Due to low cost,high capacity,and high energy density,lithium–sulfur(Li–S)batteries have attracted much attention;however,their cycling performance was largely limited by the poor redox kinetics and low sulfur utili...Due to low cost,high capacity,and high energy density,lithium–sulfur(Li–S)batteries have attracted much attention;however,their cycling performance was largely limited by the poor redox kinetics and low sulfur utilization.Herein,predicted by density functional theory calculations,single‐atomic Co‐B2N2 site‐imbedded boron and nitrogen co‐doped carbon nanotubes(SA‐Co/BNC)were designed to accomplish high sulfur loading,fast kinetic,and long service period Li–S batteries.Experiments proved that Co‐B2N2 atomic sites can effectively catalyze lithium polysulfide conversion.Therefore,the electrodes delivered a specific capacity of 1106 mAh g−1 at 0.2 C after 100 cycles and exhibited an outstanding cycle performance over 1000 cycles at 1 C with a decay rate of 0.032%per cycle.Our study offers a new strategy to couple the combined effect of nanocarriers and single‐atomic catalysts in novel coordination environments for high‐performance Li–S batteries.展开更多
Designing cost-effective and high-efficiency electrocatalysts is critical to the water splitting performance during hydrogen generation.Herein,we have developed Fe_(2)P-Co_(2)P heterostructure nanowire arrays with exc...Designing cost-effective and high-efficiency electrocatalysts is critical to the water splitting performance during hydrogen generation.Herein,we have developed Fe_(2)P-Co_(2)P heterostructure nanowire arrays with excellent lattice torsions and grain boundaries for highly efficient water splitting.According to the microstructural investigations and theoretical calculations,the lattice torsion interface not only contributes to the exposure of more active sites but also effectively tunes the adsorption energy of hydrogen/oxygen intermediates via the accumulation of charge redistribution.As a result,the Fe_(2)P-Co_(2)P heterostructure nanowire array exhibits exceptional bifunctional catalytic activity with overpotentials of 65 and 198 mV at 10 mA cm^(-2) for hydrogen and oxygen evolution reactions,respectively.Moreover,the Fe_(2)P-Co_(2)P/NF-assembled electrolyzer can deliver 10 mA cm^(-2) at an ultralow voltage of1.51 V while resulting in a high solar-to-hydrogen conversion efficiency of 19.8%in the solar-driven water electrolysis cell.展开更多
Electrocatalytic nitrate reduction reaction(NO_(3)RR)offers a unique rationale for green NH_(3) synthesis,yet the lack of high-efficiency NO_(3)RR catalysts remains a great challenge.In this work,we show that Au nanoc...Electrocatalytic nitrate reduction reaction(NO_(3)RR)offers a unique rationale for green NH_(3) synthesis,yet the lack of high-efficiency NO_(3)RR catalysts remains a great challenge.In this work,we show that Au nanoclusters anchored on TiO_(2) nanosheets can efficiently catalyze the conversion of NO_(3)RR-to-NH_(3) under ambient conditions,achieving a maximal Faradic efficiency of 91%,a peak yield rate of 1923μg·h^(-1)·mgcat.-1,and high durability over 10 consecutive cycles,all of which are comparable to the recently reported metrics(including transition metal and noble metal-based catalysts)and exceed those of pristine TiO_(2).Moreover,a galvanic Zn-nitrate battery using the catalyst as the cathode was proposed,which shows a power density of 3.62 mW·cm^(-2) and a yield rate of 452μg·h^(-1)·mgcat.-1.Theoretical simulations further indicate that the atomically dispersed Au clusters can promote the adsorption and activation of NO_(3)-species,and reduce the NO_(3)RR-to-NH_(3) barrier,thus leading to an accelerated cathodic reaction.This work highlights the importance of metal clusters for the NH_(3) electrosynthesis and nitrate removal.展开更多
The chemical evolution and pressure-temperature conditions of subduction zone magmatism along ancient suture zones in orogenic belts can provide important information regarding plate convergence processes in paleo-oce...The chemical evolution and pressure-temperature conditions of subduction zone magmatism along ancient suture zones in orogenic belts can provide important information regarding plate convergence processes in paleo-oceans.Carboniferous magmatism in West Junggar is key to understanding the tectonothermal and subduction history of the Junggar Ocean,which was a branch of the Paleo-Asian Ocean,as well as the accretionary processes in the southwestern Central Asian Orogenic Belt(CAOB).We undertook a geochronological,mineralogical,geochemical,and Sr-Nd-Hf-Pb isotopic study of volcanic rocks from the Baikouquan area of West Junggar.We used these data to determine the petrogenesis,mantle source,and pressure-temperature conditions of these magmas,and further constrain the subduction and tectonic history of the Junggar Ocean.The studied volcanic rocks yielded zircon U-Pb ages of 342-337 Ma and are characterized by enrichments of large-ion lithophile elements(LILEs),and depletions in high-field-strength elements(HFSEs),indicative of an island arc affinity.The volcanic rocks have positiveƐNd(t)(5.83-7.04)andƐHf(t)(13.47-15.74)values,87Sr/86Sr(t)ratios of 0.704023-0.705658,and radiogenic 207Pb/204Pb(t)and 208Pb/204Pb(t)ratios at a given 206Pb/204Pb(t)ratio,indicative of a depleted mantle source contaminated by subduction-related materials.Geochemical modeling calculations indicate that≤1%of a subduction component comprising fluid and sediment melt could have generated the source of the parental melts of the Baikouquan volcanic rocks.Clinopyroxene phenocrysts in the volcanic rocks are classified as high-and low-Ti clinopyroxene,and pressure-temperature calculations suggest the host rocks formed at high temperatures(~1300℃)and shallow to moderate depths(<2 GPa).The magma was probably generated by hot and hydrous melting in a mantle wedge in response to subduction of young,hot oceanic lithosphere.The present results,combined with published data,suggest that the Baikouquan volcanic rocks record a transition in tectonic setting from normal cold to anomalous hot subduction of young oceanic lithosphere close to a mid-ocean ridge.This indicates ridge subduction began shortly after 337 Ma.Our results provide new insights into the tectonomagmatic evolution during intra-oceanic subduction prior to ridge subduction.展开更多
