Polyhydroxyalkanoate(PHA),a well-known biodegradable polymer,featuresβ-lactones as its monomers,which can be selectively synthesized through ring-expansion carbonylation of epoxides using well-defined[Lewis acid]^(+)...Polyhydroxyalkanoate(PHA),a well-known biodegradable polymer,featuresβ-lactones as its monomers,which can be selectively synthesized through ring-expansion carbonylation of epoxides using well-defined[Lewis acid]^(+)[Co(CO)_(4)]^(-)catalysts.However,the decomposition of[Co(CO)_(4)]^(-)species at temperatures exceeding 80℃presents a hurdle for the development of commercially viable processes under high-temperature reaction conditions to reduce reaction time.Drawing insights from stable{(acyl)Co(CO)n}intermediates involved in historical HCo(CO)_(4)-catalyzed hydroformylation processes,we sought to the high-temperature catalytic activity of epoxide ring-expansion carbonylation.The developed catalyst system,[(acetyl)Co(CO)_(2)dppp]and[(TPP)CrCl],exhibited exceptional catalytic performance with an unprecedented initial turnover frequency of 4700 h^(-1)at 100℃and a turnover numbers of 93000.Notably,the catalyst displayed outstanding stability,operating at 80℃for 168 h while selectively generatingβ-lactones.展开更多
Cobalt has excellent electrochemical,magnetic,and heat properties.As a strategic resource,it has been applied in many hightech products.However,the recent rapid growth of the battery industry has substantially deplete...Cobalt has excellent electrochemical,magnetic,and heat properties.As a strategic resource,it has been applied in many hightech products.However,the recent rapid growth of the battery industry has substantially depleted cobalt resources,leading to a crisis of cobalt resource supply.The paper examines cobalt ore reserves and distribution,and the recent development and consumption of cobalt resources are summarized as well.In addition,the principles,advantages and disadvantages,and research status of various methods are discussed comprehensively.It can be concluded that the use of diverse sources(Cu-Co ores,Ni-Co ores,zinc plant residues,and waste cobalt products)for cobalt production should be enhanced to meet developmental requirements.Furthermore,in recovery technology,the pyro-hydrometallurgical process employs pyrometallurgy as the pretreatment to modify the phase structure of cobalt minerals,enhancing its recovery in the hydrometallurgical stage and facilitating high-purity cobalt production.Consequently,it represents a promising technology for future cobalt recovery.Lastly,based on the above conclusions,the prospects for cobalt are assessed regarding cobalt ore processing and sustainable cobalt recycling,for which further study should be conducted.展开更多
Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corros...Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corrosion caused by the harmful chlorine.In contrast to the oxygen evolution reaction (OER)and chlorin ion oxidation reaction (ClOR),glycerol oxidation reaction (GOR) is more thermodynamically and kinetically favorable alternative.Herein,a Ru doping cobalt phosphide (Ru-CoP_(2)) is proposed as a robust bifunctional electrocatalyst for seawater electrolysis and GOR,for the concurrent productions of hydrogen and value-added formate.The in situ and ex situ characterization analyses demonstrated that Ru doping featured in the dynamic reconstruction process from Ru-CoP_(2)to Ru-CoOOH,accounting for the superior GOR performance.Further coupling GOR with hydrogen evolution was realized by employing Ru-CoP_(2)as both anode and cathode,requiring only a low voltage of 1.43 V at 100 mA cm^(-2),which was 250 m V lower than that in alkaline seawater.This work guides the design of bifunctional electrocatalysts for energy-efficient seawater electrolysis coupled with biomass resource upcycling.展开更多
Copper and cobalt were recovered from SICOMINES mining waste rock in the Democratic Republic of Congo.The process mineralogy of the samples was analyzed using scanning electron microscopy and energy dispersive spectro...Copper and cobalt were recovered from SICOMINES mining waste rock in the Democratic Republic of Congo.The process mineralogy of the samples was analyzed using scanning electron microscopy and energy dispersive spectroscopy.The results showed that copper minerals exhibited various forms and uneven particle sizes,while cobalt existed in the form of highly dispersed asbolane,and large amounts of easily slimed gangue minerals were filled in the samples,making it difficult to separate copper and cobalt minerals.The particle size range plays a decisive role in selecting the separation method for the copper−cobalt ore.Gravity separation was suitable for particles ranging from 43 to 246μm,while flotation was more effective for particles below 43μm.After ore grinding and particle size classification,applying a combined gravity separation(shaking table)−flotation method yielded concentrated minerals with a copper recovery of 72.83%and a cobalt recovery of 31.13%.展开更多
