Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the develop...Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.展开更多
Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement.Unlike the previously reported singleatom or dual-atom configura...Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement.Unlike the previously reported singleatom or dual-atom configurations,we designed a new type of binary-atom catalyst,through engineering Fe-N_(4)electronic structure with adjacent Co-N_(2)C_(2)and nitrogen-coordinated Co nanoclusters,as oxygen electrocatalysts.The resultant optimized electronic structure of the Fe-N_(4)active center favors the binding capability of intermediates and enhances oxygen reduction reaction(ORR)activity in both alkaline and acid conditions.In addition,anchoring M-N-C atomic sites on highly graphitized carbon supports guarantees of efficient charge-and mass-transports,and escorts the high bifunctional catalytic activity of the entire catalyst.Further,through the combination of electrochemical studies and in-situ X-ray absorption spectroscopy analyses,the ORR degradation mechanisms under highly oxidative conditions during oxygen evolution reaction processes were revealed.This work developed a new binary-atom catalyst and systematically investigates the effect of highly oxidative environments on ORR electrochemical behavior.It demonstrates the strategy for facilitating oxygen electrocatalytic activity and stability of the atomically dispersed M-N-C catalysts.展开更多
The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper re...The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper reviews the speciation,forms and distribution of sulfur in coal,the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis,and the sulfur regulation during coal-blending coking of high organic-sulfur coals.It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization,which raises the need of a combination of current or newly adopted characterization methods.Different from the removal of inorganic sulfur from coal,the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property,particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes.Based on the interactions among the sulfur radicals,sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char,regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is,the high volatile coals with an appropriate releasing temperature range of CH4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals,and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals.Wherein,the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.展开更多
The electroreduction reaction of CO_(2)(ECO_(2)RR)requires high-performance catalysts to convert CO_(2)into useful chemicals.Transition metal-based atomically dispersed catalysts are promising for the high selectivity...The electroreduction reaction of CO_(2)(ECO_(2)RR)requires high-performance catalysts to convert CO_(2)into useful chemicals.Transition metal-based atomically dispersed catalysts are promising for the high selectivity and activity in ECO_(2)RR.This work presents a series of atomically dispersed Co,Fe bimetallic catalysts by carbonizing the Fe-introduced Co-zeolitic-imidazolate-framework(C-Fe-Co-ZIF)for the syngas generation from ECO_(2)RR.The synergistic effect of the bimetallic catalyst promotes CO production.Compared to the pure C-Co-ZiF,C-Fe-Co-ZIF facilitates CO production with a CO Faradaic efficiency(FE)boost of 10%,with optimal FE_(CO)of 51.9%,FE_(H_(2))of 42.4%at-0.55 V,and CO current density of 8.0 mA cm^(-2)at-0.7 V versus reversible hydrogen electrode(RHE).The H_(2)/CO ratio is tunable from 0.8 to 4.2 in a wide potential window of-0.35 to-0.8 V versus RHE.The total FE_(CO+H_(2))maintains as high as 93%over 10 h.The proper adding amount of Fe could increase the number of active sites and create mild distortions for the nanoscopic environments of Co and Fe,which is essential for the enhancement of the CO production in ECO_(2)RR.The positive impacts of Cu-Co and Ni-Co bimetallic catalysts demonstrate the versatility and potential application of the bimetallic strategy for ECO_(2)RR.展开更多
Molecularly thin water layer, with a hydrogen bonding network different from those in bulk water and ice, has unique properties and is generally involved in many important processes such as wetting, erosion, atmospher...Molecularly thin water layer, with a hydrogen bonding network different from those in bulk water and ice, has unique properties and is generally involved in many important processes such as wetting, erosion, atmosphere chemical reaction, protein folding and biomolecular interaction. Here, we report a new water layer structure at room temperature, which is found inside nanobubbles by using synchrotron based scanning transmission soft X-ray microscopy(STXM). The three peaks 535.0, 536.8 and 540.9 e V at O K edge inside the nanobubbles show a novel characteristics of very thin water layers, which has never been observed before.展开更多