The coupling of energy-saving small molecule conversion reactions and hydrogen evolution reaction(HER)in seawater electrolytes can reduce the energy consumption of seawater electrolysis and mitigate chlorine corrosion...The coupling of energy-saving small molecule conversion reactions and hydrogen evolution reaction(HER)in seawater electrolytes can reduce the energy consumption of seawater electrolysis and mitigate chlorine corrosion issues.However,the fabrication of efficient multifunctional catalysts for this promising technology is of great challenge.Herein,a heterostructured catalyst comprising CoP and Ni_(2)P on nickel foam(CoP/Ni_(2)P@NF)is reported for hydrazine oxidation(HzOR)-assisted alkaline seawater splitting.The coupling of CoP and Ni_(2)P optimizes the electronic structure of the active sites and endows excellent electrocatalytic performance for HzOR and HER.Impressively,the two-electrode HzOR-assisted alkaline seawater splitting(OHzS)cell based on the CoP/Ni_(2)P@NF required only 0.108 V to deliver 100 mA·cm^(−2),much lower than 1.695 V for alkaline seawater electrolysis cells.Moreover,the OHzS cell exhibits satisfactory stability over 48 h at a high current density of 500 mA·cm^(−2).Furthermore,the CoP/Ni_(2)P@NF heterostructured catalyst also efficiently catalyzed glucose oxidation,methanol oxidation,and urea oxidation in alkaline seawater electrolytes.This work paves a path for high-performance heterostructured catalyst preparation for energy-saving seawater electrolysis for H_(2) production.展开更多
Layered double hydroxides have demonstrated great potential for the oxygen evolution reaction,which is a crucial half-reaction of overall water splitting.However,it remains challenging to apply layered double hydroxid...Layered double hydroxides have demonstrated great potential for the oxygen evolution reaction,which is a crucial half-reaction of overall water splitting.However,it remains challenging to apply layered double hydroxides in other electrochemical reactions with high efficiency and stability.Herein,we report two-dimensional multifunctional layered double hydroxides derived from metalorganic framework sheet precursors supported by nanoporous gold with high porosity,which exhibit appealing performances toward oxygen/hydrogen evolution reactions,hydrazine oxidation reaction,and overall hydrazine splitting.The as-prepared catalyst only requires an overpotential of 233 mV to reach 10 mA·cm^(-2) toward oxygen evolution reaction.The overall hydrazine splitting cell only needs a cell voltage of 0.984 V to deliver 10 mA·cm^(-2),which is far more superior than that of the overall water splitting system(1.849 V).The appealing performances of the catalyst can be contributed to the synergistic effect between the metal components of the layered double hydroxides and the supporting effect of the nanoporous gold substrate,which could endow the sample with high surface area and excellent conductivity,resulting in superior activity and stability.展开更多
Aqueous rechargeable Zn–gas batteries are regarded as promising energy storage and conversion devices due to their high safety and inherent environmental friendliness.However,the energy efficiency and power density o...Aqueous rechargeable Zn–gas batteries are regarded as promising energy storage and conversion devices due to their high safety and inherent environmental friendliness.However,the energy efficiency and power density of Zn–gas batteries are restricted by the kinetically sluggish cathode reactions,such as oxygen evolution reaction(OER)during charging and oxygen reduction reaction(ORR)/carbon dioxide reduction reaction(CO_(2)RR)/nitrogen reduction reaction(NRR)/nitric oxide reduction reaction(NORR)during discharge.In this review,battery configurations and fundamental reactions in Zn–gas batteries are first introduced,including Zn–air,Zn-CO_(2),Zn-N_(2),and Zn-NO batteries.Afterward,recent advances in active site engineering for enhancing the intrinsic catalytic activities of cathode catalysts are summarized.Subsequently,the structure and surface regulation strategies of cathode materials for optimizing the three-phase interface and improving the performance of Zn–gas batteries are discussed.Finally,some personal perspectives for the future development of Zn–gas batteries are presented.展开更多
Mantle heterogeneity has revealed systematic differences in Pb isotopic compositions between the Indian OceanSouth Atlantic mantle in the Southern Hemisphere and the Pacific Ocean-North Atlantic mantle in the Northern...Mantle heterogeneity has revealed systematic differences in Pb isotopic compositions between the Indian OceanSouth Atlantic mantle in the Southern Hemisphere and the Pacific Ocean-North Atlantic mantle in the Northern Hemisphere.This large-scale difference in mantle isotopes in the Southern Hemisphere is known as the DUPAL anomaly,but its origin remains controversial.Based on a systematic review of the Nd-Pb isotopic evolution of the Tethyan mantle domain,this study identified the long-term presence of the DUPAL anomaly in this domain since the early Paleozoic,characterized by long-term and high mantle thorium/uranium(Th/U)ratios.By comparing the Nd-Pb isotopic compositions of the Tethyan mantle domain with the Panthalassic-Pacific mantle domain(the Paleo-Asian,Paleo-Pacific,and modern Pacific oceans),it is shown that the mantle initially had low Th/U features due to early Earth crust-mantle differentiation,with the crust having high Th/U ratios.As such,the mantle initially had uniformly low Th/U ratios that were inherited throughout the Panthalassic-Pacific mantle domain.However,the plate tectonics and continental collisions in the Tethyan domain affected its characteristics,leading to the long-term and large-scale DUPAL anomaly.During the opening of and subduction in the Tethys Ocean,Gondwanaland fragmentation and frequent continent-continent collisions led to long-term and extensive crust-mantle interactions and the continuous input of highTh/U mantle sources,which thus modified the mantle.This process formed not only the unique DUPAL anomaly in the Tethyan mantle domain,but also the Tethyan tectonic domain dominated by continental collisions.Moreover,the high DUPAL anomaly in the Proto-and Paleo-Tethyan mantle domains records the effects of mantle plumes,which might have occurred primarily during the formation of the Proto-and Paleo-Tethys oceans during the early evolution of the Tethyan domain.Therefore,the inherent coupling of mantle domain properties and plate tectonic mechanisms provides important insights for understanding plate tectonics and geodynamic processes in the Tethyan domain.展开更多
As an ideal carbon-free energy carrier,ammonia plays an indispensable role in modern society.The conventional industrial synthesis of NH3 by the Haber-Bosch technique under harsh reaction conditions results in serious...As an ideal carbon-free energy carrier,ammonia plays an indispensable role in modern society.The conventional industrial synthesis of NH3 by the Haber-Bosch technique under harsh reaction conditions results in serious energy consumption and environmental pollution.Therefore,it is essential to develop NH3 synthesis tactics under benign conditions.Electrochemical synthesis of NH_(3) has the advantages of mild reaction conditions and environmental friendliness,and has become a hotspot for research in recent years.It has been reported that zinc-nitrogen batteries(ZNBs),such as Zn-N_(2),Zn-NO,Zn-NO_(3)^(-),and Zn-NO_(2)^(-)batteries,can not only reduce nitrogenous species to ammonia but also have concomitant power output.However,the common drawbacks of these battery systems are unsatisfactory power density and ammonia production.In this review,the latest progress of ZNBs including the reaction mechanism of the battery and reactor design principles is systematically summarized.Subsequently,active site engineering of cathode catalysts is discussed,including vacancy defects,chemical doping,and heterostructure engineering.Finally,some insights are provided to improve the performance of ZNBs from a practical perspective of view.展开更多