In recent years,metal phosphosulfides have attracted great attention as the promising anode materials in sodium/potassium batteries because of their incorporation of the advantages of metal phosphides and sulfides.How...In recent years,metal phosphosulfides have attracted great attention as the promising anode materials in sodium/potassium batteries because of their incorporation of the advantages of metal phosphides and sulfides.However,they are also confronted with the problem of unstable battery performance due to the heavy volume expansion and sluggish ion reaction kinetics.Herein,yolk-shell cobalt phosphosulfide nanocrystals encapsulating into multi-heterogeneous atom(N,P,S)-doped carbon framework(Co_(9)S_(8)/CoP@NPSC)were constructed by employing dodecahedral ZIF-67 as precursor and a polymer as carbon sources through simultaneous sulfidation and phosphorization processes.The synergistic effect of Co_(9)S_(8)and CoP component and the yolk-shell structure greatly improve the bettery performance and structural stability.In addition,the multiple hetero-atoms doped carbon frameworks enhance the conductivity of the electrode materials and increase the spacing of carbon layers to supply sufficient active sites and facilitate the Na^(+)/K^(+)transport.The electrochemical results demonstrated that Co_(9)S_(8)/CoP@NPSC exhibited the pleasant reversible capacity(360.47 mAh/g at 1 A/g)after 300 cycles and an unpredictable cycling stability(103.22 mAh/g after 1000 cycles)in the SIBs application.The ex-situ XRD and XPS analyses were further applied to study the sodium ion storage mechanism and the multi-step phase transition reaction of the yolk-shell heterogeneous structure.This work provides new perspectives for the preparation of novel structure metal phosphosulfide and their applications in anode materials for sodium/potassium batteries and other secondary batteries.展开更多
This work reveals the significant effects of cobalt(Co)on the microstructure and impact toughness of as-quenched highstrength steels by experimental characterizations and thermo-kinetic analyses.The results show that ...This work reveals the significant effects of cobalt(Co)on the microstructure and impact toughness of as-quenched highstrength steels by experimental characterizations and thermo-kinetic analyses.The results show that the Co-bearing steel exhibits finer blocks and a lower ductile-brittle transition temperature than the steel without Co.Moreover,the Co-bearing steel reveals higher transformation rates at the intermediate stage with bainite volume fraction ranging from around 0.1 to 0.6.The improved impact toughness of the Co-bearing steel results from the higher dense block boundaries dominated by the V1/V2 variant pair.Furthermore,the addition of Co induces a larger transformation driving force and a lower bainite start temperature(BS),thereby contributing to the refinement of blocks and the increase of the V1/V2 variant pair.These findings would be instructive for the composition,microstructure design,and property optimization of high-strength steels.展开更多
In the process of electroless cobalt plating,the saccharin additive can significantly change the surface morphology,texture orientation,and conductivity of the cobalt coating layer.When the amount of saccharin was 3 m...In the process of electroless cobalt plating,the saccharin additive can significantly change the surface morphology,texture orientation,and conductivity of the cobalt coating layer.When the amount of saccharin was 3 mg·L^(-1),the cobalt coating transformed from disordered large grains to a honeycomb structure,with a preferred orientation of(002)facet on hexago-nal close-packed(HCP)cobalt crystals.The resistivity of the cobalt film decreased to 14.4μΩ·cm,and further decreased to 10.7μΩ·cm after the annealing treatment.When the concentration of saccharin was increased,the grain size was gradually refined and a“stone forest”structure was observed,with the preferred orientation remaining unchanged.The addition of saccharin also slightly improves the purity of cobalt coating to a certain extent.Through the study of the crystallization behavior of cobalt electroless plating,saccharin molecules can adsorb to specific c-sites on the cobalt dense crystal plane,inhibiting the growth of abc stacking arrangement and inducing the crystal growth in ab stacking mode,thereby achieving optimal growth of HCP(002)texture.展开更多
A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal st...A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.展开更多
The reduction smelting process for cobalt recovery from converter slag of the Chambishi Copper Smelter in Zambia was studied. The effects of reducing agent dosage, smelting temperature and time and the addition of sla...The reduction smelting process for cobalt recovery from converter slag of the Chambishi Copper Smelter in Zambia was studied. The effects of reducing agent dosage, smelting temperature and time and the addition of slag modifiers （CaO and TiO2） were investigated. In addition, the depleted slag and cobalt-bearing alloy were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Under the determined conditions, 94.02% Co, 95.76% Cu and less than 18% Fe in the converter slag were recovered. It was found that the main phases of depleted slag were fayalite and hercynite; and the cobalt-bearing alloy mainly contained metallic copper, Fe-Co-Cu alloys and a small amount of sulfide.展开更多
In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.The...In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions.Herein,we report a cobalt-catalyzed migratory carboncarbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl-and alkyl-functionalized cyclooctenes.Preliminary mechanistic studies suggest the oxidation-induced cisbicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction,which promotes the development of other diverse migratory cross-coupling of borate complexes.展开更多