Oxygen reduction/evolution reactions(ORR/OERs)catalysts play a key role in the metal‐air battery and water‐splitting process.Herein,we developed a facile template‐free method to fabricate a new type of non–noble m...Oxygen reduction/evolution reactions(ORR/OERs)catalysts play a key role in the metal‐air battery and water‐splitting process.Herein,we developed a facile template‐free method to fabricate a new type of non–noble metal‐based hybrid catalyst which consists of binary FeNi alloy/nitride nanocrystals with graphitic‐shell and biomass‐derived N‐doped carbon(NC)(FexNiyN@C/NC).This novel nanostructure exhibits superior performance for ORR/OER,which can be attributed to the strong interactions between the graphitic‐shell encapsulated FeNi alloy/nitride nanocrystals and the N‐doped porous carbon substrate.The X‐ray absorption spectroscopy technique was employed to reveal the underlying mechanisms for the excellent performance.The assembled Zn‐air battery device exhibits outstanding charging/discharging performance and cycling stability,indicating the great potential of this type of novel catalysts.展开更多
Biomolecules with a broad range of structure and heteroatom-containing groups offer a great opportunity for rational design of promising electrocatalysts via versatile chemistry.In this study,uniform folic acid-Co nan...Biomolecules with a broad range of structure and heteroatom-containing groups offer a great opportunity for rational design of promising electrocatalysts via versatile chemistry.In this study,uniform folic acid-Co nanotubes(FA-Co NTs) were hydrothermally prepared as sacrificial templates for highly porous Co and N co-doped carbon nanotubes(Co-N/CNTs) with well-controlled size and morphology.The formation mechanism of FA-Co NTs was investigated and FA-Co-hydrazine coordination interaction together with the H-bond interaction between FA molecules was characterized to be the driving force for growth of one-dimensional nanotubes.Such distinct metal-ligand interaction afforded the resultant CNTs rich Co-N_x sites,hierarchically porous structure and Co nanoparticle-embedded conductive network,thus an overall good electrocatalytic activity for oxygen reduction.Electrochemical tests showed that Co-N/CNTs-900 promoted an efficient 4 e ORR process with an onset potential of 0.908 V vs.RHE,a limiting current density of 5.66 mA cm^(-2) at 0.6 V and a H_2 O_2 yield lower than 5%,comparable to that of 20%Pt/C catalyst.Moreover,the catalyst revealed very high stability upon continuous operation and remarkable tolerance to methanol.展开更多
Subcritical and supercritical water gasification of petroleum coke and asphaltene was performed at variable temperatures(350–650°C),feed concentrations(15–30 wt%)and reaction times(15–60 min).Nickel-impregnate...Subcritical and supercritical water gasification of petroleum coke and asphaltene was performed at variable temperatures(350–650°C),feed concentrations(15–30 wt%)and reaction times(15–60 min).Nickel-impregnated activated carbon(Ni/AC)was synthesized as a catalyst for enhancing syngas yields at optimal gasification conditions(650°C,15 wt%and 60 min).Structural chemistry of precursors and chars developed at different gasification temperatures was studied using physicochemical and synchrotronbased approaches such as carbon–hydrogen–nitrogen–sulfur(CHNS)analysis,thermogravimetric and differential thermogravimetric analysis(TGA/DTA),scanning electron microscopy(SEM),Fourier-Transform Infrared spectroscopy(FTIR),Raman spectroscopy,X-ray diffraction(XRD)and X-ray absorption spectroscopy(XAS).Asphaltene testified to be a better precursor for catalytic hydrothermal gasification leading to 11.97 mmol/g of total gas yield compared to petroleum coke(8.04 mmol/g).In particular,supercritical water gasification using 5 wt%Ni/AC at 650°C with 15 wt%feed concentration for 60 min resulted in 4.17 and 2.98 mmol/g of H_2from asphaltene and petroleum coke,respectively.Under the same conditions,the respective CH_4yields from catalytic gasification of asphaltene and petroleum coke were 2.54and 1.07 mmol/g.Nonetheless,asphaltene also seemed to an attractive feedstock for the production of highly aromatic chars through hydrothermal gasification.展开更多
Different sizes of layered CoOOH were synthesized by the molten-salt-assisted method at different temperatures.X-ray diffraction and scanning electron microscope studies reveal that CoOOH grew at(003)with increasing t...Different sizes of layered CoOOH were synthesized by the molten-salt-assisted method at different temperatures.X-ray diffraction and scanning electron microscope studies reveal that CoOOH grew at(003)with increasing temperature,and its size can reach dozens of microns.X-ray absorption near edge structure and XPS studies demonstrate that the Co valence state of CoOOH-750 is trivalent,and X-ray Absorption Fine Structure shows that it had a higher symmetry and lower disorder degree,indicating that CoOOH-750 has higher crystallinity and Co3+.The results of electrochemical tests show that CoOOH-750 exhibited the best oxygen-evolution-reaction(OER)catalytic activity.展开更多