Designing advanced and cost-effective electrocatalytic system for nitric oxide(NO)reduction reaction(NORR)is vital for sustainable NH_(3) production and NO removal,yet it is a challenging task.Herein,it is shown that ...Designing advanced and cost-effective electrocatalytic system for nitric oxide(NO)reduction reaction(NORR)is vital for sustainable NH_(3) production and NO removal,yet it is a challenging task.Herein,it is shown that phosphorus(P)-doped titania(TiO_(2))nanotubes can be adopted as highly efficient catalyst for NORR.The catalyst demonstrates impressive performance in ionic liquid(IL)-based electrolyte with a remarkable high Faradaic efficiency of 89%and NH3 yield rate of 425μg·h^(−1)·mg_(cat).^(−1),being close to the best-reported results.Noteworthy,the obtained performance metrics are significantly larger than those for N_(2) reduction reaction.It also shows good durability with negligible activity decay even after 10 cycles.Theoretical simulations reveal that the introduction of P dopants tunes the electronic structure of Ti active sites,thereby enhancing the NO adsorption and facilitating the desorption of ^(*)NH_(3).Moreover,the utilization of IL further suppresses the competitive hydrogen evolution reaction.This study highlights the advantage of the catalyst−electrolyte engineering strategy for producing NH_(3) at a high efficiency and rate.展开更多
Facilitated by reactive oxygen species(ROS)-involved therapies,tumor cells undergo immunogenic cell death(ICD)to stimulate long-term immunity response.However,it is hard to trigger abundant and large-scale ICD for sat...Facilitated by reactive oxygen species(ROS)-involved therapies,tumor cells undergo immunogenic cell death(ICD)to stimulate long-term immunity response.However,it is hard to trigger abundant and large-scale ICD for satisfactory cancer immunotherapy.Herein,a multifunctional sonosensitizer that consists of Au single atoms and clusters anchored on TiO_(2)nanosheets(named Au_(S/C)-TiO_(2))is reported for augmented sonodynamic therapy(SDT)and glucose depletion,which ultimately induce robust ICD due to the improved ROS generation and strong endoplasmic reticulum(ER)stress.The synergy effect between Au cluster/single atom with TiO_(2)nanosheets intensifies apoptosis and ICD pathways to inhibit 80%of tumor cells through in vivo analyses.Furthermore,immune cells in vivo analyses verify the effectiveness of Au_(S/C)-TiO_(2)sonosensitizer towards the induction of antitumor immunity.This study thus reveals that simultaneous presence of ROS generation and strong ER stress can efficiently evoke a strong ICD-mediated immune response.展开更多
Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of...Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of active oxygen species generated in this reaction is still a challenging target.Herein,MgO nanosheets and single-atom Pt loaded MgO(Pt SA/MgO)nanosheets were synthesized and used as catalysts in toluene oxidation.The activation process of molecular oxygen and oxidation performance on the two catalysts were contrastively investigated.The Pt SA/MgO exhibited significantly enhanced catalytic activity compared to MgO.The oxygen vacancies can be easily generated on the Pt SA/MgO surface,which facilitate the activation of molecular oxygen and the formation of active oxygen species.Based on the experimental data and theoretical calculations,an active oxygen species promoted oxidation mechanism for toluene was proposed.In the presence of H2O,the molecular oxygen is more favorable to be dissociated to generate•OH on the oxygen vacancies of the Pt SA/MgO surface,which is the dominant active oxygen species.We anticipate that this work may shed light on further investigation of t10.1007/s12274-020-2765-1he oxidation mechanism of toluene and other VOCs over noble metal catalysts.展开更多
An effective electrocatalyst being highly active in all pH range for oxygen reduction reaction(ORR)is crucial for energy conversion and storage devices.However,most of the high-efficiency ORR catalysis was reported in...An effective electrocatalyst being highly active in all pH range for oxygen reduction reaction(ORR)is crucial for energy conversion and storage devices.However,most of the high-efficiency ORR catalysis was reported in alkaline conditions.Herein,we demonstrated the preparation of atomically dispersed Fe-Zn pairs anchored on porous N-doped carbon frameworks(Fe-Zn-SA/NC),which works efficiently as ORR catalyst in the whole pH range.It achieves high half-wave potentials of 0.78,0.85 and 0.72 V in 0.1 M HClO4,0.1 M KOH and 0.1 M phosphate buffer saline(PBS)solutions,respectively,as well as respectable stability.The performances are even comparable to Pt/C.Furthermore,when assembled into a Zn-air battery,the high power density of 167.2 mWcm−2 and 120 h durability reveal the feasibility of Fe-Zn-SA/NC in real energy-related devices.Theoretical calculations demonstrate that the superior catalytic activity of Fe-Zn-SA/NC can be contributed to the lower energy barriers of ORR at the Fe-Zn-N6 centers.This work demonstrates the potential of Fe-Zn pairs as alternatives to the Pt catalysts for efficient catalytic ORR and provides new insights of dual-atom catalysts for other energy conversion related catalytic reactions.展开更多
Natural organisms contain rich elements and naturally optimized smart structures,both of which have inspired various innovative concepts and desig ns in human society.In particular,several natural organisms have been ...Natural organisms contain rich elements and naturally optimized smart structures,both of which have inspired various innovative concepts and desig ns in human society.In particular,several natural organisms have been used as element sources to synthesize low-cost and environmentally friendly electrocatalysts for the oxygen reduction reaction(ORR)in fuel cells and metal-air batteries,which are clean energy devices.However,to date,no naturally optimized smart structures have been employed in the synthesis of ORR catalysts,including graphene-based materials.Here,we demonstrate a novel strategy to synthesize graphene-graphite films(GGFs)by heating butterfly wings coated with FeCI3 in N2,in which the full power of natural organisms is utilized.The wings work not only as an element source for GGF generation but also as a porous supporting structure for effective nitrogen doping,two-dimensional spreading,and double-face exposure of the GGFs.These GGFs exhibit a half-wave potential of 0.942 V and a H2O2 yield of<0.07%for ORR electrocatalysis;these values are comparable to those for the best commercial Pt/C and all previously reported ORR catalysts in alkaline media.This two-in-one strategy is also successful with cicada and dragonfly wings,indicating that it is a universal,green,and cost-effective method for developing high-performance graphene-based materials.展开更多