pH-dependent multiple equilibria in cobalt sulfate-gluconate baths were calculated using stability constants adopted from literature.Changes of the bath speciation were then discussed in terms of spectrophotometric ex...pH-dependent multiple equilibria in cobalt sulfate-gluconate baths were calculated using stability constants adopted from literature.Changes of the bath speciation were then discussed in terms of spectrophotometric experiments and buffering properties of the solutions(pH 3-10).Cyclic voltammetry indicated changes in electrochemical behavior of cobalt species caused by different ionic compositions of the electrolytes.Tafel slopes were calculated and discussed in relation to electroreduction of cobalt species.Chronoamperometric studies showed 3D instantaneous nucleation of cobalt followed by diffusion-controlled growth,but it was disturbed at higher pH due to the release of cation from gluconate complexes as a limiting step.Diffusion coefficients of cobalt species were found.Changes in the pH were also reflected by modifications of morphology(SEM),development of preferred orientation planes(XRD,texture coefficients)and current efficiency,but not the thickness of the coatings deposited at constant potential of-1.0 V(vs Ag/AgCl).Anodic stripping analysis showed changes in anodic responses originated from the existence of preferentially oriented planes in cobalt layers.展开更多
The asymmetric addition of aromatic organometallic compounds to the carbonyl group(C-3)of isatins,catalyzed by transition metals,has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindo...The asymmetric addition of aromatic organometallic compounds to the carbonyl group(C-3)of isatins,catalyzed by transition metals,has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles.Here,an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides(both aryl and heteroaryl).Utilizing chiral cobalt complexes as catalysts,and the presence of a diboron reagent B_(2)nep_(2)as both a reducing agent and determinant in enantiocontrol,has resulted in the triumphantly achieved synthesis of enantioenriched products.Compared to reported strategies,this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups,such as halides and borate esters,while also eliminating the need for organometallic reagents as required in previous strategies.Through experimental investigations,the presence of aryl-cobalt species during the addition process was confirmed,rather than in-situ generation of an arylboron reagent.Furthermore,the successful attainment of the R absolute configuration through aryl addition was demonstrated.展开更多
The origin of the misorientations after fcc(face-centered cubic)to hcp(hexagonal close-packed)transformation in pure cobalt was elucidated by utilizing the electron backscatter diffraction(EBSD)technique and transform...The origin of the misorientations after fcc(face-centered cubic)to hcp(hexagonal close-packed)transformation in pure cobalt was elucidated by utilizing the electron backscatter diffraction(EBSD)technique and transformation crystallographic models.It is found the Shoji−Nishiyama orientation relationship during fcc→hcp transformation leads to four hcp variants,characterized by a common misorientation angle of 70.5°with respect to the<1120>direction,which is the predominant misorientation observed.Other statistically significant misorientation angles between hcp grains,including 32°,36°,38°,60°,71°and 86°−91°,are also identified.These newly observed misorientation angles are linked to the microstructure of the fcc matrix at elevated temperatures,with twin structures in the fcc matrix being the primary cause.Furthermore,a novel method is proposed for estimating the fraction of twins in the fcc grains based on misorientation angles between hcp variants,which is found to be consistent with experimental observations.In-situ EBSD observations validate the possible origin of fcc twins from the hcp→fcc transformation.展开更多
Propane dehydrogenation(PDH)has emerged as a key on-purpose technology for the production of propylene,but it often depends on toxic chromium and expensive platinum catalysts,highlighting the need for environmentally ...Propane dehydrogenation(PDH)has emerged as a key on-purpose technology for the production of propylene,but it often depends on toxic chromium and expensive platinum catalysts,highlighting the need for environmentally friendly and cost-effective alternatives.In this study,we developed a facile impregnation method to fabricate unsaturated Co single-atoms with a tricoordinated Co_(1)O_(3)H_(x) structure by regulating silanol nests in purely siliceous Beta zeolites.Detailed PDH catalytic tests and characterizations revealed a positive correlation between the presence of silanol nests and enhanced catalytic activity.Additionally,the unsaturated Co single-atoms exhibited a carbon deposition rate more than an order of magnitude slower than that of Co nanoparticles.Notably,the optimized Co_(0.3%)/deAl-meso-Beta catalyst achieved a record-high propylene formation rate of 21.2 mmol_(C3H6) g_(cat)^(-1) h^(-1),with an exceptional propylene selectivity of 99.1%at 550℃.Moreover,the Co_(0.3%)/deAl-meso-Beta catalyst demonstrated excellent stability,with negligible deactivation after 5 consecutive regeneration cycles.This study emphasizes the pivotal role of silanol nests of zeolites in stabilizing and modulating the coordination environment of metallic active sites,providing valuable insights for the design of high-activity,high-stability,and low-cost PDH catalysts.展开更多
