Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated el...Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.展开更多
Transformation of glycerol into value-added che micals via electro-oxidation using the green electricity is considered as a sustainable and promising process.Whereas,the synthesis of specific C3 products such as glyce...Transformation of glycerol into value-added che micals via electro-oxidation using the green electricity is considered as a sustainable and promising process.Whereas,the synthesis of specific C3 products such as glyceric acid(GLA)from electro-oxidation of glycerol still suffers from poor catalytic performance.Here,we used a two-step deposition strategy to prepare Au-CeO_(2)/CNT catalyst for highly efficient electrosynthesis of GLA from glycerol oxidation under alkaline conditions.Upon treating 0.5 mol/L glycerol at 1.12 V(vs.RHE)for 12 h in 1.0 mol/L KOH solution,the glycerol conversion and GLA selectivity over Au-CeO_(2)/CNT achieve 99.7%and 50.0%,respectively.The glycerol conversion doubles when an optimal amount of CeO_(2)is introduced to the Au/CNT catalyst,Au-CeO_(2)/CNT provides numerous active sites at ternary junctions of Au-CeO_(2)-CNT,which effectively suppress the adsorption of GLA on the surface of Au nanoparticles and prevent the nanoparticles from serious agglomeration,thereby facilitate the glycerol-to-GLA conversion with considerable cyclability.This study provides valuable insight into the rational design of high-performance catalysts for alcohol electro-oxidation.展开更多
With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk che...With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).展开更多
Carbon monoxide(CO)oxidation is crucial for pollutant removal and hydrogen purification.In recent years,copper–cerium(Cu–Ce)-mixed oxide catalysts have attracted significant attention due to their excellent activity a...Carbon monoxide(CO)oxidation is crucial for pollutant removal and hydrogen purification.In recent years,copper–cerium(Cu–Ce)-mixed oxide catalysts have attracted significant attention due to their excellent activity and stability in CO oxida-tion.This study presents an innovative,environmentally friendly electrosynthesis method for producing stable,structured Cu–Ce catalysts in mesh form.This approach addresses the limitations of traditional pellet catalysts,such as fragility and poor thermal conductivity.The results demonstrated that incorporating cerium(Ce)enhanced the catalytic activity for CO oxidation threefold.A series of in situ characterizations revealed that the introduction of Ce led to the formation of a Cu–Ce mixed oxide solid solution,which significantly improved catalytic performance.Furthermore,higher pretreatment tem-peratures facilitated the decomposition of Ce compounds(nitrate and hydroxide),which promotes the formation of Cu–Ce solid solutions and increases the concentration of active intermediate species(Cu^(+)-CO)during the reaction.This process ultimately enhanced the catalyst’s activity.展开更多
Electrochemical synthesis of value-added chemicals represents a promising approach to address multidisciplinary demands.This technology establishes direct pathways for electricity-to-chemical conversion while signific...Electrochemical synthesis of value-added chemicals represents a promising approach to address multidisciplinary demands.This technology establishes direct pathways for electricity-to-chemical conversion while significantly reducing the carbon footprint of chemical manufacturing.It simultaneously optimizes chemical energy storage and grid management,offering sustainable solutions for renewable energy utilization and overcoming geographical constraints in energy distribution.As a critical nexus between renewable energy and green chemistry,electrochemical synthesis serves dual roles in energy transformation and chemical production,emerging as a vital component in developing carbon-neutral circular economies.Focusing on key small molecules(H_(2)O,CO_(2),N_(2),O_(2)),this comment examines fundamental scientific challenges and practical barriers in electrocatalytic conversion processes,bridging laboratory innovations with industrial-scale implementation.展开更多
Developing energy-efficient nitrite-to-ammonia(NO_(2)RR)conversion technologies while simultaneously enabling the electrochemical upcycling of waste polyethylene terephthalate(PET)plastics into highvalue-added chemica...Developing energy-efficient nitrite-to-ammonia(NO_(2)RR)conversion technologies while simultaneously enabling the electrochemical upcycling of waste polyethylene terephthalate(PET)plastics into highvalue-added chemicals is of great significance.Herein,an atomic oxygen vacancy(V_(o))engineering is developed to optimize the catalytic performance of V_(o2)-Co(OH)F nanoarray towards the NO_(2)RR and PET-derived ethylene glycol oxidation reaction(EGOR).The optimal V_(o2)-Co(OH)F achieves an ultralow operating potential of -0.03 V vs.RHE at -100 mA cm^(-2)and a remarkable NH_(3)Faradaic efficiency(FE)of 98.4% at -0.2 V vs.RHE for NO_(2)RR,and a high formate FE of 98.03% for EGOR.Operando spectroscopic analysis and theoretical calculations revealed that oxygen vacancies play a crucial role in optimizing the electronic structure of V_(o2)-Co(OH)F,modulating the adsorption free energies of key reaction intermediates,and lowering the reaction energy barrier,thereby enhancing its overall catalytic performance.Remarkably,the V_(o2)-Co(OH)F-based NO_(2)RR||EGOR electrolyzer realized high NH_(3)and formate yield rates of 33.9 and 44.9 mg h^(-1)cm^(-2)at 1.7 V,respectively,while demonstrating outstanding long-term stability over 100 h.This work provides valuable insights into the rational design of advanced electrocatalysts for co-electrolysis systems.展开更多
