydrogenation and*NH_(3) separation.This work proves the feasibility of mixedvalence catalysts for nitrogen reduction and thus opening a new avenue towards artificial nitrogenfixation catalysts. 展开更多
关键词 N2 reduction reaction(nrr) MIXED-VALENCE Linear correlations nitrogen fixation N_(2)activation
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CeO_(x)-supported monodispersed MoO_(3) clusters for high-efficiency electrochemical nitrogen reduction under ambient condition 被引量:1
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作者 Jie Liu Guanghua Wang +4 位作者 Shiyuan Zhou Sangui Liu Gen Li Hong-Gang Liao Shi-Gang Sun 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2021年第5期186-192,共7页
Developing efficient and low-cost electrocatalysts is essential for the electroreduction of N_(2) to NH_(3).Here,highly monodispersed MoO_(3) clusters loaded on a coral-like CeO_(x)compound with abundant oxygen vacanc... Developing efficient and low-cost electrocatalysts is essential for the electroreduction of N_(2) to NH_(3).Here,highly monodispersed MoO_(3) clusters loaded on a coral-like CeO_(x)compound with abundant oxygen vacancies are successfully prepared by an impregnation-reduction method.The MoO_(3) clusters with small sizes of 2.6±0.5 nm are induced and anchored by the oxygen vacancies of CeO_(x),resulting in excellent nitrogen reduction reaction(NRR)performance.Additionally,the synergistic effects between MoO_(3) and CeO_(x)lead to a further improvement of the electrochemical performance.The as-prepared MoO_(3)-CeO_(x)catalyst shows an NH_(3) yield rate of 32.2 μg h^(-1) mg^(-1) cat and a faradaic efficiency of 7.04%at-0.75 V(vs.reversible hydrogen electrode)in 0.01 M Dulbecco’s Phosphate Buffered Saline.Moreover,it displays decent electrochemical stability over 30,000 s.Besides,the electrochemical NRR mechanism for MoO_(3)-CeO_(x)is investigated by in-situ Fourier transform infrared spectroscopy.N-H stretching,H-N-H bending,and N-N stretching are detected during the reaction,suggesting that an associative pathway is followed.This work provides an approach to designing and synthesizing potential electrocatalysts for NRR. 展开更多
关键词 electrochemical nitrogen reduction reaction Mo-based catalysts Monodispersed clusters Oxygen vacancies
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Fe–N–C single atom catalysts for the electrochemical conversion of carbon,nitrogen and oxygen elements 被引量:2
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作者 Jian Huang Qiao Zhang +1 位作者 Jie Ding Yueming Zhai 《Materials Reports(Energy)》 2022年第3期22-37,共16页
Single atom catalysts(SACs)are constituted by isolated active metal centers,which are heterogenized on inert supports such as graphene,porous carbon,and amorphous carbon.The thermal stability,electronic properties,and... Single atom catalysts(SACs)are constituted by isolated active metal centers,which are heterogenized on inert supports such as graphene,porous carbon,and amorphous carbon.The thermal stability,electronic properties,and catalytic activities of the metal center can be controlled via manipulating the neighboring heteroatoms such as nitrogen,oxygen,and sulfur.Due to the atomical dispersion of the active catalytic centers,the amount of metal required for catalysis can be decreased.Furthermore,new possibilities are offered to easily control the selectivity of a given transformation process as well as to improve turnover frequencies and turnover numbers of target reactions.Among them,Fe–N–C single atom catalysts own special electronic structure,and have been widely used in many fields