To accelerate the kinetics of oxygen evolution reaction(OER)regarding the energy conversion and storage approaches,the discovery of desirable cost-effective and highly efficient electrocatalysts is of prime importance...To accelerate the kinetics of oxygen evolution reaction(OER)regarding the energy conversion and storage approaches,the discovery of desirable cost-effective and highly efficient electrocatalysts is of prime importance.This study demonstrates a layered CaCo_2O_4with a two-dimensional nanoplate structure,which possesses electrocatalytic activity for OER.The OER activity was achieved on CaCo_2O_4with a Tafel slope of 71 mV dec^(-1)and a current density of 10 mA cm^(-2)at an overpotential of 371 mV,which was more active than the similar structure LiCoO_2catalyst.Combined with X-ray absorption fine structure and density functional theory calculations,the enhanced OER activity and stability are mainly attributed to the unique electronic structure derived from the interaction of Ca and Co,and improved electrical conductivity.CaCo_2O_4can be developed as a highly active and earth-abundant catalyst for OER in energy conversion and storage technologies.展开更多
Electrochemical reduction of CO_(2)to formate is economically attractive but improving the reaction selectivity and activity remains challenging.Herein,we introduce boron(B)atoms to modify the local electronic structu...Electrochemical reduction of CO_(2)to formate is economically attractive but improving the reaction selectivity and activity remains challenging.Herein,we introduce boron(B)atoms to modify the local electronic structure of bismuth with positive valence sites for boosting conversion of CO_(2)into formate with high activity and selectivity in a wide potential window.By combining experimental and computational investigations,our study indicates that B dopant differentiates the proton participations of rate-determining steps in CO_(2)reduction and in the competing hydrogen evolution.By comparing the experimental observations with the density functional theory,the dominant mechanistic pathway of B promoted formate generation and the B concentration modulated effects on the catalytic property of Bi are unravelled.This comprehensive study offers deep mechanistic insights into the reaction pathway at an atomic and molecular level and provides an effective strategy for the rational design of highly active and selective electrocatalysts for efficient CO_(2)conversion.展开更多
Wadsley-Roth (W-R) structured oxides featured with wide channels represent one of the most promising material families showing compelling rate performance for lithium-ion batteries.Herein,we report an indepth study on...Wadsley-Roth (W-R) structured oxides featured with wide channels represent one of the most promising material families showing compelling rate performance for lithium-ion batteries.Herein,we report an indepth study on the fast and extensive intercalation chemistry of phosphorus stabilized W-R phase PNb_(9)O_(25) and its application in high energy and fast-charging devices.We explore the intercalation geometry of PNb_(9)O_(25) and identify two geometrical types of stable insertion sites with the total amount much higher than conventional intercalation-type electrodes.We reveal the ion transportation kinetics that the Li ions initially diffuse along the open type Ⅲ channels and then penetrate to edge sites with low kinetic barriers.During the lithiation,no remarkable phase transition is detected with nearly intact host phosphorous niobium oxide backbone.Therefore,the oxide framework of PNb_(9)O_(25) keeps almost unchanged with all the fast diffusion channels and insertion cavities well-maintained upon cycling,which accomplishes the unconventional electrochemical performance of W-R structured electrodes.展开更多
Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metalsulfur batteries.Motivated by a theoretical prediction,herein,we strategically propose nitrogenvacancy tantalum nit...Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metalsulfur batteries.Motivated by a theoretical prediction,herein,we strategically propose nitrogenvacancy tantalum nitride(Ta3N5-x)impregnated inside the interconnected nanopores of nitrogendecorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in roomtemperature sodium-sulfur batteries.Through a pore-constriction mechanism,the nitrogen vacancies are controllably constructed during the nucleation of Ta3N5-x.The defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level,not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials,but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion.Moreover,the interconnected continuous Ta3N5-x-in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior.Due to these attributes,the as-developed Ta3N5-x-based electrode achieves superior rate capability of 730 mAh g-1 at 3.35 A g-1,long-term cycling stability over 2000 cycles,and high areal capacity over 6 mAh cm-2 under high sulfur loading of 6.2 mg cm-2.This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries,but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.展开更多