Cobalt sulfide has received widespread attention in the advanced oxidation treatment of wastewater,and its catalytic activity is infiuenced by crystal structure and exposed active sites.This work successfully construc...Cobalt sulfide has received widespread attention in the advanced oxidation treatment of wastewater,and its catalytic activity is infiuenced by crystal structure and exposed active sites.This work successfully constructed three types of cobalt sulfides,namely Co_(9)S_(8),Co_(3)S_(4)and CoS_(2),by changing the molar ratio of cobalt to sulfur.The results showed that the degradation efficiency of Co_(9)S_(8),Co_(3)S_(4)and CoS_(2)on chloroxylenol by activated peroxomonosulfate(PMS)were 100%,88.70%and 67.73%,respectively.Combined with density functional theory(DFT),the structural properties and reaction energy barriers of different cobaltsulfur ratios were calculated.As the ratio of cobalt to sulfur increases,the sulfur vacancies realized a fuller exposure of active sites(Co_(surf.)^(2+))on the surface of the catalysts,with a highly linear relationship with the reaction rate constant(R^(2)=0.945).This work explores the structure-activity relationship between cobalt sulfur ratio and degradation efficiency,which can guide new catalyst synthesis.展开更多
An efficient catalytic system was developed to remove various organic pollutants by simultaneously using low-level cobalt ions,calcium carbonate micro-particles and peroxymonosulfate(PMS).A simple base-induced precipi...An efficient catalytic system was developed to remove various organic pollutants by simultaneously using low-level cobalt ions,calcium carbonate micro-particles and peroxymonosulfate(PMS).A simple base-induced precipitation was used to successfully loaded Co-centered reactive sites onto the surface of CaCO_(3)microparticles.Under optimal conditions at 25°C,10 mg/L methylene blue(MB)could be completely degraded within 10 min with 480μg/L Co^(2+),0.4 g/L CaCO_(3)microparticles(or 0.4 g/L Co@CaCO_(3))and 0.1 g/L PMS.The MB degradation followed the pseudo first order kinetics with a rate constant of 0.583 min^(−1),being 8.3,11.5 and 53.0 times that by using Co-OH(0.07 min^(−1)),Co^(2+)(0.044 min^(−1))and CaCO_(3)(0.011 min^(−1))as the catalyst,respectively.It was confirmed that there was a synergistic effect in the catalytic activity between Co species and the CaCO_(3)particles but the major contributor was the highly dispersed Co species.When Co^(2+)-containing simulated electroplating wastewater was used as the Co^(2+)source,not only the added MB was also completely degraded within 5 min in this catalytic system,but also the coexisting heavy metal ions were substantially removed.The presently developed method was applied to simultaneously treat organic wastewater and heavy metals wastewater.The present method was also successfully used to efficiently degrade other organic pollutants including bisphenol A,sulfamethoxazole,rhodamine B,tetrabromobisphenol A,ofloxacin and benzoic acid.A catalytic mechanism was proposed for the PMS activation by Co@CaCO_(3).The surface of CaCO_(3)particles favors the adsorption of Co^(2+).More importantly,the surface of CaCO_(3)particles provides plentiful surface-OH and-CO_(3)^(2+),and these surface groups complex with Co^(2+)to producemore catalytically active species such as surface[CoOH]^(−),resulting in rapid Co^(2+)/Co^(3+)cycling and electron transfer.These interactions cause the observed synergistic effect between Co species and CaCO_(3)particles in PMS activation.Due to good cycle stability,strong anti-interference ability and wide universality,the new method will have broad application prospects.展开更多
The Kitaev honeycomb model has received significant attention due to its exactly solvable quantum spin liquid ground states and fractionalized excitations.Layered cobalt oxides have been considered as a promising plat...The Kitaev honeycomb model has received significant attention due to its exactly solvable quantum spin liquid ground states and fractionalized excitations.Layered cobalt oxides have been considered as a promising platform for realizing this model.However,in contrast to the conventional wisdom regarding the single-q zigzag magnetic order inferred from previous studies of the candidate materials Na_(2)IrO_(3) and α-RuCl_(3),recent experiments on two representative honeycomb cobalt oxides,hexagonal Na_(2)Co_(2)TeO_(6) and monoclinic Na_(3)Co_(2)SbO_(6),have uncovered evidence for more complex multi-q zigzag order variants.This review surveys the experimental strategies used to distinguish between single-and multi-q orders,along with the crystallographic symmetries of cobalt oxides,in comparison with previously studied systems.The general formation mechanism of multi-q order is also briefly discussed.The goal is to provide a solid ground for examining the relevance of multi-q order in honeycomb cobalt oxides and discuss its implications for the microscopic model of these intriguing quantum magnets.展开更多