开发高效且性能稳定的氧析出(OER)、氧还原(ORR)和氢析出(HER)三功能催化剂是制备能源存储与转换设备的关键.本文使用一步磷化法,在氮磷共掺杂碳基上制备了Fe Co金属合金/磷化物催化剂(Fe Co-P/PNC).该催化剂显示了良好的ORR性能,展现了...开发高效且性能稳定的氧析出(OER)、氧还原(ORR)和氢析出(HER)三功能催化剂是制备能源存储与转换设备的关键.本文使用一步磷化法,在氮磷共掺杂碳基上制备了Fe Co金属合金/磷化物催化剂(Fe Co-P/PNC).该催化剂显示了良好的ORR性能,展现了0.86 V (vs.RHE,相对于可逆氢电极)的半波电位;在OER和HER反应中,催化剂在10 m A cm^(-2)的电流密度下的过电位分别为350和158 m V.密度泛函理论计算表明,磷在Fe Co磷化物和碳基体中皆起主导作用,使得该催化剂同时具有良好的ORR、OER和HER功能.以Fe Co-P/PNC为空气阴极组装的水系电池和柔性锌-空气电池的峰值功率密度分别为195.1和90.8 m W cm^(-2),且两种电池均具有优异的充放电性能、长寿命和高柔性.此外,自供能的整体水分解系统表现出较低的(1.71 V)工作电压以驱动10 m A cm^(-2)的电流密度,进一步证实了该催化剂出色的多功能性.展开更多
Electrochemical nitric oxide reduction reaction(NORR)to produce ammonia(NH3)under ambient conditions is a promising alternative to the energy and carbon-intensive Haber–Bosch approach,but its performance is still imp...Electrochemical nitric oxide reduction reaction(NORR)to produce ammonia(NH3)under ambient conditions is a promising alternative to the energy and carbon-intensive Haber–Bosch approach,but its performance is still improved.Herein,molybdenum carbides(MoC)nanocrystals confined by nitrogen-doped carbon nanosheets are first designed as an efficient and durable electrocatalyst for catalyzing the reduction of NO to NH3 with maximal Faradaic efficiency of 89%±2%and a yield rate of 1,350±15μg·h^(−1)·cm^(−2) at the applied potential of−0.8 V vs.reversible hydrogen electrode(RHE)as well as high stable activity with negligible current density and NH3 yield rate decays over a 30 h continue the test.Moreover,as a proof-of-concept of Zn–NO battery,it achieves a peak power density of 1.8 mW·cm^(−2) and a large NH3 yield rate of 782±10μg·h^(−1)·cm^(−2),which are comparable to the best-reported results.Theoretical calculations reveal that the MoC(111)has a strong electronic interaction with NO molecules and thus lowering the energy barrier of the potential-determining step and suppressing hydrogen evolution kinetics.This work suggests that Mo-based materials are a powerful platform providing great opportunities to explore highly selective and active catalysts for NH3 production.展开更多
Developing efficient seawater-electrolysis system for mass production of hydrogen is highly desirable due to the abundance of seawater.However,continuous electrolysis with seawater feeding boosts the concentration of ...Developing efficient seawater-electrolysis system for mass production of hydrogen is highly desirable due to the abundance of seawater.However,continuous electrolysis with seawater feeding boosts the concentration of sodium chloride in the electrolyzer,leading to severe electrode corrosion and chlorine evolution.Herein,the common-ion effect was utilized into the electrolyzer to depress the solubility of NaCl.Specifically,utilization of 6M NaOH halved the solubility of NaCl in the electrolyte,affording efficient,durable,and sustained seawater electrolysis in NaCl-saturated electrolytes with triple production of H_(2),O_(2),and crystalline NaCl.Ternary NiCoFe phosphide was employed as a bifunctional anode and cathode in simulative and Ca/Mg-free seawater-electrolysis systems,which could stably work under 500 mA/cm^(2) for over 100 h.We attribute the high stability to the increased Na^(+)concentration,which reduces the concentration of dissolved Cl-in the electrolyte according to the common-ion effect,resulting in crystallization of NaCl,eliminated anode corrosion,and chlorine oxidation during continuous supplementation of Ca/Mg-free seawater to the electrolysis system.展开更多
The electrosynthesis of hydrogen peroxide(H2O2)from oxygen reduction reaction(ORR)via a two-electron pathway provides an appealing alternative to the energy-intensive anthraquinone route;however,the development of ORR...The electrosynthesis of hydrogen peroxide(H2O2)from oxygen reduction reaction(ORR)via a two-electron pathway provides an appealing alternative to the energy-intensive anthraquinone route;however,the development of ORR with high selectivity and durability for H2O2 production is still challenging.Herein,we demonstrate an active and stable catalyst,composing of highly dispersed Ag nanoclusters on N-doped hollow carbon spheres(NC-Ag/NHCS),which can effectively reduce O2 molecules into H2O2 with a selectivity of 89%–91%in a potential range from 0.2 to 0.7 V(vs.reversible hydrogen electrode(RHE))in acidic media.Strikingly,NC-Ag/NHCS achieve a mass activity of 27.1 A·g^(−1) and a yield rate of 408 mmol·gcat.^(−1)·h^(−1) at 0.7 V,both of which are comparable with the best-reported results.Furthermore,NC-Ag/NHCS enable catalyzing H2O2 production with a stable current density over 48-h electrolysis and only about 9.8%loss in selectivity after 10,000 cycles.Theoretical analyses indicate that Ag nanoclusters can contribute more electrons to favor the protonation of adsorbed O2,thus leading to a high H2O2 selectivity.This work confirms the great potential of metal nanocluster-based materials for H2O2 electrosynthesis under ambient conditions.展开更多
基金Yunnan Expert Workstation,Grant/Award Number:202005AF150028Program for the Outstanding Young Talents of Hebei Province,China,Grant/Award Number:YGZ+6 种基金Guangdong Innovative and Entrepreneurial Team Program,Grant/Award Number:2016ZT06C517Guangdong Science and Technology Department,Grant/Award Number:2020B0909030004National Natural Science Foundation of China,Grant/Award Numbers:21601136,22075211,52071125Outstanding Youth Project of Guangdong Natural Science Foundation,Grant/Award Number:2021B1515020051Natural Science Foundation of Hebei Province,China,Grant/Award Numbers:B2020202052,B2021202028,E2020202071Chunhui Project of Ministry of Education of the People's Republic of China,Grant/Award Number:Z2017010Science and Technology Program of Guangzhou,Grant/Award Number:2019050001。
文摘Due to low cost,high capacity,and high energy density,lithium–sulfur(Li–S)batteries have attracted much attention;however,their cycling performance was largely limited by the poor redox kinetics and low sulfur utilization.Herein,predicted by density functional theory calculations,single‐atomic Co‐B2N2 site‐imbedded boron and nitrogen co‐doped carbon nanotubes(SA‐Co/BNC)were designed to accomplish high sulfur loading,fast kinetic,and long service period Li–S batteries.Experiments proved that Co‐B2N2 atomic sites can effectively catalyze lithium polysulfide conversion.Therefore,the electrodes delivered a specific capacity of 1106 mAh g−1 at 0.2 C after 100 cycles and exhibited an outstanding cycle performance over 1000 cycles at 1 C with a decay rate of 0.032%per cycle.Our study offers a new strategy to couple the combined effect of nanocarriers and single‐atomic catalysts in novel coordination environments for high‐performance Li–S batteries.