The polymer electrolyte membrane(PEM)electrolyzers are burdened with costly iridium(Ir)-based catalysts and high operation overpotentials for the oxygen evolution reaction(OER).The development of earth-abundant,highly...The polymer electrolyte membrane(PEM)electrolyzers are burdened with costly iridium(Ir)-based catalysts and high operation overpotentials for the oxygen evolution reaction(OER).The development of earth-abundant,highly active,and durable electrocatalysts to replace Ir is a critical step in reducing the cost of green hydrogen production.Here we develop a Ru5Mo4Ox binary oxide catalyst that exhibits high activity and stability in acidic OER.The electron-withdrawing property of Mo enriches the electrophilic surface oxygen species,which promotes acidic OER to proceed via the adsorbate evolution pathway.As a result,we achieve a 189 mV overpotential at 10 mA·cm^(-2) and a Tafel slope of 48.8 mV·dec^(-1).Our catalyst demonstrates a substantial 18-fold increase in intrinsic activity,as evaluated by turnover frequency,compared to commercially available RuO_(2) and IrO_(2) catalysts.Moreover,we report a stable OER operation at 10 mA·cm^(-2) for 100 h with a low degradation rate of 2.05 mV·h^(-1).展开更多
基金the financial support of Guangdong Basic and Applied Basic Research Foundation (No. 2023A1515010940)Shenzhen Natural Science Fund (the Stable Support Plan Program No. 20220809160022001)the Shenzhen Science and Technology Programs (No. ZDSYS20220527171401003, KQTD20190929173914967)。
文摘Constructing the efficacious and applicable bifunctional electrocatalysts and establishing out the mechanisms of organic electro-oxidation by replacing anodic oxygen evolution reaction(OER) are critical to the development of electrochemicallydriven technologies for efficient hydrogen production and avoid CO_(2) emission. Herein, the hetero-nanocrystals between monodispersed Pt(~ 2 nm) and Ni_(3)S_(2)(~ 9.6 nm) are constructed as active electrocatalysts through interfacial electronic modulation, which exhibit superior bi-functional activities for methanol selective oxidation and H_(2) generation. The experimental and theoretical studies reveal that the asymmetrical charge distribution at Pt–Ni_(3)S_(2) could be modulated by the electronic interaction at the interface of dual-monodispersed heterojunctions, which thus promote the adsorption/desorption of the chemical intermediates at the interface. As a result, the selective conversion from CH_(3)OH to formate is accomplished at very low potentials(1.45 V) to attain 100 m A cm^(-2) with high electronic utilization rate(~ 98%) and without CO_(2) emission. Meanwhile, the Pt–Ni_(3)S_(2) can simultaneously exhibit a broad potential window with outstanding stability and large current densities for hydrogen evolution reaction(HER) at the cathode. Further, the excellent bi-functional performance is also indicated in the coupled methanol oxidation reaction(MOR)//HER reactor by only requiring a cell voltage of 1.60 V to achieve a current density of 50 m A cm^(-2) with good reusability.
基金funded by the National Natural Science Foundation of China (22208331, 52003300)the Natural Sciences and Engineering Research Council of Canada (NSERC)+4 种基金the Fonds de Recherche du Québec-Nature et Technologies (FRQNT)Centre Québécois sur les Materiaux Fonctionnels (CQMF), McGill Universityécole de Technologie Supérieure (éTS)Institut National de la Recherche Scientifique (INRS)the support from the Marcelle-Gauvreau Engineering Research Chair program
文摘Regulating the local configuration of atomically dispersed transition-metal atom catalysts is the key to oxygen electrocatalysis performance enhancement.Unlike the previously reported singleatom or dual-atom configurations,we designed a new type of binary-atom catalyst,through engineering Fe-N_(4)electronic structure with adjacent Co-N_(2)C_(2)and nitrogen-coordinated Co nanoclusters,as oxygen electrocatalysts.The resultant optimized electronic structure of the Fe-N_(4)active center favors the binding capability of intermediates and enhances oxygen reduction reaction(ORR)activity in both alkaline and acid conditions.In addition,anchoring M-N-C atomic sites on highly graphitized carbon supports guarantees of efficient charge-and mass-transports,and escorts the high bifunctional catalytic activity of the entire catalyst.Further,through the combination of electrochemical studies and in-situ X-ray absorption spectroscopy analyses,the ORR degradation mechanisms under highly oxidative conditions during oxygen evolution reaction processes were revealed.This work developed a new binary-atom catalyst and systematically investigates the effect of highly oxidative environments on ORR electrochemical behavior.It demonstrates the strategy for facilitating oxygen electrocatalytic activity and stability of the atomically dispersed M-N-C catalysts.