of electrocatalysis.This review aims to summarize the synthesis of Fe–N–C based on anchoring individual iron atoms on carbon/graphene.The spin-related properties of Fe–N–C catalysts are described,including the relation between spin and electron structure of Fe–N x as well as the coupling between electronic structure of Fe–N x and electronic(orbit)of CO_(2),N_(2)and O_(2).Next,mechanistic investigations conducted to un-derstand the specific behavior of Fe–N–C catalysts are highlighted,including C,N,O electro-reduction.Finally,some issues related to the future developments of Fe–N–C are put forward and corresponding feasible solutions are offered. 展开更多
关键词 Single atom catalysts Fe-N-C synthesis Spin electrochemical conversion CO_(2)reduction reaction nitrogen reduction reaction Oxygen reduction reaction
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Perspectives on electrochemical nitrogen fixation catalyzed by two-dimensional MXenes 被引量:2
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作者 Tiezhu Guo Di Zhou Chuanfang(John)Zhang 《Materials Reports(Energy)》 2022年第1期3-16,共14页
Ammonia is the most basic raw material in industrial and agricultural production.The current industrial production of ammonia relies on the Haber-Bosch process with high energy consumption.To overcome this shortcoming... Ammonia is the most basic raw material in industrial and agricultural production.The current industrial production of ammonia relies on the Haber-Bosch process with high energy consumption.To overcome this shortcoming,the development of electrocatalytic ammonia synthesis under moderate conditions is considered as a potential alternative technology.The two-dimensional(2D)MXenes family has been proved promising as electrocatalysts,but from the currently available literature,it is hard to find a systematic review on MXenes-catalyzed ammonia synthesis.So in the present review,we summarize the key perspectives on that topic in recent years as well as outline,from a prospective view,strategies of catalyst design.We analyze in detail the methods for preparing high performance MXenes-based catalysts and the corresponding underlying mechanisms,and also discuss the criteria and potential challenges,expecting to provide inspiration for the development of efficient MXenes-based route to electrochemical ammonia fixation. 展开更多
关键词 2D materials MXenes Ammonia synthesis Electrocatalytic nitrogen reduction reaction (nrr) ELECTROCATALYSTS
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Coupling Fe and Mo single atoms on hierarchical N-doped carbon nanotubes enhances electrochemical nitrogen reduction reaction performance
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作者 Wenjie Cui Baokang Geng +6 位作者 Xiang Chu Jianing He Lingxi Jia Xiaoxiao Han Xiao Wang Shuyan Song Hongjie Zhang 《Nano Research》 SCIE EI CSCD 2023年第4期5743-5749,共7页
Electrochemical nitrogen reduction reaction(NRR)paves a new way to cost-efficient production of ammonia,but is still challenging in the sluggish kinetics caused by hydrogen evolution reaction competition and chemical ... Electrochemical nitrogen reduction reaction(NRR)paves a new way to cost-efficient production of ammonia,but is still challenging in the sluggish kinetics caused by hydrogen evolution reaction competition and chemical inertness of N≡N bond.Herein,we report a“dual-site”strategy for boosting NRR performance.A high-performance catalyst is successfully constructed by anchoring isolated Fe and Mo atoms on hierarchical N doped carbon nanotubes through a facile self-sacrificing template route,which exhibits