基金financially supported by the National Natural Science Foundation of China(U2002213)the Creative Project of Engineering Research Center of Alternative Energy Materials&Devices,Ministry of Education,Sichuan University(AEMD202207)+7 种基金the Open Foundation of Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials of Guangxi University(2022GXYSOF10)the Guangdong Colleges&Universities Characteristic Innovation Project(2021KTSCX263)the Guangdong Education&Scientific Research Project(2021GXJK535)the Guangzhou Panyu Polytechnic Science&Technology Project(2021KJ01)the East-Land Middle-aged and Young Backbone Teacher of Yunnan University(C176220200)the Yunnan Applied Basic Research Projects(202001BB050006,202001BB050007)the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University(2019FY003025)the Double First Class University Plan(C176220100042)。
文摘Designing cost-effective and high-efficiency electrocatalysts is critical to the water splitting performance during hydrogen generation.Herein,we have developed Fe_(2)P-Co_(2)P heterostructure nanowire arrays with excellent lattice torsions and grain boundaries for highly efficient water splitting.According to the microstructural investigations and theoretical calculations,the lattice torsion interface not only contributes to the exposure of more active sites but also effectively tunes the adsorption energy of hydrogen/oxygen intermediates via the accumulation of charge redistribution.As a result,the Fe_(2)P-Co_(2)P heterostructure nanowire array exhibits exceptional bifunctional catalytic activity with overpotentials of 65 and 198 mV at 10 mA cm^(-2) for hydrogen and oxygen evolution reactions,respectively.Moreover,the Fe_(2)P-Co_(2)P/NF-assembled electrolyzer can deliver 10 mA cm^(-2) at an ultralow voltage of1.51 V while resulting in a high solar-to-hydrogen conversion efficiency of 19.8%in the solar-driven water electrolysis cell.
基金supported by the National Natural Science Foundation of China(Nos.22075211 and 51971157)the Guangzhou Basic&Applied Basic Research Project(No.202201011853)+2 种基金the Shenzhen Science and Technology Program(Nos.JCYJ20210324115412035,JCYJ20210324123202008,JCYJ20210324122803009,and ZDSYS20210813095534001)the Guangdong Basic and Applied Basic Research Foundation(No.2021A1515110880)the Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800).
文摘Electrocatalytic nitrate reduction reaction(NO_(3)RR)offers a unique rationale for green NH_(3) synthesis,yet the lack of high-efficiency NO_(3)RR catalysts remains a great challenge.In this work,we show that Au nanoclusters anchored on TiO_(2) nanosheets can efficiently catalyze the conversion of NO_(3)RR-to-NH_(3) under ambient conditions,achieving a maximal Faradic efficiency of 91%,a peak yield rate of 1923μg·h^(-1)·mgcat.-1,and high durability over 10 consecutive cycles,all of which are comparable to the recently reported metrics(including transition metal and noble metal-based catalysts)and exceed those of pristine TiO_(2).Moreover,a galvanic Zn-nitrate battery using the catalyst as the cathode was proposed,which shows a power density of 3.62 mW·cm^(-2) and a yield rate of 452μg·h^(-1)·mgcat.-1.Theoretical simulations further indicate that the atomically dispersed Au clusters can promote the adsorption and activation of NO_(3)-species,and reduce the NO_(3)RR-to-NH_(3) barrier,thus leading to an accelerated cathodic reaction.This work highlights the importance of metal clusters for the NH_(3) electrosynthesis and nitrate removal.
基金supported financially by funds from the National Natural Science Foundation of China (92055208,41888101)the Guangxi Science Innovation Base Construction Foundation (GuikeZY21195031)+2 种基金the Fifth Bagui Scholar Innovation Project of Guangxi Province (to XU Jifeng)Gansu Province Youth Science and Technology Fund Project (23JRRG0017)Guangxi Young and Middle-aged Teachers'Basic Competence Enhancement Program (2023KY0270).
文摘The chemical evolution and pressure-temperature conditions of subduction zone magmatism along ancient suture zones in orogenic belts can provide important information regarding plate convergence processes in paleo-oceans.Carboniferous magmatism in West Junggar is key to understanding the tectonothermal and subduction history of the Junggar Ocean,which was a branch of the Paleo-Asian Ocean,as well as the accretionary processes in the southwestern Central Asian Orogenic Belt(CAOB).We undertook a geochronological,mineralogical,geochemical,and Sr-Nd-Hf-Pb isotopic study of volcanic rocks from the Baikouquan area of West Junggar.We used these data to determine the petrogenesis,mantle source,and pressure-temperature conditions of these magmas,and further constrain the subduction and tectonic history of the Junggar Ocean.The studied volcanic rocks yielded zircon U-Pb ages of 342-337 Ma and are characterized by enrichments of large-ion lithophile elements(LILEs),and depletions in high-field-strength elements(HFSEs),indicative of an island arc affinity.The volcanic rocks have positiveƐNd(t)(5.83-7.04)andƐHf(t)(13.47-15.74)values,87Sr/86Sr(t)ratios of 0.704023-0.705658,and radiogenic 207Pb/204Pb(t)and 208Pb/204Pb(t)ratios at a given 206Pb/204Pb(t)ratio,indicative of a depleted mantle source contaminated by subduction-related materials.Geochemical modeling calculations indicate that≤1%of a subduction component comprising fluid and sediment melt could have generated the source of the parental melts of the Baikouquan volcanic rocks.Clinopyroxene phenocrysts in the volcanic rocks are classified as high-and low-Ti clinopyroxene,and pressure-temperature calculations suggest the host rocks formed at high temperatures(~1300℃)and shallow to moderate depths(<2 GPa).The magma was probably generated by hot and hydrous melting in a mantle wedge in response to subduction of young,hot oceanic lithosphere.The present results,combined with published data,suggest that the Baikouquan volcanic rocks record a transition in tectonic setting from normal cold to anomalous hot subduction of young oceanic lithosphere close to a mid-ocean ridge.This indicates ridge subduction began shortly after 337 Ma.Our results provide new insights into the tectonomagmatic evolution during intra-oceanic subduction prior to ridge subduction.
基金the National Natural Science Foundation of China(Nos.22075211 and 22275166)the Zhejiang Provincial Natural Science Foundation of China(No.LZ21E020003).
文摘The coupling of energy-saving small molecule conversion reactions and hydrogen evolution reaction(HER)in seawater electrolytes can reduce the energy consumption of seawater electrolysis and mitigate chlorine corrosion issues.However,the fabrication of efficient multifunctional catalysts for this promising technology is of great challenge.Herein,a heterostructured catalyst comprising CoP and Ni_(2)P on nickel foam(CoP/Ni_(2)P@NF)is reported for hydrazine oxidation(HzOR)-assisted alkaline seawater splitting.The coupling of CoP and Ni_(2)P optimizes the electronic structure of the active sites and endows excellent electrocatalytic performance for HzOR and HER.Impressively,the two-electrode HzOR-assisted alkaline seawater splitting(OHzS)cell based on the CoP/Ni_(2)P@NF required only 0.108 V to deliver 100 mA·cm^(−2),much lower than 1.695 V for alkaline seawater electrolysis cells.Moreover,the OHzS cell exhibits satisfactory stability over 48 h at a high current density of 500 mA·cm^(−2).Furthermore,the CoP/Ni_(2)P@NF heterostructured catalyst also efficiently catalyzed glucose oxidation,methanol oxidation,and urea oxidation in alkaline seawater electrolytes.This work paves a path for high-performance heterostructured catalyst preparation for energy-saving seawater electrolysis for H_(2) production.