Achieving industrial-level electrochemical CO_(2)reduction to formate remains a significant challenge due to limitations in catalyst selectivity and interfacial proton management at high current densities.In a recent ...Achieving industrial-level electrochemical CO_(2)reduction to formate remains a significant challenge due to limitations in catalyst selectivity and interfacial proton management at high current densities.In a recent study,Prof.Guo and colleagues report the development of Turingstructured electrocatalysts,which incorporate reaction-diffusion-inspired topologies to engineer mesoscale surface patterns.This design enables precise modulation of the interfacial microenvironment,enhancing CO_(2)activation and suppressing competing hydrogen evolution.The resulting catalysts achieve efficient and stable CO_(2)-to-formate conversion under industrially relevant conditions,offering a promising strategy for scalable carbon-neutral chemical production.展开更多
Compared to aqueous-phase electrocatalytic nitrogen reduction reaction(NRR),lithium-mediated NRR(Li-NRR)theoretically enhances the intrinsic activity of NH3 production through spontaneous exothermic reactions between ...Compared to aqueous-phase electrocatalytic nitrogen reduction reaction(NRR),lithium-mediated NRR(Li-NRR)theoretically enhances the intrinsic activity of NH3 production through spontaneous exothermic reactions between Li and N_(2).However,the in-situ generated solid electrolyte interphase(SEI)during the reaction slows down the Li^(+)transport and nucleation kinetics,which further hinders the subsequent activation and protonation processes.Herein,a sophisticated amorphous-crystalline heterostructured SEI of Zn-LiF is formed by additive engineering.The concerted electron interplay between amorphous and crystalline domains is prone to generate lithiophobic Zn and lithiophilic LiF sites,where lithiophobic Zn accelerates Li^(+)diffusion within the SEI and avoids high concentration polarization,and lithiophilic LiF ensures homogeneous nucleation of diffused Li^(+)and its participation in subsequent reactions.Therefore,compared to conventional SEI,a more than 8-fold performance improvement is achieved in the additive-engineered heterogeneous lithiophobic-lithiophilic SEI,which exhibits a high NH_(3)yield rate of 11.58 nmol s^(−1)cm^(−2)and a Faradaic efficiency of 32.97%.Thus,exploiting the synergistic effects in heterogeneous lithiophobic-lithiophilic structures to achieve functional complementarity between different components opens a new avenue toward high-performance Li-NRR.展开更多
Paired electrosynthesis has received considerable attention as a consequence of simultaneously synthesizing target products at both cathode and anode,whereas the related synthetic efficiency in batch reactors is still...Paired electrosynthesis has received considerable attention as a consequence of simultaneously synthesizing target products at both cathode and anode,whereas the related synthetic efficiency in batch reactors is still undesirable under certain circumstances.Encouragingly,laminar microfluidic reactor offers prospective options that possess controllable flow characteristics such as enhanced mass transport,precise laminar flow control and the ability to expand production scale progressively.In this comprehensive review,the underlying fundamentals of the paired electrosynthesis are initially summarized,followed by categorizing the paired electrosynthesis including parallel paired electrosynthesis,divergent paired electrosynthesis,convergent paired electrosynthesis,sequential paired electrosynthesis and linear paired electrosynthesis.Thereafter,a holistic overview of microfluidic reactor equipment,integral fundamentals and research methodology as well as channel extension and scale-up strategies is proposed.The established fundamentals and evaluated metrics further inspired the applications of microfluidic reactors in paired electrosynthesis.This work stimulated the overwhelming investigation of mechanism discovery,material screening strategies,and device assemblies.展开更多
The recycling of plastics is a significant global concern.Due to the thermosetting properties of melamineformaldehyde(MF)resin plastics,which make heating and melting difficult,their recycling and reuse pose substanti...The recycling of plastics is a significant global concern.Due to the thermosetting properties of melamineformaldehyde(MF)resin plastics,which make heating and melting difficult,their recycling and reuse pose substantial challenges.In this study,we developed nitrogen-doped(N-doped)carbon materials through scalable carbonization of MF resin plastic waste.This metal-free N-doped carbon catalyst achieved a hydrogen peroxide(H_(2)O_(2))production rate of 971.6 mmol gcatalyst^(-1)h^(-1)with a Faradaic efficiency for H_(2)O_(2)(FEH_(2)O_(2))exceeding 90%under acidic conditions.Additionally,a flow cell utilizing this carbon catalyst demonstrated a production rate of 11.3 mol cm^(-2)h^(-1)(22.5 mol g_(catalyst)^(-1)h^(-1))and maintained a record-high current density of approximately 530 mA cm^(-2)over 300 h.In-situ electrochemical surface-enhanced Raman spectroscopy and density functional theory calculations revealed the presence of porphyrin-like carbon defects,which serve as active sites for the continuous and stable generation of^(*)OOH species.The nitrogen-doped carbon materials obtained from large-scale carbonization of MF plastic waste exhibit abundant active sites,making them highly promising electrocatalysts for the two-electron oxygen reduction reaction(2e^(-)ORR).展开更多