基金financial support of National Natural Science Foundation of China(U1910201,21878208)Transformation of Scientific and Technological Achievements Programs of Higher Education Institutions in Shanxi(TSTAP)Shanxi Province Science Foundation for Key Program(201901D111001(ZD))。
文摘The utilization of high-sulfur coal is becoming more urgent due to the excessive utilization of low-sulfur,high-quality coal resources,and sulfur removal from high-sulfur coal is the most important issue.This paper reviews the speciation,forms and distribution of sulfur in coal,the sulfur removal from raw coal,the thermal transformation of sulfur during coal pyrolysis,and the sulfur regulation during coal-blending coking of high organic-sulfur coals.It was suggested that the proper characterization of sulfur in coal cannot be obtained only by either chemical method or instrumental characterization,which raises the need of a combination of current or newly adopted characterization methods.Different from the removal of inorganic sulfur from coal,the organic sulfur can only be partly removed by chemical technologies;and the coal structure and property,particularly high-sulfur coking coals which have caking ability,may be altered and affected by the pretreatment processes.Based on the interactions among the sulfur radicals,sulfur-containing and hydrogen-containing fragments during coal pyrolysis and the reactions with minerals or nascent char,regulating the sulfur transformation behavior in the process of thermal conversion is the most effective way to utilize high organic-sulfur coals in the coke-making industry.An in-situ regulation approach of sulfur transformation during coal-blending coking has been suggested.That is,the high volatile coals with an appropriate releasing temperature range of CH4 overlapping well with that of H2 S from high organic-sulfur coals is blended with high organic-sulfur coals,and the C–S/C–C bonds in some sulfur forms are catalytically broken and immediately hydrogenated by the hydrogencontaining radicals generated from high volatile coals.Wherein,the effect of mass transfer on sulfur regulation during the coking process should be considered for the larger-scale coking tests through optimizing the ratios of different coals in the coal blend.
基金This work is supported financially by the Natural Sciences and Engineering Research Council of Canada(NSERC),the Fonds de Recherche du Québec-Nature et Technologies(FRQNT)Centre Québécois sur les Materiaux Fonctionnels(CQMF),the Canada Foundation for Innovation(CFI)+1 种基金Institut National de la Recherche Scientifique(INRS).The XAS characterizations were performed at the Canadian Light Source(CLS),which is financially supported by NSERC,CFIthe University of Saskatchewan,the Government of Saskatchewan,Western Economic Diversification Canada,the National Research Council of Canada,and the Canadian Institutes of Health Research。
文摘The electroreduction reaction of CO_(2)(ECO_(2)RR)requires high-performance catalysts to convert CO_(2)into useful chemicals.Transition metal-based atomically dispersed catalysts are promising for the high selectivity and activity in ECO_(2)RR.This work presents a series of atomically dispersed Co,Fe bimetallic catalysts by carbonizing the Fe-introduced Co-zeolitic-imidazolate-framework(C-Fe-Co-ZIF)for the syngas generation from ECO_(2)RR.The synergistic effect of the bimetallic catalyst promotes CO production.Compared to the pure C-Co-ZiF,C-Fe-Co-ZIF facilitates CO production with a CO Faradaic efficiency(FE)boost of 10%,with optimal FE_(CO)of 51.9%,FE_(H_(2))of 42.4%at-0.55 V,and CO current density of 8.0 mA cm^(-2)at-0.7 V versus reversible hydrogen electrode(RHE).The H_(2)/CO ratio is tunable from 0.8 to 4.2 in a wide potential window of-0.35 to-0.8 V versus RHE.The total FE_(CO+H_(2))maintains as high as 93%over 10 h.The proper adding amount of Fe could increase the number of active sites and create mild distortions for the nanoscopic environments of Co and Fe,which is essential for the enhancement of the CO production in ECO_(2)RR.The positive impacts of Cu-Co and Ni-Co bimetallic catalysts demonstrate the versatility and potential application of the bimetallic strategy for ECO_(2)RR.
基金Supported by the National Natural Science Foundation of China(Nos.11079050,11290165 and 11305252)the National Basic Research Program of China(No.2013CB932801)+1 种基金the Program of the Chinese Academy of Sciences(Nos.KJCX2-EW-W09 and KJZD-EW-M03)the Key Laboratory of Interfacial Physics and Technology of the Chinese Academy of Sciences,and the Open Research Project of the Large Scientific Facility of the Chinese Academy of Sciences:Study on Self-assembly Technology and Nanometer Array with Ultra-high Density
文摘Molecularly thin water layer, with a hydrogen bonding network different from those in bulk water and ice, has unique properties and is generally involved in many important processes such as wetting, erosion, atmosphere chemical reaction, protein folding and biomolecular interaction. Here, we report a new water layer structure at room temperature, which is found inside nanobubbles by using synchrotron based scanning transmission soft X-ray microscopy(STXM). The three peaks 535.0, 536.8 and 540.9 e V at O K edge inside the nanobubbles show a novel characteristics of very thin water layers, which has never been observed before.