Simultaneous recovery of Ni and Co from Fe(Ⅲ)and AI is a critical challenge in hydrometallurgical processes.Recognized solvent extraction systems often struggle with selectivity and effective performance in mixed met...Simultaneous recovery of Ni and Co from Fe(Ⅲ)and AI is a critical challenge in hydrometallurgical processes.Recognized solvent extraction systems often struggle with selectivity and effective performance in mixed metal ion environments.Herein,a new synergistic solvent extraction(SSX)system comprised of a novel pyridine analog,N,N-bis(pyridin-2-ylmethyl)dodecan-1-amine(BPMDA),and dinonylnaphthalene sulfonic acid(DNNSA)with tributyl phosphate as phase modifier is introduced.The SSX system demonstrates high extraction performance achieving>90%for Ni and>97%for Co in a singlestage extraction process,with high selectivity.Under optimal conditions,the selectivity sequence is observed as Co^(2+)(>97%)>Ni^(2+)(>90%)>Mn^(2+)(<20%)>Fe^(3+)(<10%)>Mg^(2+)(<5%)>Al^(3+)(<2%)>Ca^(2+)(<1%).Spectroscopic analysis evidences the preferential binding of BPMDA with Ni and Co in the presence of DNNSA,concurrently achieving a significant reduction in the co-extraction of Fe(Ⅲ)and Al.The selective complexation of Ni and Co using the SSX system offers a highly efficient and selective approach for their extraction,with promising potential for applications in recovery-based processes.展开更多
The dehydrogenation of alkanes has emerged as a vital complementary process to address the increasing global demand for olefins.A key challenge remains in the construction of novel active centers that offer superior a...The dehydrogenation of alkanes has emerged as a vital complementary process to address the increasing global demand for olefins.A key challenge remains in the construction of novel active centers that offer superior activity,stability,and cost-effectiveness.Herein,tricoordinated cobalt atoms were successfully fabricated through an in-situ ligand-protected synthesis by introducing tungsten atoms into zeolite frameworks.These unsaturated Co species efficiently activate C-H bonds while suppressing C-C bond cleavage,resulting in exceptional catalytic activity and olefin selectivity in both propane and ethane dehydrogenation reactions.The optimized Co_(0.2%)@0.01W-S-1 catalyst demonstrated an impressive propylene formation rate of 15.2 molC_(3H6)gcC h^(-1)at 823 K and an ethylene formation rate of 240.3mol_(C2H4)g_(Co)^(-1)h^(-1)at 913 K,with propylene and ethylene selectivities of 99.0%and 97.5%,respectively.These results not only significantly surpass conventional tetracoordinated Co catalysts but also rival some Pt-based catalysts under similar conditions.Importantly,the catalyst exhibited excellent stability in dehydrogenation reactions,with no significant loss in catalytic activity after five consecutive regeneration cycles.This work offers valuable insights into the design of zeolite-supported non-precious metal catalysts with high activity and durability for efficient alkane dehydrogenation.展开更多
The oxygen evolution reaction(OER)is regarded as the bottleneck of electrolytic water splitting.Thus,developing robust earth-abundant electrocatalysts for efficient OER has received a great deal of attention and it is...The oxygen evolution reaction(OER)is regarded as the bottleneck of electrolytic water splitting.Thus,developing robust earth-abundant electrocatalysts for efficient OER has received a great deal of attention and it is an ongoing scientific challenge.Herein,hierarchical hollow nanorods assembled with ultrathin mesoporous cobalt silicate hydroxide nanosheets(denoted as CoSi)were successfully fabricated,using the silica nanotube derived from halloysite as a sacrificial template,via a simple hydrothermal method.The resulting cobalt silicate hydroxide nanosheets stack with thicknesses∼10 nm,as confirmed by transmis-sion electron microscopy.The elaborated nanoarchitecture possesses a high specific surface area(SSA)al-lowing good exposure to the cobalt active centers exhibiting superior catalytic activity vs analogs synthe-sized using sodium silicate.Among all as-prepared CoSi samples,those synthesized at 150℃(CoSi-150)exhibited the minimum overpotential of∼347 mV at a current density of 10 mA cm^(-2).In addition,CoSi-150 also exhibited superior performance against typical cobalt-based catalysts,and its surface hydroxyl groups were beneficial for the enhancement of OER performance.Furthermore,the CoSi-150 showed ex-cellent durability and stability after the 105 s chronopotentiometry test in 1 M KOH.This design concept provides a new strategy for the low-cost preparation of high-quality cobalt water splitting electrocata-lysts.展开更多
文摘Polyhydroxyalkanoate(PHA),a well-known biodegradable polymer,featuresβ-lactones as its monomers,which can be selectively synthesized through ring-expansion carbonylation of epoxides using well-defined[Lewis acid]^(+)[Co(CO)_(4)]^(-)catalysts.However,the decomposition of[Co(CO)_(4)]^(-)species at temperatures exceeding 80℃presents a hurdle for the development of commercially viable processes under high-temperature reaction conditions to reduce reaction time.Drawing insights from stable{(acyl)Co(CO)n}intermediates involved in historical HCo(CO)_(4)-catalyzed hydroformylation processes,we sought to the high-temperature catalytic activity of epoxide ring-expansion carbonylation.The developed catalyst system,[(acetyl)Co(CO)_(2)dppp]and[(TPP)CrCl],exhibited exceptional catalytic performance with an unprecedented initial turnover frequency of 4700 h^(-1)at 100℃and a turnover numbers of 93000.Notably,the catalyst displayed outstanding stability,operating at 80℃for 168 h while selectively generatingβ-lactones.