Organic electrosynthesis as an emerging green and advantageous alternative to traditional synthetic methods has achieved remarkable progress in recent years because sustainable electricity can be employed as traceless...Organic electrosynthesis as an emerging green and advantageous alternative to traditional synthetic methods has achieved remarkable progress in recent years because sustainable electricity can be employed as traceless redox agents. To surmount the over-oxidation/reduction issues of direct electrolysis,mediated or indirect electrochemical processes are attaining remarkable significance and promoting the selectivity of products. Molecular electrocatalysts, benefiting from the easily electronic and steric modulation, suffers from readily degradation issue in most cases. Remarkably, heterogeneous catalysts have drawn more attention due to their high activity, stability, and recyclability. Hence, in this review, the most recent growth of heterogeneous catalysts modified electrodes for organic electrosynthesis were summarized, highlighting structural optimization and electrochemical performance of these materials as well as reaction mechanism. Furthermore, key challenges and future directions in this area were also discussed.展开更多
A new green technique for producing chromic acid via an electrosynthesis method was studied.The kinetic experiments were carried out on the direct electrosynthesis reaction of chromic acid from sodium dichromate in a ...A new green technique for producing chromic acid via an electrosynthesis method was studied.The kinetic experiments were carried out on the direct electrosynthesis reaction of chromic acid from sodium dichromate in a self-made electrosynthesis reactor with a multiple-unit metal oxides combination anode,a stainless steel cathode,and a reinforcing combination Nafion 324 cation exchange membrane.The apparent kinetic data were experimentally measured at different reaction time under different reaction conditions by relating many essential cell processes and their interaction,as well as their synergistic effect to the whole electrochemical synthesis process.The results show that the electrosynthesis reaction process follows a quasi-first-order reaction kinetic characteristic.The apparent kinetic model of the electrosynthesis reaction was established,and kinetic parameters were calculated.展开更多
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 engineere...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.展开更多
Microbial electrosynthesis(MES) can potentially provide a mean for storing renewable energy surpluses as chemical energy. However, the fluctuating nature of these energy sources may represent a threat to MES, as the m...Microbial electrosynthesis(MES) can potentially provide a mean for storing renewable energy surpluses as chemical energy. However, the fluctuating nature of these energy sources may represent a threat to MES, as the microbial communities that develop on the biocathode rely on the continuous existence of a polarized electrode. This work assesses how MES performance, product generation and microbial community evolution are affected by a long-period(6 weeks) power off(open circuit). Acetogenic and H2-producing bacteria activity recovered after reconnection. However, few days later syntrophic acetate oxidation bacteria and H2-consuming methanogens became dominant, producing CH4 as the main product, via electromethanogenesis and the syntrophic interaction between eubacterial and archaeal communities which consume both the acetic acid and the hydrogen present in the cathode environment. Thus,the system proved to be resilient to a long-term power interruption in terms of electroactivity. At the same time, these results demonstrated that the system could be extensively affected in both end product generation and microbial communities.展开更多
Oxygen evolution reaction(OER) is a key process for electrochemical water splitting due to its intrinsic large overpotential. Recently, layered double hydroxides(LDHs), especially Ni Fe-LDH, have been regarded as high...Oxygen evolution reaction(OER) is a key process for electrochemical water splitting due to its intrinsic large overpotential. Recently, layered double hydroxides(LDHs), especially Ni Fe-LDH, have been regarded as highly performed electrocatalysts for OER in alkaline condition. Here we first present a new class of Ni La-LDH electrocatalyst synthesized by an electrochemical process for efficient water splitting. The as-prepared NiL a-LDH nanosheet arrays(NSAs) give remarkable electrochemical activity and durability under alkaline environments, with a low overpotential of 209 mV for OER to deliver a current density of 10 mA cm^-2, surpassing most of previous reported LDHs eletrocatalysts. The presence of NiLa-LDH in this work extends the studies about LDHs-based electrocatalysts, which will benefit the development of electrochemical energy storage and conversion systems.展开更多
A one-step molten salt electrochemical strategy was proposed to synthesize SiC nanoparticles from ultra-fine silicon dioxide/carbon(SiO_(2)/C)mixtures.The electrosynthesis process and physicochemical properties of the...A one-step molten salt electrochemical strategy was proposed to synthesize SiC nanoparticles from ultra-fine silicon dioxide/carbon(SiO_(2)/C)mixtures.The electrosynthesis process and physicochemical properties of the synthesized products were systematically analyzed via X-ray diffraction,electron microscopy,Raman spectroscopy and photoluminescence spectroscopy,etc.A combined chemical/electrochemical reaction,electrochemical deoxidation,and in-situ carbonization reaction mechanism was proposed to reveal the electrochemical synthesis process of SiC nanoparticles from SiO_(2)/C in molten CaCl_(2).The as-prepared SiC with particle size ranging from 8 to 14 nm possesses a polycrystalline structure.In addition,the SiC nanoparticles demonstrate obvious photoluminescence property due to the synergetic size effect and microstructural characteristics.展开更多