a remarkably improved NH3 yield rate of 26.8μg·h^(−1)·mg with 11.8%Faradaic efficiency,which is 2.5 and 1.6 times larger than those of Fe/NC and Mo/NC.The enhancement can be attributed to the unique hierarchical structure that profits from the contact of electrode and electrolyte,thus improving the mass and electron transport.More importantly,the in situ Fourier transform infrared spectroscopy(in situ FTIR)result firmly demonstrates the crucial role of the coupling of Fe and Mo atoms,which can efficiently boost the generation and transmission of*N2Hy intermediates,leading to an accelerated reaction rate. 展开更多
关键词 dual-site single atom hard template synergetic effect nitrogen reduction reaction(nrr)
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Recent advances and challenges of nitrogen/nitrate electro catalytic reduction to ammonia synthesis
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作者 Junwen CAO Yikun HU +2 位作者 Yun ZHENG Wenqiang ZHANG Bo YU 《Frontiers in Energy》 SCIE EI CSCD 2024年第2期128-140,共13页
The Haber-Bosch process is the most widely used synthetic ammonia technology at present.Since its invention,it has provided an important guarantee for global food security.However,the traditional Haber-Bosch ammonia s... The Haber-Bosch process is the most widely used synthetic ammonia technology at present.Since its invention,it has provided an important guarantee for global food security.However,the traditional Haber-Bosch ammonia synthesis process consumes a lot of energy and causes serious environmental pollution.Under the serious pressure of energy and environment,a green,clean,and sustainable ammonia synthesis route is urgently needed.Electrochemical synthesis of ammonia is a green and mild new method for preparing ammonia,which can directly convert nitrogen or nitrate into ammonia using electricity driven by solar,wind,or water energy,without greenhouse gas and toxic gas emissions.Herein,the basic mechanism of the nitrogen reduction reaction(NRR)to ammonia and nitrate reduction reaction(NO_(3)^(-))to ammonia were discussed.The representative approaches and major technologies,such as lithium mediated electrolysis and solid oxide electrolysis cell(SOEC)electrolysis for NRR,high activity catalyst and advanced electrochemical device fabrication for(NO_(3)^(-))RR and electrochemical ammonia synthesis were summarized.Based on the above discussion and analysis,the main challenges and development directions for electrochemical ammonia synthesis were further proposed. 展开更多
关键词 electrochemical ammonia synthesis nitrogen NITRATE nitrogen reduction reaction(nrr)to ammonia nitrate reduction reaction(NO_(3)^(-))RR
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交流磁场对M-BTC材料电化学氮还原(NRR)性能的影响
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作者 高朋召 张佩 +5 位作者 李玉玲 马冯 覃航 刘小磐 郭文明 肖汉宁 《湖南大学学报(自然科学版)》 EI CAS CSCD 北大核心 2022年第6期162-171,共10页
本文采用水热法合成了四种MOFs催化剂,分别通过XRD、SEM及IR表征了催化剂的组成和微观结构,进而研究了催化剂的NRR活性,最后探究了交流磁场对催化剂NRR活性的影响及作用机制.结果表明:四种催化剂中,Fe-BTC在-0.376 V(vs.RHE)和80℃时具... 本文采用水热法合成了四种MOFs催化剂,分别通过XRD、SEM及IR表征了催化剂的组成和微观结构,进而研究了催化剂的NRR活性,最后探究了交流磁场对催化剂NRR活性的影响及作用机制.结果表明:四种催化剂中,Fe-BTC在-0.376 V(vs.RHE)和80℃时具有最高的氨产率和法拉第效率,分别为3.63×10^(-10) mol s^(1) cm^(-2)和0.31%;在恒电位下,当交流磁场的强度为4.355 mT,频率为50 kHz时,催化剂的氨产率和法拉第效率最大,分别为3.61×10^(-9) mol s^(-1) cm^(-2)和5.67%,比无磁场时分别提高约10倍和18倍,这种增效一方面源于交流磁场增加了N_(2)在Fe-BTC表面的吸附量,另一方面,交流磁场产生的感应电动势与电场本身的电势的叠加作用,为NRR反应提供了额外能量所致. 展开更多
关键词 电催化氮还原反应 金属有机框架 交流磁场 氨产率 法拉第效率
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碳载金属单原子催化剂的电合成氨进展