基金the financial support of Guangxi Science and Technology Major Project(Guike AA22068078)the Natural Science Foundation of Henan Province(No.222300420548)+2 种基金Henan Province Science and Technology Research and Development plan joint Fund(No.232301420043)the Key Project of the National Key Research and Development Program of China(No.2021YFC2902604)Modern Analysis and Computing Centre in Zhengzhou University。
文摘Cobalt has excellent electrochemical,magnetic,and heat properties.As a strategic resource,it has been applied in many hightech products.However,the recent rapid growth of the battery industry has substantially depleted cobalt resources,leading to a crisis of cobalt resource supply.The paper examines cobalt ore reserves and distribution,and the recent development and consumption of cobalt resources are summarized as well.In addition,the principles,advantages and disadvantages,and research status of various methods are discussed comprehensively.It can be concluded that the use of diverse sources(Cu-Co ores,Ni-Co ores,zinc plant residues,and waste cobalt products)for cobalt production should be enhanced to meet developmental requirements.Furthermore,in recovery technology,the pyro-hydrometallurgical process employs pyrometallurgy as the pretreatment to modify the phase structure of cobalt minerals,enhancing its recovery in the hydrometallurgical stage and facilitating high-purity cobalt production.Consequently,it represents a promising technology for future cobalt recovery.Lastly,based on the above conclusions,the prospects for cobalt are assessed regarding cobalt ore processing and sustainable cobalt recycling,for which further study should be conducted.
基金National Natural Science Foundation of China (Nos. 42276035, 22309030)Guangdong Basic and Applied Basic Research Foundation (Nos. 2023A1515012589,2020A1515110473)Key Plat Form Programs and Technology Innovation Team Project of Guangdong Provincial Department of Education (Nos. 2019GCZX002, 2020KCXTD011)。
文摘Seawater electrolysis is a promising approach for sustainable energy without relying on precious freshwater.However,the large-scale seawater electrolysis is hindered by low catalytic efficiency and severe anode corrosion caused by the harmful chlorine.In contrast to the oxygen evolution reaction (OER)and chlorin ion oxidation reaction (ClOR),glycerol oxidation reaction (GOR) is more thermodynamically and kinetically favorable alternative.Herein,a Ru doping cobalt phosphide (Ru-CoP_(2)) is proposed as a robust bifunctional electrocatalyst for seawater electrolysis and GOR,for the concurrent productions of hydrogen and value-added formate.The in situ and ex situ characterization analyses demonstrated that Ru doping featured in the dynamic reconstruction process from Ru-CoP_(2)to Ru-CoOOH,accounting for the superior GOR performance.Further coupling GOR with hydrogen evolution was realized by employing Ru-CoP_(2)as both anode and cathode,requiring only a low voltage of 1.43 V at 100 mA cm^(-2),which was 250 m V lower than that in alkaline seawater.This work guides the design of bifunctional electrocatalysts for energy-efficient seawater electrolysis coupled with biomass resource upcycling.
基金National Key Research and Development Program of China(No.2020YFC1909202)Major Science and Technology Program of Yunnan Province,China(No.202202AB080012)for financial support。
文摘Copper and cobalt were recovered from SICOMINES mining waste rock in the Democratic Republic of Congo.The process mineralogy of the samples was analyzed using scanning electron microscopy and energy dispersive spectroscopy.The results showed that copper minerals exhibited various forms and uneven particle sizes,while cobalt existed in the form of highly dispersed asbolane,and large amounts of easily slimed gangue minerals were filled in the samples,making it difficult to separate copper and cobalt minerals.The particle size range plays a decisive role in selecting the separation method for the copper−cobalt ore.Gravity separation was suitable for particles ranging from 43 to 246μm,while flotation was more effective for particles below 43μm.After ore grinding and particle size classification,applying a combined gravity separation(shaking table)−flotation method yielded concentrated minerals with a copper recovery of 72.83%and a cobalt recovery of 31.13%.