基金This study was supported by the Natural Sciences and Engineering Research Council of Canada(NSERC)the National Natural Science Foundation of China(21972017)+2 种基金Canada Foundation for Innovation(CFI)Centre Québécois sur les Materiaux Fonctionnels,Fondsde Recherche du Québec‐Nature et TechnologiesInstitut National de la Recherche Scientifique.Mingjie Wu gratefully acknowledges the scholarships from the China Scholarship Council.
文摘Oxygen reduction/evolution reactions(ORR/OERs)catalysts play a key role in the metal‐air battery and water‐splitting process.Herein,we developed a facile template‐free method to fabricate a new type of non–noble metal‐based hybrid catalyst which consists of binary FeNi alloy/nitride nanocrystals with graphitic‐shell and biomass‐derived N‐doped carbon(NC)(FexNiyN@C/NC).This novel nanostructure exhibits superior performance for ORR/OER,which can be attributed to the strong interactions between the graphitic‐shell encapsulated FeNi alloy/nitride nanocrystals and the N‐doped porous carbon substrate.The X‐ray absorption spectroscopy technique was employed to reveal the underlying mechanisms for the excellent performance.The assembled Zn‐air battery device exhibits outstanding charging/discharging performance and cycling stability,indicating the great potential of this type of novel catalysts.
基金supported by the National Natural Science Foundation of China (Nos. 51902204, 21975163)the Bureau of Industry and Information Technology of Shenzhen (No. 201901171518)the support provided by Instrumental Analysis Center of Shenzhen University (Xili Campus)。
文摘Biomolecules with a broad range of structure and heteroatom-containing groups offer a great opportunity for rational design of promising electrocatalysts via versatile chemistry.In this study,uniform folic acid-Co nanotubes(FA-Co NTs) were hydrothermally prepared as sacrificial templates for highly porous Co and N co-doped carbon nanotubes(Co-N/CNTs) with well-controlled size and morphology.The formation mechanism of FA-Co NTs was investigated and FA-Co-hydrazine coordination interaction together with the H-bond interaction between FA molecules was characterized to be the driving force for growth of one-dimensional nanotubes.Such distinct metal-ligand interaction afforded the resultant CNTs rich Co-N_x sites,hierarchically porous structure and Co nanoparticle-embedded conductive network,thus an overall good electrocatalytic activity for oxygen reduction.Electrochemical tests showed that Co-N/CNTs-900 promoted an efficient 4 e ORR process with an onset potential of 0.908 V vs.RHE,a limiting current density of 5.66 mA cm^(-2) at 0.6 V and a H_2 O_2 yield lower than 5%,comparable to that of 20%Pt/C catalyst.Moreover,the catalyst revealed very high stability upon continuous operation and remarkable tolerance to methanol.
基金the Natural Sciences and Engineering Research Council of Canada (NSERC)Canada Research Chair program for funding this bioenergy research
文摘Subcritical and supercritical water gasification of petroleum coke and asphaltene was performed at variable temperatures(350–650°C),feed concentrations(15–30 wt%)and reaction times(15–60 min).Nickel-impregnated activated carbon(Ni/AC)was synthesized as a catalyst for enhancing syngas yields at optimal gasification conditions(650°C,15 wt%and 60 min).Structural chemistry of precursors and chars developed at different gasification temperatures was studied using physicochemical and synchrotronbased approaches such as carbon–hydrogen–nitrogen–sulfur(CHNS)analysis,thermogravimetric and differential thermogravimetric analysis(TGA/DTA),scanning electron microscopy(SEM),Fourier-Transform Infrared spectroscopy(FTIR),Raman spectroscopy,X-ray diffraction(XRD)and X-ray absorption spectroscopy(XAS).Asphaltene testified to be a better precursor for catalytic hydrothermal gasification leading to 11.97 mmol/g of total gas yield compared to petroleum coke(8.04 mmol/g).In particular,supercritical water gasification using 5 wt%Ni/AC at 650°C with 15 wt%feed concentration for 60 min resulted in 4.17 and 2.98 mmol/g of H_2from asphaltene and petroleum coke,respectively.Under the same conditions,the respective CH_4yields from catalytic gasification of asphaltene and petroleum coke were 2.54and 1.07 mmol/g.Nonetheless,asphaltene also seemed to an attractive feedstock for the production of highly aromatic chars through hydrothermal gasification.
基金This work was supported by“Transformational Technologies for Clean Energy and Demonstration”,Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA21080200).