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作者 李沐霖 谢一萌 +3 位作者 宋静婷 杨级 董金超 李剑锋 《Chinese Journal of Catalysis》 SCIE CAS CSCD 2024年第5期42-67,共26页
氨不仅是生产农业肥料和医药分子的关键原料,同时因其具备高能量密度和零碳排放的特性,也被视为极具潜力的能源载体.鉴于当前对环保和可持续发展的迫切需求,实现氨分子的绿色合成已成为重要任务.其中,利用可再生能源驱动的电化学合成氨... 氨不仅是生产农业肥料和医药分子的关键原料,同时因其具备高能量密度和零碳排放的特性,也被视为极具潜力的能源载体.鉴于当前对环保和可持续发展的迫切需求,实现氨分子的绿色合成已成为重要任务.其中,利用可再生能源驱动的电化学合成氨技术,因其对环境友好和高效性,被视为替代传统哈伯-博世工艺的绿色路径,具有广阔的应用前景.在电化学催化合成氨的研究中,单原子催化剂(SAC)因其独特的性质而备受关注.SAC的孤立金属中心不仅提高了金属原子的利用率,而且有效抑制了氮-氮偶联反应,从而显著提升了催化合成氨的效率,成为当前的研究热点.本文综述了SAC电催化合成氨领域的最新研究进展,旨在为科研工作者提供基础的理论和实验参考.系统总结了不同氮源(包括氮气、硝酸根、亚硝酸根及一氧化氮)合成氨的研究进展,并深入探讨了催化剂的理论和实验设计、催化活性中心的种类及其催化活性,以及真实反应过程中的催化动态行为.首先,介绍了自然和人工固氮系统中的氮循环路径.自然固氮系统展示了氮气、氮氧化物、氨的循环路径,为不同氮物种合成氨方法提供了可借鉴的思路;而人工氮循环则阐述了社会发展、工业生产对自然循环氮平衡的破坏,凸显了电化学人工固氮的必要性.随后,基于理论模拟方法,在原子和分子尺度上总结了不同氮物种在催化剂表面的反应过程.例如,在氮气合成氨过程中探讨了涉及的解离路径、交替缔合及远端缔合路径等.本文详细阐述了催化活性结构的理论筛选方法的重要性,并介绍了如何通过结构稳定性评估、反应物种的吸附活性以及催化活性及选择性的综合考量,来确定最佳的催化活性中心种类及微观结构.随后,总结了科研人员基于理论筛选结果,采用热解策略制备碳载金属SAC的研究进展.这些策略包括,碳基底与金属络合物的混合热解策略、金属有机框架衍生策略、金属辅助小分子热解策略、吸附活性策略及模板牺牲辅助策略等.同时,系统地总结了不同SAC对四种氮前驱体还原反应的催化活性.此外,深入地讨论了催化活性中心如Cu和Fe单原子在合成氨反应过程中的结构动态演化行为,强调了非原位结构可能仅是单原子前驱体,而反应过程中演变结构才是真实催化活性中心.这对于深入理解SAC电催化合成氨的机理和提高催化效率有一定的借鉴意义.最后,本文简要探讨了单原子催化剂在合成氨领域所面临的挑战及发展机遇.主要包括(1)发展更为精准的理论预测方法,实现从静态计算向动态模拟的转变,以更准确地预测和解析催化剂在实际反应中的行为机制;(2)积极发展多原子协同位点,从金属单原子到双甚至三原子团簇,利用多原子间的协同作用提升催化效率;(3)发展可替代氨合成路径,如低温等离子体耦合电化学合成氨技术,以推动氨合成技术的绿色化和高效化;(4)结合动态谱学技术的发展及应用,通过在原位甚至工况条件下的探究,深入解析动态反应过程,为催化剂的进一步优化提供科学依据.通过发展更为精准的理论预测方法、多原子协同位点、可替代氨合成路径以及结合动态谱学技术的进步,我们有望推动单原子催化剂在合成氨领域的应用取得更大突破. 展开更多
关键词 合成氨 氮转化反应 电化学还原 单原子催化剂 氮气 氮氧化物
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A photo-assisted electrochemical-based demonstrator for green ammonia synthesis 被引量:2
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作者 Xiaolu Liu Zhurui Shen +8 位作者 Xinyue Peng Lu Tian Ran Hao Lu Wang Yangfan Xu Yuping Liu Christos T.Maravelias Wei Li Geoffrey A.Ozin 《Journal of Energy Chemistry》 SCIE EI CAS CSCD 2022年第5期826-834,共9页
Bridging laboratory research and practical utilization is of crucial importance for the development of green ammonia synthetic technologies. A decentralized photo-assisted electrochemical-based demonstrator has been p... Bridging laboratory research and practical utilization is of crucial importance for the development of green ammonia synthetic technologies. A decentralized photo-assisted electrochemical-based demonstrator has been proposed for green ammonia synthesis from renewable electricity, air and water, where well-known defect-laden WO_(3) is used as the working electrode, and a commercially available PV panel supplies renewable electricity. In this demonstrator, defect-laden WO_(3) exhibits the optimum electrochemical NH_(3) formation rate(4.51 × 10^(-12)mol s^(-1)cm^(-2)) in 0.1 M K_(2)SO_(4)in a photovoltaic electrochemical(PV-EC) system. A system-level energy and cost analysis was conducted to investigate its economic viability and a general evaluation tool for system performance and cost estimation was proposed. This advance enables the possibility of integrating the small-scale green ammonia demonstrator into a stand-alone farm system. 展开更多
关键词 Ammonia synthesis electrochemical demonstrator ELECTROCATALYSIS nitrogen reduction reaction System-level energy and cost analysis
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Tuning Double Layer Structure of WO3 Nanobelt for Promoting the Electrochemical Nitrogen Reduction Reaction in Water 被引量:1
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作者 洪清水 李唐懿 +9 位作者 郑世胜 陈海标 楚鸿豪 许宽达 李舜宁 梅宗维 赵庆贺 任文举 赵文光 潘锋 《Chinese Journal of Structural Chemistry》 SCIE CAS CSCD 2021年第4期519-526,408,共9页