基金supported by National Natural Science Foundation of China(Nos.52472194,52101243)Natural Science Foundation of Guangdong Province,China(No.2023A1515012619)the Science and Technology Planning Project of Guangzhou(No.202201010565)。
文摘In recent years,metal phosphosulfides have attracted great attention as the promising anode materials in sodium/potassium batteries because of their incorporation of the advantages of metal phosphides and sulfides.However,they are also confronted with the problem of unstable battery performance due to the heavy volume expansion and sluggish ion reaction kinetics.Herein,yolk-shell cobalt phosphosulfide nanocrystals encapsulating into multi-heterogeneous atom(N,P,S)-doped carbon framework(Co_(9)S_(8)/CoP@NPSC)were constructed by employing dodecahedral ZIF-67 as precursor and a polymer as carbon sources through simultaneous sulfidation and phosphorization processes.The synergistic effect of Co_(9)S_(8)and CoP component and the yolk-shell structure greatly improve the bettery performance and structural stability.In addition,the multiple hetero-atoms doped carbon frameworks enhance the conductivity of the electrode materials and increase the spacing of carbon layers to supply sufficient active sites and facilitate the Na^(+)/K^(+)transport.The electrochemical results demonstrated that Co_(9)S_(8)/CoP@NPSC exhibited the pleasant reversible capacity(360.47 mAh/g at 1 A/g)after 300 cycles and an unpredictable cycling stability(103.22 mAh/g after 1000 cycles)in the SIBs application.The ex-situ XRD and XPS analyses were further applied to study the sodium ion storage mechanism and the multi-step phase transition reaction of the yolk-shell heterogeneous structure.This work provides new perspectives for the preparation of novel structure metal phosphosulfide and their applications in anode materials for sodium/potassium batteries and other secondary batteries.
基金supported by the National Natural Science Foundation of China(No.52271089)the financial support from the C hina Postdoctoral Science Foundation(No.2023M732192)。
文摘This work reveals the significant effects of cobalt(Co)on the microstructure and impact toughness of as-quenched highstrength steels by experimental characterizations and thermo-kinetic analyses.The results show that the Co-bearing steel exhibits finer blocks and a lower ductile-brittle transition temperature than the steel without Co.Moreover,the Co-bearing steel reveals higher transformation rates at the intermediate stage with bainite volume fraction ranging from around 0.1 to 0.6.The improved impact toughness of the Co-bearing steel results from the higher dense block boundaries dominated by the V1/V2 variant pair.Furthermore,the addition of Co induces a larger transformation driving force and a lower bainite start temperature(BS),thereby contributing to the refinement of blocks and the increase of the V1/V2 variant pair.These findings would be instructive for the composition,microstructure design,and property optimization of high-strength steels.
基金supported by National Natural Science Foundation of China(22402115,22472094)Shaanxi Special Fund for Talent Introduction(100090/1204071055).
文摘In the process of electroless cobalt plating,the saccharin additive can significantly change the surface morphology,texture orientation,and conductivity of the cobalt coating layer.When the amount of saccharin was 3 mg·L^(-1),the cobalt coating transformed from disordered large grains to a honeycomb structure,with a preferred orientation of(002)facet on hexago-nal close-packed(HCP)cobalt crystals.The resistivity of the cobalt film decreased to 14.4μΩ·cm,and further decreased to 10.7μΩ·cm after the annealing treatment.When the concentration of saccharin was increased,the grain size was gradually refined and a“stone forest”structure was observed,with the preferred orientation remaining unchanged.The addition of saccharin also slightly improves the purity of cobalt coating to a certain extent.Through the study of the crystallization behavior of cobalt electroless plating,saccharin molecules can adsorb to specific c-sites on the cobalt dense crystal plane,inhibiting the growth of abc stacking arrangement and inducing the crystal growth in ab stacking mode,thereby achieving optimal growth of HCP(002)texture.
文摘A low-cost 1D cobalt-based coordination polymer(CP)[Co(BGPD)(DMSO)_(2)(H_(2)O)_(2)](Co-BD;H2BGPD=N,N'-bis(glycinyl)pyromellitic diimide;DMSO=dimethyl sulfoxide)was synthesized by a simple method,and its crystal structure was characterized.In a three-electrode system,Co-BD,as the electrode material for supercapacitors,achieved a specific capacitance of 830 F·g^(-1)at 1 A·g^(-1),equivalent to a specific capacity of 116.4 mAh·g^(-1),and exhibited high-rate capability,reaching 212 F·g^(-1)at 20 A·g^(-1).Impressively,Co-BD||rGO(reduced graphene oxide),representing an asymmetrical supercapacitor,owns a higher energy density of 14.2 Wh·kg^(-1)at 0.80 kW·kg^(-1),and an excellent cycle performance(After 4000 cycles at 1 A·g^(-1),the capacitance retention was up to 94%).CCDC:2418872.