文摘Different sizes of layered CoOOH were synthesized by the molten-salt-assisted method at different temperatures.X-ray diffraction and scanning electron microscope studies reveal that CoOOH grew at(003)with increasing temperature,and its size can reach dozens of microns.X-ray absorption near edge structure and XPS studies demonstrate that the Co valence state of CoOOH-750 is trivalent,and X-ray Absorption Fine Structure shows that it had a higher symmetry and lower disorder degree,indicating that CoOOH-750 has higher crystallinity and Co3+.The results of electrochemical tests show that CoOOH-750 exhibited the best oxygen-evolution-reaction(OER)catalytic activity.
基金supported by the "Strategic Priority Research Program" of the Chinese Academy of Sciences (XDA02040600)supported by the Canadian Foundation for Innovation+5 种基金Natural Sciences and Engineering Research Council of Canadathe University of Saskatchewanthe Government of SaskatchewanWestern Economic Diversification Canadathe National Research Council Canadathe Canadian Institutes of Health Research
文摘To accelerate the kinetics of oxygen evolution reaction(OER)regarding the energy conversion and storage approaches,the discovery of desirable cost-effective and highly efficient electrocatalysts is of prime importance.This study demonstrates a layered CaCo_2O_4with a two-dimensional nanoplate structure,which possesses electrocatalytic activity for OER.The OER activity was achieved on CaCo_2O_4with a Tafel slope of 71 mV dec^(-1)and a current density of 10 mA cm^(-2)at an overpotential of 371 mV,which was more active than the similar structure LiCoO_2catalyst.Combined with X-ray absorption fine structure and density functional theory calculations,the enhanced OER activity and stability are mainly attributed to the unique electronic structure derived from the interaction of Ca and Co,and improved electrical conductivity.CaCo_2O_4can be developed as a highly active and earth-abundant catalyst for OER in energy conversion and storage technologies.
基金This work was supported by the Shenzhen Science and Technology Program(KQTD20190929173914967)。
文摘Electrochemical reduction of CO_(2)to formate is economically attractive but improving the reaction selectivity and activity remains challenging.Herein,we introduce boron(B)atoms to modify the local electronic structure of bismuth with positive valence sites for boosting conversion of CO_(2)into formate with high activity and selectivity in a wide potential window.By combining experimental and computational investigations,our study indicates that B dopant differentiates the proton participations of rate-determining steps in CO_(2)reduction and in the competing hydrogen evolution.By comparing the experimental observations with the density functional theory,the dominant mechanistic pathway of B promoted formate generation and the B concentration modulated effects on the catalytic property of Bi are unravelled.This comprehensive study offers deep mechanistic insights into the reaction pathway at an atomic and molecular level and provides an effective strategy for the rational design of highly active and selective electrocatalysts for efficient CO_(2)conversion.
基金supported by the National Natural Science Foundation of China (51774251)the Hebei Natural Science Foundation for Distinguished Young Scholars (B2017203313)+7 种基金the Hundred Excellent Innovative Talents Support Program in Hebei Province (SLRC2017057)the Scientific Research Foundation for the Returned Overseas Chinese Scholars (CG2014003002)the Canada Foundation for Innovationthe Government of OntarioOntario Research Fund - Research Excellencethe University of Torontosupported by the National Natural Science Foundation of China (51702207 and 11972219)the Program for Professor of Special Appointment (Young Eastern Scholar Program) at Shanghai Institutions of Higher Learning。
文摘Wadsley-Roth (W-R) structured oxides featured with wide channels represent one of the most promising material families showing compelling rate performance for lithium-ion batteries.Herein,we report an indepth study on the fast and extensive intercalation chemistry of phosphorus stabilized W-R phase PNb_(9)O_(25) and its application in high energy and fast-charging devices.We explore the intercalation geometry of PNb_(9)O_(25) and identify two geometrical types of stable insertion sites with the total amount much higher than conventional intercalation-type electrodes.We reveal the ion transportation kinetics that the Li ions initially diffuse along the open type Ⅲ channels and then penetrate to edge sites with low kinetic barriers.During the lithiation,no remarkable phase transition is detected with nearly intact host phosphorous niobium oxide backbone.Therefore,the oxide framework of PNb_(9)O_(25) keeps almost unchanged with all the fast diffusion channels and insertion cavities well-maintained upon cycling,which accomplishes the unconventional electrochemical performance of W-R structured electrodes.