Microbial electrosynthesis system (MES) is a promising method that can use carbon dioxide,which is a greenhouse gas,to produce methane which acts as an energy source,without using organic substances.However,this bioel...Microbial electrosynthesis system (MES) is a promising method that can use carbon dioxide,which is a greenhouse gas,to produce methane which acts as an energy source,without using organic substances.However,this bioelectrical reduction reaction can proceed at a certain high applied voltage when coupled with water oxidation in the anode coated with metallic catalyst.When coupled with the oxidation of HS–to SO_(4)^(2-),methane production is thermodynamically more feasible,thus implying its production at a considerably lower applied voltage.In this study,we demonstrated the possibility of electrotrophic methane production coupled with HS–oxidation in a cost-effective bioanode chamber in the MES without organic substrates at a low applied voltage of 0.2 V.In addition,microbial community analyses of biomass enriched in the bioanode and biocathode were used to reveal the most probable pathway for methane production from HS–oxidation.In the bioanode,electroautotrophic SO_(4)^(2-)production accompanied with electron donation to the electrode is performed mainly by the following two steps:first,incomplete sulfide oxidation to sulfur cycle intermediates (SCI) is performed;then the produced SCI are disproportionated to HS^(–)and SO_(4)^(2-).In the biocathode,methane is produced mainly via H_(2)and acetate by electronaccepting syntrophic bacteria,homoacetogens,and acetoclastic archaea.Here,a new ecofriendly MES with biological H_(2)S removal is established.展开更多
High/medium entropy alloys(HEAs/MEAs)with high electrocatalytic activity have attracted great attention in water electrolysis applications.However,facile synthesis of self-supporting high/medium entropy alloys electro...High/medium entropy alloys(HEAs/MEAs)with high electrocatalytic activity have attracted great attention in water electrolysis applications.However,facile synthesis of self-supporting high/medium entropy alloys electrocatalysts with rich active sites through classical metallurgical methods is still a challenge.Here,a self-supporting porous FeCoNi MEA electrocatalyst with nanosheets-shaped surface for oxygen evolution reaction(OER)was prepared by a one-step electrochemical process from the metal oxides in molten CaCl_(2).The formation of the FeCoNi MEA is attributed to the oxides electro-reduction,high-temperature diffusion and solid solution.Additionally,the morphology and structure of the FeCoNi MEA can be precisely controlled by adjusting the electrolysis time and temperature.The electronic structure regulation and the reduced energy barrier of OER from the“cocktail effect”,the abundant exposed active sites brought by surface ultrathin nanosheets,the good electronic conductivity and electrochemical stability from the self-supporting structure enable the FeCoNi MEA electrode shows high-performance OER electrocatalysis,exhibiting a low overpotential of 233 mV at a current density of 10 mA cm^(-2),a low Tafel slope of 29.8 mV dec^(-1),and an excellent stability for over 500 h without any obvious structural destruction.This work demonstrates a facile one-step electrochemical metallurgical approach for fabricating self-supporting HEAs/MEAs electrocatalysts with nanosized surface for the application in water electrolysis.展开更多
Hydrogen peroxide(H2O2)is one of the 100 most important chemicals involved in multiple chemical processes including paper and textile manufacturing,waste degradation,and pharmaceutical production[1].Compared with the ...Hydrogen peroxide(H2O2)is one of the 100 most important chemicals involved in multiple chemical processes including paper and textile manufacturing,waste degradation,and pharmaceutical production[1].Compared with the current industrial process to produce H2O2 following the anthraquinone oxidation/reduction method,electrochemical reduction of oxygen to H2O2 through a two-electron pathway constitutes an environmental friendly alternative route[2-4].Unfortunately,the electrogeneration of H2O2 from two-electron reduction of oxygen feedstock is kinetically sluggish and therefore requires electrocatalysts with high reactivity,high selectivity,and good stability[5,6].展开更多
基金supported by the National Key R&D Program of China(2024YFA1211004)the National Natural Science Foundation of China(22402150,22072107)+1 种基金the Natural Science Foundation of Shanghai(23ZR1464800,24ZR1470200)the Foundation of State Key Laboratory of Pollution Control and Resource Reuse(Tongji University)。
文摘Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.
基金Project supported by the National Natural Science Foundation of China(22161033,21875125)the Natural Science Foundation of Inner Mongolia Autonomous Region of China(2023ZD11)+1 种基金the 111 Project(D20033)the"Grassland Talent"Program and"Grassland Talent"Innovation Team of Inner Mongolia。
文摘Transformation of glycerol into value-added che micals via electro-oxidation using the green electricity is considered as a sustainable and promising process.Whereas,the synthesis of specific C3 products such as glyceric acid(GLA)from electro-oxidation of glycerol still suffers from poor catalytic performance.Here,we used a two-step deposition strategy to prepare Au-CeO_(2)/CNT catalyst for highly efficient electrosynthesis of GLA from glycerol oxidation under alkaline conditions.Upon treating 0.5 mol/L glycerol at 1.12 V(vs.RHE)for 12 h in 1.0 mol/L KOH solution,the glycerol conversion and GLA selectivity over Au-CeO_(2)/CNT achieve 99.7%and 50.0%,respectively.The glycerol conversion doubles when an optimal amount of CeO_(2)is introduced to the Au/CNT catalyst,Au-CeO_(2)/CNT provides numerous active sites at ternary junctions of Au-CeO_(2)-CNT,which effectively suppress the adsorption of GLA on the surface of Au nanoparticles and prevent the nanoparticles from serious agglomeration,thereby facilitate the glycerol-to-GLA conversion with considerable cyclability.This study provides valuable insight into the rational design of high-performance catalysts for alcohol electro-oxidation.
基金supported by the National Natural Science Foundation of China(Nos.22175174 and 52332007).