Electrochemical fixation of nitrogen to ammonia with highly active,highly selective and low cost electrocatalysts is a sustainable alternative to the extremely energy-and capital-intensive Haber-Bosch process.Herein,w... Electrochemical fixation of nitrogen to ammonia with highly active,highly selective and low cost electrocatalysts is a sustainable alternative to the extremely energy-and capital-intensive Haber-Bosch process.Herein,we demonstrate a near electroneutral WO3 nanobelt catalyst to be a promising electrocatalyst for selective and efficient nitrogen reduction.The concept of near electroneutral interface is demonstrated by fabricating WO3 nanobelts with small zeta potential value on carbon fiber paper,which ensures a loose double layer structure of the electrode/electrolyte interface and allows nitrogen molecules access the active sites more easily and regulates proton transfer to increase the catalytic selectivity.The WO3/CFP electrode with optimal surface charge achieves a NH3 yield rate of 4.3μg·h-1·mg-1 and a faradaic efficiency of 37.3%at-0.3 V vs.RHE,rivalling the performance of the state-of-the-art nitrogen reduction reaction electrocatalysts.The result reveals that an unobstructed gas-diffusion pathway for continually supplying enough nitrogen to the active catalytic sites is of great importance to the overall catalytic performance. 展开更多
关键词 electrochemical nitrogen reduction reaction zeta potential nitrogen diffusion and transport process WO3 nanobelts first-principles calculations
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Recent progress in electrochemical synthesis of carbon-free hydrogen carrier ammonia and ammonia fuel cells:A review 被引量:1
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作者 Feng Du Wei Sun +1 位作者 Hui Luo Chang Ming Li 《Materials Reports(Energy)》 2022年第4期3-18,共16页
Ammonia(NH3)is a cornerstone widely used in the modern agriculture and industry,the annual global production gradually increases to almost 200 million tons.Nearly 80%of the produced NH3 is used in the fertilizer indus... Ammonia(NH3)is a cornerstone widely used in the modern agriculture and industry,the annual global production gradually increases to almost 200 million tons.Nearly 80%of the produced NH3 is used in the fertilizer industry and is essential for the development of global agriculture and consequently for maintaining population growth.Furthermore,NH3 can power hydrogen(H2)fueled devices,such as H2 fuel cells(FC),to use the interconversion between chemical energy and electric energy of nitrogen(N2)cycle,which can effectively alleviate the intermittent problems of renewable energy.However,the problems faced by NH3 in storage and release still restrict its development.Herein,this review introduces the latest research and development of electrochemical NH3 synthesis and direct NH3 FC,as well as outlines the technical challenges,possible improvement measures and development perspectives.N2 reduction reaction(NRR)and nitrate reduction reaction(NO3RR)are two potential approaches for electrochemical NH3 synthesis.However,the existing research foundation still faces challenges in achieving high selectivity and efficiency.Direct NH3 FC are easy to transport and are expected to be widely used in mobile energy consuming equipment,but also limited by the lack of highly active and stable NH3 oxidation electrocatalysts.The perspectives of ammonia fuel cells as an alternative green energy are discussed. 展开更多
关键词 Electrocatalysis nitrogen reduction reaction(nrr) Nitrate reduction reaction(NO3RR) Carbon-free hydrogen carrier Ammonia fuel cells