基金support from University of Waterloo,Waterloo Institute for Nanotechnology,and Natural Sciences and Engineering Research Council of Canada(NSERC).This work was also supported by the Outstanding Youth Project of Guangdong Natural Science Foundation(2021B1515020051)Department of Science and Technology of Guangdong Province(2019JC01L203 and 2020B0909030004)+1 种基金the Natural Science Foundation of Ningxia(2023AAC01003)the Foundation of State Key Laboratory of High Efficiency Utilization of Coal and Green Chemical Engineering(2022-K79).
文摘Resolving low sulfur reaction activity and severe polysulfide dissolution remains challenging in metalsulfur batteries.Motivated by a theoretical prediction,herein,we strategically propose nitrogenvacancy tantalum nitride(Ta3N5-x)impregnated inside the interconnected nanopores of nitrogendecorated carbon matrix as a new electrocatalyst for regulating sulfur redox reactions in roomtemperature sodium-sulfur batteries.Through a pore-constriction mechanism,the nitrogen vacancies are controllably constructed during the nucleation of Ta3N5-x.The defect manipulation on the local environment enables well-regulated Ta 5d-orbital energy level,not only modulating band structure toward enhanced intrinsic conductivity of Ta-based materials,but also promoting polysulfide stabilization and achieving bifunctional catalytic capability toward completely reversible polysulfide conversion.Moreover,the interconnected continuous Ta3N5-x-in-pore structure facilitates electron and sodium-ion transport and accommodates volume expansion of sulfur species while suppressing their shuttle behavior.Due to these attributes,the as-developed Ta3N5-x-based electrode achieves superior rate capability of 730 mAh g-1 at 3.35 A g-1,long-term cycling stability over 2000 cycles,and high areal capacity over 6 mAh cm-2 under high sulfur loading of 6.2 mg cm-2.This work not only presents a new sulfur electrocatalyst candidate for metal-sulfur batteries,but also sheds light on the controllable material design of defect structure in hopes of inspiring new ideas and directions for future research.
基金support from the National Natural Science Foundation of China(No.52103300)the Guangdong Basic and Applied Basic Research Foundation(No.2023A1515010572)+7 种基金the Shenzhen Science and Technology Program(Nos.JCYJ20210324132806017 and GXWD20220811163904001)the Innovation Material Research Center of Harbin Institute of Technology,Shenzhen for the instrumentation assistance.Y.H.W.acknowledges the funding support from the National Natural Science Foundation of China(No.22179088)the Natural Science Foundation of Jiangsu Province of China(No.BK20210699)the National Natural Science Fund for Excellent Young Scientists Fund Program(Overseas)the Program for Jiangsu Specially-Appointed Professors,the Program of Soochow Innovation and Entrepreneurship Leading Talents(No.ZXL2022450)the start-up supports of Soochow University,Suzhou Key Laboratory of Functional Nano&Soft Materials,the Collaborative Innovation Center of Suzhou Nano Science&Technology,the 111 Project,the Joint International Research Laboratory of Carbon-Based Functional Materials and Devices.J.Z.acknowledges the funding support from the State Key Laboratory of Urban Water Resources&Environment(Harbin Institute of Technology)(No.2022TS36)Computer time made available by the National Supercomputing Center of China in Shenzhen(Shenzhen Cloud Computing Center)is gratefully acknowledged.J.L.acknowledges the start-up funding support from Shanghai Jiao Tong University(No.WH220432516)This research used synchrotron resources of the Advanced Photon Source,an Office of Science User Facility operated for the US Department of Energy Office of Science by Argonne National Laboratory and was supported by the US Department of Energy under contract No.DE-AC02-06CH11357 and the Canadian Light Source and its funding partners.
文摘The polymer electrolyte membrane(PEM)electrolyzers are burdened with costly iridium(Ir)-based catalysts and high operation overpotentials for the oxygen evolution reaction(OER).The development of earth-abundant,highly active,and durable electrocatalysts to replace Ir is a critical step in reducing the cost of green hydrogen production.Here we develop a Ru5Mo4Ox binary oxide catalyst that exhibits high activity and stability in acidic OER.The electron-withdrawing property of Mo enriches the electrophilic surface oxygen species,which promotes acidic OER to proceed via the adsorbate evolution pathway.As a result,we achieve a 189 mV overpotential at 10 mA·cm^(-2) and a Tafel slope of 48.8 mV·dec^(-1).Our catalyst demonstrates a substantial 18-fold increase in intrinsic activity,as evaluated by turnover frequency,compared to commercially available RuO_(2) and IrO_(2) catalysts.Moreover,we report a stable OER operation at 10 mA·cm^(-2) for 100 h with a low degradation rate of 2.05 mV·h^(-1).