文摘With the rapid evolution of contemporary society,there is an increasing demand for the production of bulk chemicals such as fertilizers,fuels,and pharmaceuticals.However,current synthetic approaches for these bulk chemicals predominantly depend on conventional fossil fuel-based chemical refining processes.This dependence poses a substantial challenge to both environmental sustainability and energy resources[1].An example of this issue is the synthesis of hydroxylamine(NH2OH).
基金supported by the National Key R&D Program of China(No.2022YFB3805504)the National Natu-ral Science Foundation of China(No.22078089)+2 种基金the Shanghai Pilot Program for Basic Research(No.22TQ1400100-7)the Basic Research Program of Science and Technology Commission of Shanghai Munici-pality(No.22JC1400600)the Fundamental Research Funds for the Central Universities.
文摘Carbon monoxide(CO)oxidation is crucial for pollutant removal and hydrogen purification.In recent years,copper–cerium(Cu–Ce)-mixed oxide catalysts have attracted significant attention due to their excellent activity and stability in CO oxida-tion.This study presents an innovative,environmentally friendly electrosynthesis method for producing stable,structured Cu–Ce catalysts in mesh form.This approach addresses the limitations of traditional pellet catalysts,such as fragility and poor thermal conductivity.The results demonstrated that incorporating cerium(Ce)enhanced the catalytic activity for CO oxidation threefold.A series of in situ characterizations revealed that the introduction of Ce led to the formation of a Cu–Ce mixed oxide solid solution,which significantly improved catalytic performance.Furthermore,higher pretreatment tem-peratures facilitated the decomposition of Ce compounds(nitrate and hydroxide),which promotes the formation of Cu–Ce solid solutions and increases the concentration of active intermediate species(Cu^(+)-CO)during the reaction.This process ultimately enhanced the catalyst’s activity.
文摘Electrochemical synthesis of value-added chemicals represents a promising approach to address multidisciplinary demands.This technology establishes direct pathways for electricity-to-chemical conversion while significantly reducing the carbon footprint of chemical manufacturing.It simultaneously optimizes chemical energy storage and grid management,offering sustainable solutions for renewable energy utilization and overcoming geographical constraints in energy distribution.As a critical nexus between renewable energy and green chemistry,electrochemical synthesis serves dual roles in energy transformation and chemical production,emerging as a vital component in developing carbon-neutral circular economies.Focusing on key small molecules(H_(2)O,CO_(2),N_(2),O_(2)),this comment examines fundamental scientific challenges and practical barriers in electrocatalytic conversion processes,bridging laboratory innovations with industrial-scale implementation.
基金financially supported by the National Natural Science Foundation of China(22205205)the Fundamental Research Funds of Zhejiang Sci-Tech University(ZSTU,25262157Y)the staff of beamline BL11B and BL13SSW at Shanghai Synchrotron Radiation Facility for experimental support。
文摘Developing energy-efficient nitrite-to-ammonia(NO_(2)RR)conversion technologies while simultaneously enabling the electrochemical upcycling of waste polyethylene terephthalate(PET)plastics into highvalue-added chemicals is of great significance.Herein,an atomic oxygen vacancy(V_(o))engineering is developed to optimize the catalytic performance of V_(o2)-Co(OH)F nanoarray towards the NO_(2)RR and PET-derived ethylene glycol oxidation reaction(EGOR).The optimal V_(o2)-Co(OH)F achieves an ultralow operating potential of -0.03 V vs.RHE at -100 mA cm^(-2)and a remarkable NH_(3)Faradaic efficiency(FE)of 98.4% at -0.2 V vs.RHE for NO_(2)RR,and a high formate FE of 98.03% for EGOR.Operando spectroscopic analysis and theoretical calculations revealed that oxygen vacancies play a crucial role in optimizing the electronic structure of V_(o2)-Co(OH)F,modulating the adsorption free energies of key reaction intermediates,and lowering the reaction energy barrier,thereby enhancing its overall catalytic performance.Remarkably,the V_(o2)-Co(OH)F-based NO_(2)RR||EGOR electrolyzer realized high NH_(3)and formate yield rates of 33.9 and 44.9 mg h^(-1)cm^(-2)at 1.7 V,respectively,while demonstrating outstanding long-term stability over 100 h.This work provides valuable insights into the rational design of advanced electrocatalysts for co-electrolysis systems.
基金financially supported by the National Natural Science Foundation of China(No.22209024)Tongcheng R&D Foundation(No.CPCIF-RA-0102)the State Key Laboratory of Advanced Fiber Materials,Donghua University
文摘Achieving industrial-level electrochemical CO_(2)reduction to formate remains a significant challenge due to limitations in catalyst selectivity and interfacial proton management at high current densities.In a recent study,Prof.Guo and colleagues report the development of Turingstructured electrocatalysts,which incorporate reaction-diffusion-inspired topologies to engineer mesoscale surface patterns.This design enables precise modulation of the interfacial microenvironment,enhancing CO_(2)activation and suppressing competing hydrogen evolution.The resulting catalysts achieve efficient and stable CO_(2)-to-formate conversion under industrially relevant conditions,offering a promising strategy for scalable carbon-neutral chemical production.