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Crystal defect engineering of Bi_(2)Te_(3)nanosheets by Ce doping for efficient electrocatalytic nitrogen reduction 被引量:1
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作者 Jianli Nan Yongqin Liu +2 位作者 Daiyong Chao Youxing Fang Shaojun Dong 《Nano Research》 SCIE EI CSCD 2023年第5期6544-6551,共8页
Electrochemical nitrogen reduction reaction(NRR)is a promising method for the synthesis of ammonia(NH3).However,the electrochemical NRR process remains a great challenge in achieving a high NH3 yield rate and a high F... Electrochemical nitrogen reduction reaction(NRR)is a promising method for the synthesis of ammonia(NH3).However,the electrochemical NRR process remains a great challenge in achieving a high NH3 yield rate and a high Faradaic efficiency(FE)due to the extremely strong N≡N bonds and the competing hydrogen evolution reaction(HER).Recently,bismuth telluride(Bi_(2)Te_(3))with two-dimensional layered structure has been reported as a promising catalyst for N_(2)fixation.Herein,to further enhance its NRR activity,a general doping strategy is developed to introduce and modulate the crystal defects of Bi_(2)Te_(3)nanosheets by adjusting the amount of Ce dopant(denoted as Ce_(x)-Bi_(2)Te_(3),where x represents the designed molar ratio of Ce/Bi).Meanwhile,the crystal defects can be designed and controlled by means of ion substitution and charge compensation.At−0.60 V versus the reversible hydrogen electrode(RHE),Ce_(0.3)-Bi_(2)Te_(3)exhibits a high NH_(3) yield(78.2μg·h^(−1)·mgcat^(−1)),a high FE(19.3%),excellent structural and electrochemical stability.Its outstanding catalytic activity is attributed to the tunable crystal defects by Ce doping.This work not only contributes to enhancing the NRR activity of Bi_(2)Te_(3)nanosheets,but also provides a reliable approach to prepare high-performance electrocatalysts by controlling the type and concentration of crystal defects for artificial N_(2)fixation. 展开更多
关键词 electrochemical ammonia synthesis nitrogen reduction reaction (bismuth telluride)Bi_(2)Te_(3)nanosheets Ce doping crystal defects
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Iron-group electrocatalysts for ambient nitrogen reduction reaction in aqueous media 被引量:14
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作者 Benyuan Ma Haitao Zhao +7 位作者 Tingshuai Li Qian Liu Yongsong Luo Chengbo Li Siyu Lu Abdullah M.Asiri Dongwei Ma Xuping Sun 《Nano Research》 SCIE EI CAS CSCD 2021年第3期555-569,共15页
Electrochemical nitrogen reduction reaction(NRR)is considered as an alternative to the industrial Haber-Bosch process for NH3 production due to both low energy consumption and environment friendliness.However,the majo... Electrochemical nitrogen reduction reaction(NRR)is considered as an alternative to the industrial Haber-Bosch process for NH3 production due to both low energy consumption and environment friendliness.However,the major problem of electrochemical NRR is the unsatisfied efficiency and selectivity of electrocatalyst.As one group of the cheapest and most abundant transition metals,iron-group(Fe,Co,Ni and Cu)electrocatalysts show promising potential on cost and performance advantages as ideal substitute for traditional noble-metal catalysts.In this minireview,we summarize recent advances of iron-group-based materials(including their oxides,hydroxides,nitrides,sulfides and phosphides,etc.)as non-noble metal electrocatalysts towards ambient N2-to-NH3 conversion in aqueous media.Strategies to boost NRR performances and perspectives for future developments are discussed to provide guidance for the field of NRR studies. 展开更多