基金supported by the National Natural Science Foundation of China(Grant Nos.51971157 and 22075211)Shenzhen Science and Technology Program(Grant Nos.JCYJ20210324115412035,JCYJ20210324123202008,JCYJ20210324122803009 and ZDSYS20210813095534001)Guangdong Foundation for Basic and Applied Basic Research Program(Grant No.2021A1515110880).
文摘Layered double hydroxides have demonstrated great potential for the oxygen evolution reaction,which is a crucial half-reaction of overall water splitting.However,it remains challenging to apply layered double hydroxides in other electrochemical reactions with high efficiency and stability.Herein,we report two-dimensional multifunctional layered double hydroxides derived from metalorganic framework sheet precursors supported by nanoporous gold with high porosity,which exhibit appealing performances toward oxygen/hydrogen evolution reactions,hydrazine oxidation reaction,and overall hydrazine splitting.The as-prepared catalyst only requires an overpotential of 233 mV to reach 10 mA·cm^(-2) toward oxygen evolution reaction.The overall hydrazine splitting cell only needs a cell voltage of 0.984 V to deliver 10 mA·cm^(-2),which is far more superior than that of the overall water splitting system(1.849 V).The appealing performances of the catalyst can be contributed to the synergistic effect between the metal components of the layered double hydroxides and the supporting effect of the nanoporous gold substrate,which could endow the sample with high surface area and excellent conductivity,resulting in superior activity and stability.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(No.LZ21E020003)the National Natural Science Foundation of China(Nos.21905246,22075211,21601136,51971157,and 51621003)Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800).
文摘Aqueous rechargeable Zn–gas batteries are regarded as promising energy storage and conversion devices due to their high safety and inherent environmental friendliness.However,the energy efficiency and power density of Zn–gas batteries are restricted by the kinetically sluggish cathode reactions,such as oxygen evolution reaction(OER)during charging and oxygen reduction reaction(ORR)/carbon dioxide reduction reaction(CO_(2)RR)/nitrogen reduction reaction(NRR)/nitric oxide reduction reaction(NORR)during discharge.In this review,battery configurations and fundamental reactions in Zn–gas batteries are first introduced,including Zn–air,Zn-CO_(2),Zn-N_(2),and Zn-NO batteries.Afterward,recent advances in active site engineering for enhancing the intrinsic catalytic activities of cathode catalysts are summarized.Subsequently,the structure and surface regulation strategies of cathode materials for optimizing the three-phase interface and improving the performance of Zn–gas batteries are discussed.Finally,some personal perspectives for the future development of Zn–gas batteries are presented.
基金supported by the National Natural Science Foundation of China (Grant No. 92055208)the Guangxi Science Innovation Base Construction Foundation (Grant No. GuikeZY21195031)+2 种基金the Fifth Bagui Scholar Innovation Project of Guangxi Province (to Xu Jifeng)the Xinjiang Tianchi Distinguished Expert grant awarded to Xijun LIUthe Guangxi Key Mineral Resources Deep Exploration Talent Highland
文摘Mantle heterogeneity has revealed systematic differences in Pb isotopic compositions between the Indian OceanSouth Atlantic mantle in the Southern Hemisphere and the Pacific Ocean-North Atlantic mantle in the Northern Hemisphere.This large-scale difference in mantle isotopes in the Southern Hemisphere is known as the DUPAL anomaly,but its origin remains controversial.Based on a systematic review of the Nd-Pb isotopic evolution of the Tethyan mantle domain,this study identified the long-term presence of the DUPAL anomaly in this domain since the early Paleozoic,characterized by long-term and high mantle thorium/uranium(Th/U)ratios.By comparing the Nd-Pb isotopic compositions of the Tethyan mantle domain with the Panthalassic-Pacific mantle domain(the Paleo-Asian,Paleo-Pacific,and modern Pacific oceans),it is shown that the mantle initially had low Th/U features due to early Earth crust-mantle differentiation,with the crust having high Th/U ratios.As such,the mantle initially had uniformly low Th/U ratios that were inherited throughout the Panthalassic-Pacific mantle domain.However,the plate tectonics and continental collisions in the Tethyan domain affected its characteristics,leading to the long-term and large-scale DUPAL anomaly.During the opening of and subduction in the Tethys Ocean,Gondwanaland fragmentation and frequent continent-continent collisions led to long-term and extensive crust-mantle interactions and the continuous input of highTh/U mantle sources,which thus modified the mantle.This process formed not only the unique DUPAL anomaly in the Tethyan mantle domain,but also the Tethyan tectonic domain dominated by continental collisions.Moreover,the high DUPAL anomaly in the Proto-and Paleo-Tethyan mantle domains records the effects of mantle plumes,which might have occurred primarily during the formation of the Proto-and Paleo-Tethys oceans during the early evolution of the Tethyan domain.Therefore,the inherent coupling of mantle domain properties and plate tectonic mechanisms provides important insights for understanding plate tectonics and geodynamic processes in the Tethyan domain.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.22075211,22109118,22275166,21601136,and 51971157)Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800)+1 种基金Shenzhen Science and Technology Program(Nos.JCYJ20210324123202008,JCYJ20210324115412035,and ZDSYS20210813095534001)Guangdong Foundation for Basic and Applied Basic Research Program(No.2021A1515110880).
文摘As an ideal carbon-free energy carrier,ammonia plays an indispensable role in modern society.The conventional industrial synthesis of NH3 by the Haber-Bosch technique under harsh reaction conditions results in serious energy consumption and environmental pollution.Therefore,it is essential to develop NH3 synthesis tactics under benign conditions.Electrochemical synthesis of NH_(3) has the advantages of mild reaction conditions and environmental friendliness,and has become a hotspot for research in recent years.It has been reported that zinc-nitrogen batteries(ZNBs),such as Zn-N_(2),Zn-NO,Zn-NO_(3)^(-),and Zn-NO_(2)^(-)batteries,can not only reduce nitrogenous species to ammonia but also have concomitant power output.However,the common drawbacks of these battery systems are unsatisfactory power density and ammonia production.In this review,the latest progress of ZNBs including the reaction mechanism of the battery and reactor design principles is systematically summarized.Subsequently,active site engineering of cathode catalysts is discussed,including vacancy defects,chemical doping,and heterostructure engineering.Finally,some insights are provided to improve the performance of ZNBs from a practical perspective of view.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.22075211,21601136,and 21905246)the Key Projects of Zhejiang Natural Science Foundation(Grant No.LZ20E010001).