基金supported by the National Natural Science Foundation of China(22178361,22378402,52302310)the International Partnership Project of CAS(039GJHZ2022029GC)+3 种基金the National Key R&D Program of China(2020YFA0710200)the Foundation of the Innovation Academy for Green Manufacture Institute,Chinese Academy of Sciences(IAGM2022D07)QinChuangYuan Cites High-level Innovation and Entrepreneurship Talent Programs(QCYRCXM-2022-335)the Open Project Program of Anhui Province International Research Center on Advanced Building Materials(JZCL2303KF).
文摘Compared to aqueous-phase electrocatalytic nitrogen reduction reaction(NRR),lithium-mediated NRR(Li-NRR)theoretically enhances the intrinsic activity of NH3 production through spontaneous exothermic reactions between Li and N_(2).However,the in-situ generated solid electrolyte interphase(SEI)during the reaction slows down the Li^(+)transport and nucleation kinetics,which further hinders the subsequent activation and protonation processes.Herein,a sophisticated amorphous-crystalline heterostructured SEI of Zn-LiF is formed by additive engineering.The concerted electron interplay between amorphous and crystalline domains is prone to generate lithiophobic Zn and lithiophilic LiF sites,where lithiophobic Zn accelerates Li^(+)diffusion within the SEI and avoids high concentration polarization,and lithiophilic LiF ensures homogeneous nucleation of diffused Li^(+)and its participation in subsequent reactions.Therefore,compared to conventional SEI,a more than 8-fold performance improvement is achieved in the additive-engineered heterogeneous lithiophobic-lithiophilic SEI,which exhibits a high NH_(3)yield rate of 11.58 nmol s^(−1)cm^(−2)and a Faradaic efficiency of 32.97%.Thus,exploiting the synergistic effects in heterogeneous lithiophobic-lithiophilic structures to achieve functional complementarity between different components opens a new avenue toward high-performance Li-NRR.
基金supported by the National Natural Science Foundation of China(22178361,22378402,52302310)the International Partnership Project of CAS(039GJHZ2022029GC)+5 种基金the National Key R&D Program of China(2020YFA0710200)the foundation of the Innovation Academy for Green Manufacture Institute,Chinese Academy of Sciences(IAGM2022D07)the China Postdoctoral Science Foundation(2022M722597)QinChuangYuan Cites High-level Innovation and Entrepreneurship Talent Programs(QCYRCXM-2022-335)the Fundamental Research Funds for the Central Universities(G2022KY05111)the Open Project Program of Anhui Province International Research Center on Advanced Building Materials(JZCL2303KF)。
文摘Paired electrosynthesis has received considerable attention as a consequence of simultaneously synthesizing target products at both cathode and anode,whereas the related synthetic efficiency in batch reactors is still undesirable under certain circumstances.Encouragingly,laminar microfluidic reactor offers prospective options that possess controllable flow characteristics such as enhanced mass transport,precise laminar flow control and the ability to expand production scale progressively.In this comprehensive review,the underlying fundamentals of the paired electrosynthesis are initially summarized,followed by categorizing the paired electrosynthesis including parallel paired electrosynthesis,divergent paired electrosynthesis,convergent paired electrosynthesis,sequential paired electrosynthesis and linear paired electrosynthesis.Thereafter,a holistic overview of microfluidic reactor equipment,integral fundamentals and research methodology as well as channel extension and scale-up strategies is proposed.The established fundamentals and evaluated metrics further inspired the applications of microfluidic reactors in paired electrosynthesis.This work stimulated the overwhelming investigation of mechanism discovery,material screening strategies,and device assemblies.
基金supported by the National Natural Science Foundation of China(Grant No.22276123,22025505)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(SL2022ZD105)State Key Lab of Metal Matrix Composite。
文摘The recycling of plastics is a significant global concern.Due to the thermosetting properties of melamineformaldehyde(MF)resin plastics,which make heating and melting difficult,their recycling and reuse pose substantial challenges.In this study,we developed nitrogen-doped(N-doped)carbon materials through scalable carbonization of MF resin plastic waste.This metal-free N-doped carbon catalyst achieved a hydrogen peroxide(H_(2)O_(2))production rate of 971.6 mmol gcatalyst^(-1)h^(-1)with a Faradaic efficiency for H_(2)O_(2)(FEH_(2)O_(2))exceeding 90%under acidic conditions.Additionally,a flow cell utilizing this carbon catalyst demonstrated a production rate of 11.3 mol cm^(-2)h^(-1)(22.5 mol g_(catalyst)^(-1)h^(-1))and maintained a record-high current density of approximately 530 mA cm^(-2)over 300 h.In-situ electrochemical surface-enhanced Raman spectroscopy and density functional theory calculations revealed the presence of porphyrin-like carbon defects,which serve as active sites for the continuous and stable generation of^(*)OOH species.The nitrogen-doped carbon materials obtained from large-scale carbonization of MF plastic waste exhibit abundant active sites,making them highly promising electrocatalysts for the two-electron oxygen reduction reaction(2e^(-)ORR).