关键词 nitrogen reduction reaction electrochemical NH_(3)synthesis iron-group catalysts ambient conditions
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Fe_(2)Mo_(3)O_(8)/XC-72 electrocatalyst for enhanced electrocatalytic nitrogen reduction reaction under ambient conditions 被引量:1
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作者 Guohua Liu Lijuan Niu +5 位作者 Zhixue Ma Li An Dan Qu Dandan Wang Xiayan Wang Zaicheng Sun 《Nano Research》 SCIE EI CSCD 2022年第7期5940-5945,共6页
To perform the electrochemical nitrogen reduction reaction(NRR)under milder conditions for sustainable ammonia production,electrocatalysts should exhibit high selectivity,activity,and durability.However,the key restri... To perform the electrochemical nitrogen reduction reaction(NRR)under milder conditions for sustainable ammonia production,electrocatalysts should exhibit high selectivity,activity,and durability.However,the key restrictions are the highly stable N≡N triple bond and the competitive hydrogen evolution reaction(HER),which make it difficult to adsorb and activate N2 on the surface of electrocatalysts,leading to a low ammonia yield and Faraday efficiency.Inspired by the enzymatic nitrogenase process and using the Fe-Mo as the active center,here we report supported Fe_(2)Mo_(3)O_(8)/XC-72 as an effective and durable electrocatalyst for the NRR.Fe_(2)Mo_(3)O_(8)/XC-72 exhibited NRR activity with an NH3 yield of 30.4μg·h^(−1)·mg^(−1)(−0.3 V)and a Faraday efficiency of 8.2%(−0.3 V).Theoretical calculations demonstrated that the electrocatalytic nitrogen fixation mechanism involved the Fe atom in the Fe_(2)Mo_(3)O_(8)/XC-72 electrocatalyst acting as the main active site in the enzymatic pathway(*NH2→*NH3),which activated nitrogen molecules and promoted the NRR performance. 展开更多
关键词 nitrogen reduction reaction(nrr) Fe_(2)Mo_(3)O_(8)/XC-72 electrocatalyst density functional theory calculations
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ZrO_(2)纳米晶高效地催化电化学氮气还原成氨
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作者 白馨月 郑坤屹 +2 位作者 朱子娴 王敏 张祥 《山东化工》 CAS 2023年第12期32-35,共4页
通过电化学氮气还原反应合成氨,反应条件温和,反应过程中没有温室气体的排放,更满足“碳中和”和“碳达峰”的要求。但是,由于缺乏高效的电催化剂,产氨率和法拉第效率不高,限制该反应的工业应用。因此开发高效的催化剂是电化学氮气还原... 通过电化学氮气还原反应合成氨,反应条件温和,反应过程中没有温室气体的排放,更满足“碳中和”和“碳达峰”的要求。但是,由于缺乏高效的电催化剂,产氨率和法拉第效率不高,限制该反应的工业应用。因此开发高效的催化剂是电化学氮气还原反应中非常关键但具有挑战性的课题。用简单易控的方法合成氧化锆纳米晶,并首次将氧化锆纳米晶作为电催化剂应用于电化学氮气还原反应中,实现了高效地氨合成。电化学测试结果表明,在0.1 mol/L的盐酸溶液中,氧化锆纳米晶的催化产氨量和法拉第效率均非常高,分别为27.93μg·h^(-1)·mg^(-1)和6.18%。 展开更多
关键词 氧化锆纳米晶 电催化 电化学氮气还原反应 氨的合成
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固酶氮掺杂碳纳米复合物基燃料电池性能 被引量:3
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作者 库里松.哈衣尔别克 赵淑贤 +1 位作者 杨阳 曾涵 《物理化学学报》 SCIE CAS CSCD 北大核心 2015年第9期1715-1726,共12页
利用掺杂氮介孔材料(NDMPC)和羧甲基壳聚糖(CMCH)机械共混的纳米复合物作为固酶载体,以滴涂-干燥法分别制备了固定漆酶(Lac)阴极和固定葡萄糖氧化酶阳极,组装了有Nafion离子交换膜的葡萄糖/O2酶燃料电池.固定漆酶电极作为燃料电池阴极... 利用掺杂氮介孔材料(NDMPC)和羧甲基壳聚糖(CMCH)机械共混的纳米复合物作为固酶载体,以滴涂-干燥法分别制备了固定漆酶(Lac)阴极和固定葡萄糖氧化酶阳极,组装了有Nafion离子交换膜的葡萄糖/O2酶燃料电池.固定漆酶电极作为燃料电池阴极和氧电化学传感器的性能以结合旋转圆盘电极技术的循环伏安法、线性扫描伏安(LSV)法以及计时电流法进行表征,同时使用紫外-可见分光光度法和石墨炉原子吸收光谱法研究酶分子在电极表面的构型和估算电极表面载体对酶的担载量.测试结果表明:固酶阴极在无电子中介体时可以实现漆酶活性中心T1与导电基体之间的直接电子迁移(表观电子迁移速率为0.013 s–1),而且具有较小的氧还原超电势(150 m V).通过进一步定量比较分子内电子传递速率(1000 s–1)、底物转化速率(0.023 s–1)以及前述酶-导电基体间电子迁移速率,可以发现此电极催化氧还原循环受制于酶-电极之间的电子迁移过程;这种电极对氧的传感性能良好:低检测限(0.04μmol dm–3)、高灵敏度(12.1μAμmol–1 dm3)和良好的对氧亲和力(KM=8.2μmol dm–3),这种固酶阴极还具有良好的重现性、长期使用性、热稳定性和pH耐受性.组装的生物燃料电池的开路电压为0.38 V,最大能量输出密度为19.2μW cm–2,最佳工作条件下使用3周后输出功率密度仍可保持初始值的60%以上. 展开更多
关键词 漆酶 氮掺杂介孔碳材料 羧甲基壳聚糖 直接电子迁移 氧还原反应 电化学传感器 生物燃料电池
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