文摘Designing advanced and cost-effective electrocatalytic system for nitric oxide(NO)reduction reaction(NORR)is vital for sustainable NH_(3) production and NO removal,yet it is a challenging task.Herein,it is shown that phosphorus(P)-doped titania(TiO_(2))nanotubes can be adopted as highly efficient catalyst for NORR.The catalyst demonstrates impressive performance in ionic liquid(IL)-based electrolyte with a remarkable high Faradaic efficiency of 89%and NH3 yield rate of 425μg·h^(−1)·mg_(cat).^(−1),being close to the best-reported results.Noteworthy,the obtained performance metrics are significantly larger than those for N_(2) reduction reaction.It also shows good durability with negligible activity decay even after 10 cycles.Theoretical simulations reveal that the introduction of P dopants tunes the electronic structure of Ti active sites,thereby enhancing the NO adsorption and facilitating the desorption of ^(*)NH_(3).Moreover,the utilization of IL further suppresses the competitive hydrogen evolution reaction.This study highlights the advantage of the catalyst−electrolyte engineering strategy for producing NH_(3) at a high efficiency and rate.
基金The authors gratefully acknowledge the financial supports provided by the National Natural Science Foundation of China(No.21902119)Guangxi Provincial Natural Science Foundation(No.GUIKEAD22035044)Advanced Innovation Teams and Xinghu Scholars Program of Guangxi Medical University,and start-up funding for high-level talents from Guangxi Medical University Cancer Hospital。
文摘Facilitated by reactive oxygen species(ROS)-involved therapies,tumor cells undergo immunogenic cell death(ICD)to stimulate long-term immunity response.However,it is hard to trigger abundant and large-scale ICD for satisfactory cancer immunotherapy.Herein,a multifunctional sonosensitizer that consists of Au single atoms and clusters anchored on TiO_(2)nanosheets(named Au_(S/C)-TiO_(2))is reported for augmented sonodynamic therapy(SDT)and glucose depletion,which ultimately induce robust ICD due to the improved ROS generation and strong endoplasmic reticulum(ER)stress.The synergy effect between Au cluster/single atom with TiO_(2)nanosheets intensifies apoptosis and ICD pathways to inhibit 80%of tumor cells through in vivo analyses.Furthermore,immune cells in vivo analyses verify the effectiveness of Au_(S/C)-TiO_(2)sonosensitizer towards the induction of antitumor immunity.This study thus reveals that simultaneous presence of ROS generation and strong ER stress can efficiently evoke a strong ICD-mediated immune response.
基金This work was financially supported by National Natural Science Foundation of China (Nos. 51808037, 21601136 and 21876010)the Science & Technology Development Fund of Tianjin Education Commission for Higher Education (No. 2018KJ126)the Fundamental Research Funds for the Central Universities (No. FRF-TP-16-060A1).
文摘Catalytic oxidation of toluene over noble metal catalysts is a representative reaction for elimination of volatile organic compounds(VOCs).However,to fully understand the activation of molecular oxygen and the role of active oxygen species generated in this reaction is still a challenging target.Herein,MgO nanosheets and single-atom Pt loaded MgO(Pt SA/MgO)nanosheets were synthesized and used as catalysts in toluene oxidation.The activation process of molecular oxygen and oxidation performance on the two catalysts were contrastively investigated.The Pt SA/MgO exhibited significantly enhanced catalytic activity compared to MgO.The oxygen vacancies can be easily generated on the Pt SA/MgO surface,which facilitate the activation of molecular oxygen and the formation of active oxygen species.Based on the experimental data and theoretical calculations,an active oxygen species promoted oxidation mechanism for toluene was proposed.In the presence of H2O,the molecular oxygen is more favorable to be dissociated to generate•OH on the oxygen vacancies of the Pt SA/MgO surface,which is the dominant active oxygen species.We anticipate that this work may shed light on further investigation of t10.1007/s12274-020-2765-1he oxidation mechanism of toluene and other VOCs over noble metal catalysts.
基金This work was financially supported by National Key R&D Program of China(No.2017YFA0700104)the National Natural Science Foundation of China(Nos.22075211,21601136,51971157,51761165012,and 62005173)+2 种基金Project funded by China Postdoctoral Science Foundation(No.2020TQ0201)Tianjin Science Fund for Distinguished Young Scholars(No.19JCJQJC61800)The authors also acknowledge National Supercomputing Center in Shenzhen for providing the computational resources and materials studio(version 7.0,DMol3).
文摘An effective electrocatalyst being highly active in all pH range for oxygen reduction reaction(ORR)is crucial for energy conversion and storage devices.However,most of the high-efficiency ORR catalysis was reported in alkaline conditions.Herein,we demonstrated the preparation of atomically dispersed Fe-Zn pairs anchored on porous N-doped carbon frameworks(Fe-Zn-SA/NC),which works efficiently as ORR catalyst in the whole pH range.It achieves high half-wave potentials of 0.78,0.85 and 0.72 V in 0.1 M HClO4,0.1 M KOH and 0.1 M phosphate buffer saline(PBS)solutions,respectively,as well as respectable stability.The performances are even comparable to Pt/C.Furthermore,when assembled into a Zn-air battery,the high power density of 167.2 mWcm−2 and 120 h durability reveal the feasibility of Fe-Zn-SA/NC in real energy-related devices.Theoretical calculations demonstrate that the superior catalytic activity of Fe-Zn-SA/NC can be contributed to the lower energy barriers of ORR at the Fe-Zn-N6 centers.This work demonstrates the potential of Fe-Zn pairs as alternatives to the Pt catalysts for efficient catalytic ORR and provides new insights of dual-atom catalysts for other energy conversion related catalytic reactions.
基金the National Key R&D Program of China(No.2017YFA0700104)the National Natural Science Foundation of China(Nos.21601136 and 11404016)+1 种基金the National Program for Thousand Young Talents of China,Tianjin Municipal Education Commission,Tianjin Municipal Science and Technology Commission(No.15JCYBJC52600)the Fundamental Research Fund of Tianjin University of Technology.
文摘Natural organisms contain rich elements and naturally optimized smart structures,both of which have inspired various innovative concepts and desig ns in human society.In particular,several natural organisms have been used as element sources to synthesize low-cost and environmentally friendly electrocatalysts for the oxygen reduction reaction(ORR)in fuel cells and metal-air batteries,which are clean energy devices.However,to date,no naturally optimized smart structures have been employed in the synthesis of ORR catalysts,including graphene-based materials.Here,we demonstrate a novel strategy to synthesize graphene-graphite films(GGFs)by heating butterfly wings coated with FeCI3 in N2,in which the full power of natural organisms is utilized.The wings work not only as an element source for GGF generation but also as a porous supporting structure for effective nitrogen doping,two-dimensional spreading,and double-face exposure of the GGFs.These GGFs exhibit a half-wave potential of 0.942 V and a H2O2 yield of<0.07%for ORR electrocatalysis;these values are comparable to those for the best commercial Pt/C and all previously reported ORR catalysts in alkaline media.This two-in-one strategy is also successful with cicada and dragonfly wings,indicating that it is a universal,green,and cost-effective method for developing high-performance graphene-based materials.