基金the financial support from the National Natural Science Foundation of China (No. 22171154)the Youth Innovative Talents Recruitment and Cultivation Program of Shandong Higher Education+2 种基金the Natural Science Foundation of Shandong Province (Nos. ZR^(2)020QB114, ZR^(2)020QB008 and ZR^(2)019BB031)Jinan Science&Technology Bureau (No. 2021GXRC080)The project supported by the Foundation (No. ZZ20190312) of State Key Laboratory of Biobased Material and Green Papermaking,Qilu University of Technology (Shandong Academy of Sciences)。
文摘Organic electrosynthesis as an emerging green and advantageous alternative to traditional synthetic methods has achieved remarkable progress in recent years because sustainable electricity can be employed as traceless redox agents. To surmount the over-oxidation/reduction issues of direct electrolysis,mediated or indirect electrochemical processes are attaining remarkable significance and promoting the selectivity of products. Molecular electrocatalysts, benefiting from the easily electronic and steric modulation, suffers from readily degradation issue in most cases. Remarkably, heterogeneous catalysts have drawn more attention due to their high activity, stability, and recyclability. Hence, in this review, the most recent growth of heterogeneous catalysts modified electrodes for organic electrosynthesis were summarized, highlighting structural optimization and electrochemical performance of these materials as well as reaction mechanism. Furthermore, key challenges and future directions in this area were also discussed.
基金Supported by the National Natural Science Foundation of China(No.20676136)
文摘A new green technique for producing chromic acid via an electrosynthesis method was studied.The kinetic experiments were carried out on the direct electrosynthesis reaction of chromic acid from sodium dichromate in a self-made electrosynthesis reactor with a multiple-unit metal oxides combination anode,a stainless steel cathode,and a reinforcing combination Nafion 324 cation exchange membrane.The apparent kinetic data were experimentally measured at different reaction time under different reaction conditions by relating many essential cell processes and their interaction,as well as their synergistic effect to the whole electrochemical synthesis process.The results show that the electrosynthesis reaction process follows a quasi-first-order reaction kinetic characteristic.The apparent kinetic model of the electrosynthesis reaction was established,and kinetic parameters were calculated.
基金support from the Natural Science Foundation of Liaoning Province(general program)(2020-MS-137)T.J.White would like to thank the MOE2019-T2-2-032 grant and Monetary Academic Resources for Research Grant 001561-00001 in Nanyang Technological University,Singapore+9 种基金T.Ma would like to thank the National Natural Science Foundation of China(Nos.52071171,52202248)Liaoning BaiQianWan Talents Program(LNBQW2018B0048)Shenyang Science and Technology Project(21-108-9-04)Australian Research Council(ARC)through Future Fellowship(FT210100298,FT210100806)Discovery Project(DP220100603)Linkage Project(LP210100467,LP210200504,LP210200345,LP220100088)Industrial Transformation Training Centre(IC180100005)schemesthe Australian Government through the Cooperative Research Centres Projects(CRCPXIII000077)F.Wei would like to thank the A^(*)STAR career development fund C210112054Singapore structural metal alloy program grant No.A18b1B0061.A.K.Cheetham would like to thank the Ras al Khaimah Centre for Advanced Materials.
文摘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.
基金the Spanish“Ministerio de Educación,Cultura y Deporte”for the predoctoral FPU Grant(FPU14/01573)the‘Ministerio de Economía y Competitividad’for the support of project ref:CTQ2015-68925-R(MINECO/FEDER,EU)。
文摘Microbial electrosynthesis(MES) can potentially provide a mean for storing renewable energy surpluses as chemical energy. However, the fluctuating nature of these energy sources may represent a threat to MES, as the microbial communities that develop on the biocathode rely on the continuous existence of a polarized electrode. This work assesses how MES performance, product generation and microbial community evolution are affected by a long-period(6 weeks) power off(open circuit). Acetogenic and H2-producing bacteria activity recovered after reconnection. However, few days later syntrophic acetate oxidation bacteria and H2-consuming methanogens became dominant, producing CH4 as the main product, via electromethanogenesis and the syntrophic interaction between eubacterial and archaeal communities which consume both the acetic acid and the hydrogen present in the cathode environment. Thus,the system proved to be resilient to a long-term power interruption in terms of electroactivity. At the same time, these results demonstrated that the system could be extensively affected in both end product generation and microbial communities.
基金supported by the National Natural Science Foundation of China (21601011 and 21521005)the National Key Research and Development Programme (2017YFA0206804)the Fundamental Research Funds for the Central Universities (buctrc201506 and buctylkxj01)
文摘Oxygen evolution reaction(OER) is a key process for electrochemical water splitting due to its intrinsic large overpotential. Recently, layered double hydroxides(LDHs), especially Ni Fe-LDH, have been regarded as highly performed electrocatalysts for OER in alkaline condition. Here we first present a new class of Ni La-LDH electrocatalyst synthesized by an electrochemical process for efficient water splitting. The as-prepared NiL a-LDH nanosheet arrays(NSAs) give remarkable electrochemical activity and durability under alkaline environments, with a low overpotential of 209 mV for OER to deliver a current density of 10 mA cm^-2, surpassing most of previous reported LDHs eletrocatalysts. The presence of NiLa-LDH in this work extends the studies about LDHs-based electrocatalysts, which will benefit the development of electrochemical energy storage and conversion systems.
基金the National Natural Science Foundation of China(Nos.52022054,51974181,52004157)the Shanghai Rising-Star Program,China(No.19QA1403600)+4 种基金the Shanghai Sailing Program,China(No.21YF1412900)and the Iron and Steel Joint Research Fund of National Natural Science Foundation of China and China Baowu Steel Group Corporation Limited(No.U1860203)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning,China(No.TP2019041)the Shanghai Postdoctoral Excellence Program,China(No.2021160)the“Shuguang Program”supported by the Shanghai Education Development Foundation and the Shanghai Municipal Education Commission,China(No.21SG42).
文摘A one-step molten salt electrochemical strategy was proposed to synthesize SiC nanoparticles from ultra-fine silicon dioxide/carbon(SiO_(2)/C)mixtures.The electrosynthesis process and physicochemical properties of the synthesized products were systematically analyzed via X-ray diffraction,electron microscopy,Raman spectroscopy and photoluminescence spectroscopy,etc.A combined chemical/electrochemical reaction,electrochemical deoxidation,and in-situ carbonization reaction mechanism was proposed to reveal the electrochemical synthesis process of SiC nanoparticles from SiO_(2)/C in molten CaCl_(2).The as-prepared SiC with particle size ranging from 8 to 14 nm possesses a polycrystalline structure.In addition,the SiC nanoparticles demonstrate obvious photoluminescence property due to the synergetic size effect and microstructural characteristics.
基金supported by the Japan Society for the Promotion of Science (JSPS) through a Grant-in-Aid for Scientific Research (No. 17H01300)。
文摘Microbial electrosynthesis system (MES) is a promising method that can use carbon dioxide,which is a greenhouse gas,to produce methane which acts as an energy source,without using organic substances.However,this bioelectrical reduction reaction can proceed at a certain high applied voltage when coupled with water oxidation in the anode coated with metallic catalyst.When coupled with the oxidation of HS–to SO_(4)^(2-),methane production is thermodynamically more feasible,thus implying its production at a considerably lower applied voltage.In this study,we demonstrated the possibility of electrotrophic methane production coupled with HS–oxidation in a cost-effective bioanode chamber in the MES without organic substrates at a low applied voltage of 0.2 V.In addition,microbial community analyses of biomass enriched in the bioanode and biocathode were used to reveal the most probable pathway for methane production from HS–oxidation.In the bioanode,electroautotrophic SO_(4)^(2-)production accompanied with electron donation to the electrode is performed mainly by the following two steps:first,incomplete sulfide oxidation to sulfur cycle intermediates (SCI) is performed;then the produced SCI are disproportionated to HS^(–)and SO_(4)^(2-).In the biocathode,methane is produced mainly via H_(2)and acetate by electronaccepting syntrophic bacteria,homoacetogens,and acetoclastic archaea.Here,a new ecofriendly MES with biological H_(2)S removal is established.
基金supported by the National Natural Science Foundation of China(Nos.52022054,51974181,52004155,52004157,52374307,52304331,52334009)the National Key Research and Development Program of China(No.2022YFC2906100)+4 种基金the China Postdoctoral Science Foundation(No.2022M712023)the Science and Technology Commission of Shanghai Municipality(No.21DZ1208900)the Innovation Program of Shanghai Municipal Education Commission(No.2023ZKZD48)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning(No.TP2019041)the“Shuguang Program”supported by the Shanghai Education Development Foundation and the Shanghai Municipal Education Commission(No.21SG42).
文摘High/medium entropy alloys(HEAs/MEAs)with high electrocatalytic activity have attracted great attention in water electrolysis applications.However,facile synthesis of self-supporting high/medium entropy alloys electrocatalysts with rich active sites through classical metallurgical methods is still a challenge.Here,a self-supporting porous FeCoNi MEA electrocatalyst with nanosheets-shaped surface for oxygen evolution reaction(OER)was prepared by a one-step electrochemical process from the metal oxides in molten CaCl_(2).The formation of the FeCoNi MEA is attributed to the oxides electro-reduction,high-temperature diffusion and solid solution.Additionally,the morphology and structure of the FeCoNi MEA can be precisely controlled by adjusting the electrolysis time and temperature.The electronic structure regulation and the reduced energy barrier of OER from the“cocktail effect”,the abundant exposed active sites brought by surface ultrathin nanosheets,the good electronic conductivity and electrochemical stability from the self-supporting structure enable the FeCoNi MEA electrode shows high-performance OER electrocatalysis,exhibiting a low overpotential of 233 mV at a current density of 10 mA cm^(-2),a low Tafel slope of 29.8 mV dec^(-1),and an excellent stability for over 500 h without any obvious structural destruction.This work demonstrates a facile one-step electrochemical metallurgical approach for fabricating self-supporting HEAs/MEAs electrocatalysts with nanosized surface for the application in water electrolysis.
基金supported by the National Key Research and Development Program (2016YFA0202500 and 2016YFA0200101)the National Natural Science Foundation of China (21676160)Tsinghua University Initiative Scientific Research Program
文摘Hydrogen peroxide(H2O2)is one of the 100 most important chemicals involved in multiple chemical processes including paper and textile manufacturing,waste degradation,and pharmaceutical production[1].Compared with the current industrial process to produce H2O2 following the anthraquinone oxidation/reduction method,electrochemical reduction of oxygen to H2O2 through a two-electron pathway constitutes an environmental friendly alternative route[2-4].Unfortunately,the electrogeneration of H2O2 from two-electron reduction of oxygen feedstock is kinetically sluggish and therefore requires electrocatalysts with high reactivity,high selectivity,and good stability[5,6].