基金financially supported by the National Natural Science Foundation of China (22075211, 62005173 and 21601136)Tianjin Science Fund for Distinguished Young Scholars (19JCJQJC61800)+1 种基金the Research Fund of State Key Laboratory for Marine Corrosion and Protection of Luoyang Ship Material Research Institute (LSMRI) under the contract No. KF190411the Science and Technology Development Fund of Tianjin Education Commission for Higher Education (2018KJ126)。
文摘开发高效且性能稳定的氧析出(OER)、氧还原(ORR)和氢析出(HER)三功能催化剂是制备能源存储与转换设备的关键.本文使用一步磷化法,在氮磷共掺杂碳基上制备了Fe Co金属合金/磷化物催化剂(Fe Co-P/PNC).该催化剂显示了良好的ORR性能,展现了0.86 V (vs.RHE,相对于可逆氢电极)的半波电位;在OER和HER反应中,催化剂在10 m A cm^(-2)的电流密度下的过电位分别为350和158 m V.密度泛函理论计算表明,磷在Fe Co磷化物和碳基体中皆起主导作用,使得该催化剂同时具有良好的ORR、OER和HER功能.以Fe Co-P/PNC为空气阴极组装的水系电池和柔性锌-空气电池的峰值功率密度分别为195.1和90.8 m W cm^(-2),且两种电池均具有优异的充放电性能、长寿命和高柔性.此外,自供能的整体水分解系统表现出较低的(1.71 V)工作电压以驱动10 m A cm^(-2)的电流密度,进一步证实了该催化剂出色的多功能性.
基金supported by National Natural Science Foundation of China(Nos.22075211,22109118,21601136,51971157,and 51621003).
文摘Electrochemical nitric oxide reduction reaction(NORR)to produce ammonia(NH3)under ambient conditions is a promising alternative to the energy and carbon-intensive Haber–Bosch approach,but its performance is still improved.Herein,molybdenum carbides(MoC)nanocrystals confined by nitrogen-doped carbon nanosheets are first designed as an efficient and durable electrocatalyst for catalyzing the reduction of NO to NH3 with maximal Faradaic efficiency of 89%±2%and a yield rate of 1,350±15μg·h^(−1)·cm^(−2) at the applied potential of−0.8 V vs.reversible hydrogen electrode(RHE)as well as high stable activity with negligible current density and NH3 yield rate decays over a 30 h continue the test.Moreover,as a proof-of-concept of Zn–NO battery,it achieves a peak power density of 1.8 mW·cm^(−2) and a large NH3 yield rate of 782±10μg·h^(−1)·cm^(−2),which are comparable to the best-reported results.Theoretical calculations reveal that the MoC(111)has a strong electronic interaction with NO molecules and thus lowering the energy barrier of the potential-determining step and suppressing hydrogen evolution kinetics.This work suggests that Mo-based materials are a powerful platform providing great opportunities to explore highly selective and active catalysts for NH3 production.
基金We acknowledge helpful discussion with Prof.Hongjie Dai.This work was supported by the National Natural Science Foundation of China(NSFC)the National Key Research and Development Project(Nos.2018YFB1502401 and 2018YFA0702002)+4 种基金the Royal Society and the Newton Fund through the Newton Advanced Fellowship award(NAF\R1\191294)the Program for Changjiang Scholars and Innovation Research Team in the University(No.IRT1205)the China Postdoctoral Science Foundation(No.BX20200336)the Fundamental Research Funds for the Central Universitiesthe long-term subsidy mechanism from the Ministry of Finance and the Ministry of Education of PRC.
文摘Developing efficient seawater-electrolysis system for mass production of hydrogen is highly desirable due to the abundance of seawater.However,continuous electrolysis with seawater feeding boosts the concentration of sodium chloride in the electrolyzer,leading to severe electrode corrosion and chlorine evolution.Herein,the common-ion effect was utilized into the electrolyzer to depress the solubility of NaCl.Specifically,utilization of 6M NaOH halved the solubility of NaCl in the electrolyte,affording efficient,durable,and sustained seawater electrolysis in NaCl-saturated electrolytes with triple production of H_(2),O_(2),and crystalline NaCl.Ternary NiCoFe phosphide was employed as a bifunctional anode and cathode in simulative and Ca/Mg-free seawater-electrolysis systems,which could stably work under 500 mA/cm^(2) for over 100 h.We attribute the high stability to the increased Na^(+)concentration,which reduces the concentration of dissolved Cl-in the electrolyte according to the common-ion effect,resulting in crystallization of NaCl,eliminated anode corrosion,and chlorine oxidation during continuous supplementation of Ca/Mg-free seawater to the electrolysis system.
基金This research is supported by National Science Foundation of China under Grant No. 10671139 and the Science Foundation of Jiangsu Province under Grant No. 11071182.
基金supported by the Research Fund of State Key Laboratory for Marine Corrosion and Protection of Luoyang Ship Material Research Institute(LSMRI)(KF190411)Tianjin Natural Science Foundation(18JCQNJC77100)Beijing PARATERA Tech CO.,Ltd.for providing HPC resources that have contributed to the research results reported in this paper。
基金the National Natural Science Foundation of China(Nos.22075211,21601136,51971157,62005173,and 51621003)Guangdong Province Higher Vocational Colleges&Schools Pearl River Scholar Funded Scheme(2016),Guangdong Third Generation Semiconductor Engineering Technology Development Center(No.2020GCZX007)+2 种基金Science,Technology,and Innovation Commission of Shenzhen Municipality(No.RCBS20200714114818140)China Postdoctoral Science Foundation(No.2019M663118)School level scientific research project of Shenzhen Institute of information technology(No.PT2019E002).
文摘The electrosynthesis of hydrogen peroxide(H2O2)from oxygen reduction reaction(ORR)via a two-electron pathway provides an appealing alternative to the energy-intensive anthraquinone route;however,the development of ORR with high selectivity and durability for H2O2 production is still challenging.Herein,we demonstrate an active and stable catalyst,composing of highly dispersed Ag nanoclusters on N-doped hollow carbon spheres(NC-Ag/NHCS),which can effectively reduce O2 molecules into H2O2 with a selectivity of 89%–91%in a potential range from 0.2 to 0.7 V(vs.reversible hydrogen electrode(RHE))in acidic media.Strikingly,NC-Ag/NHCS achieve a mass activity of 27.1 A·g^(−1) and a yield rate of 408 mmol·gcat.^(−1)·h^(−1) at 0.7 V,both of which are comparable with the best-reported results.Furthermore,NC-Ag/NHCS enable catalyzing H2O2 production with a stable current density over 48-h electrolysis and only about 9.8%loss in selectivity after 10,000 cycles.Theoretical analyses indicate that Ag nanoclusters can contribute more electrons to favor the protonation of adsorbed O2,thus leading to a high H2O2 selectivity.This work confirms the great potential of metal nanocluster-based materials for H2O2 electrosynthesis under ambient conditions.