基金Project(2008BAB34B01-1)supported by the National Key Technology R&D Program of China
文摘The reduction smelting process for cobalt recovery from converter slag of the Chambishi Copper Smelter in Zambia was studied. The effects of reducing agent dosage, smelting temperature and time and the addition of slag modifiers （CaO and TiO2） were investigated. In addition, the depleted slag and cobalt-bearing alloy were characterized by X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy. Under the determined conditions, 94.02% Co, 95.76% Cu and less than 18% Fe in the converter slag were recovered. It was found that the main phases of depleted slag were fayalite and hercynite; and the cobalt-bearing alloy mainly contained metallic copper, Fe-Co-Cu alloys and a small amount of sulfide.
基金supported by the National Natural Science Foundation of China(No.22171046)the Hundred-Talent Project of Fujian(No.50021113)Fuzhou University(No.0480-00489503)。
文摘In most Suzuki–Miyaura carbon-carbon cross-coupling reactions,the borabicyclo[3.3.1]nonane scaffold(9-BBN)only serves as an auxiliary facilitating the transmetalation step and thus is transformed into by-products.There are rare examples where the 9-BBN derivatives serve as the potentially diverse C8 building blocks in cross-coupling reactions.Herein,we report a cobalt-catalyzed migratory carboncarbon cross-coupling reaction of the in situ formed 9-BBN ate complexes to afford diverse aryl-and alkyl-functionalized cyclooctenes.Preliminary mechanistic studies suggest the oxidation-induced cisbicyclo[3.3.0]oct-1-ylborane is the key intermediate in this migratory cross-coupling reaction,which promotes the development of other diverse migratory cross-coupling of borate complexes.
文摘pH-dependent multiple equilibria in cobalt sulfate-gluconate baths were calculated using stability constants adopted from literature.Changes of the bath speciation were then discussed in terms of spectrophotometric experiments and buffering properties of the solutions(pH 3-10).Cyclic voltammetry indicated changes in electrochemical behavior of cobalt species caused by different ionic compositions of the electrolytes.Tafel slopes were calculated and discussed in relation to electroreduction of cobalt species.Chronoamperometric studies showed 3D instantaneous nucleation of cobalt followed by diffusion-controlled growth,but it was disturbed at higher pH due to the release of cation from gluconate complexes as a limiting step.Diffusion coefficients of cobalt species were found.Changes in the pH were also reflected by modifications of morphology(SEM),development of preferred orientation planes(XRD,texture coefficients)and current efficiency,but not the thickness of the coatings deposited at constant potential of-1.0 V(vs Ag/AgCl).Anodic stripping analysis showed changes in anodic responses originated from the existence of preferentially oriented planes in cobalt layers.
基金the National Key R&D Program of China(No.2022YFA1503200)the National Natural Science Foundation of China(Nos.22025104,22171134,and 21972064)the Fundamental Research Funds for the Central Universities(No.020514380254)is greatly appreciated.
文摘The asymmetric addition of aromatic organometallic compounds to the carbonyl group(C-3)of isatins,catalyzed by transition metals,has emerged as a remarkably efficient method for the synthesis of chiral 3-hydroxyoxindoles.Here,an exceptionally enantioselective approach was developed for the first time to achieve a catalytic NHK reaction of isatins with aromatic halides(both aryl and heteroaryl).Utilizing chiral cobalt complexes as catalysts,and the presence of a diboron reagent B_(2)nep_(2)as both a reducing agent and determinant in enantiocontrol,has resulted in the triumphantly achieved synthesis of enantioenriched products.Compared to reported strategies,this approach exhibits remarkable compatibility with substrates bearing sensitive functional groups,such as halides and borate esters,while also eliminating the need for organometallic reagents as required in previous strategies.Through experimental investigations,the presence of aryl-cobalt species during the addition process was confirmed,rather than in-situ generation of an arylboron reagent.Furthermore,the successful attainment of the R absolute configuration through aryl addition was demonstrated.
基金supported by the National Key R&D Program of China(No.2022YFB3504403).
文摘The origin of the misorientations after fcc(face-centered cubic)to hcp(hexagonal close-packed)transformation in pure cobalt was elucidated by utilizing the electron backscatter diffraction(EBSD)technique and transformation crystallographic models.It is found the Shoji−Nishiyama orientation relationship during fcc→hcp transformation leads to four hcp variants,characterized by a common misorientation angle of 70.5°with respect to the<1120>direction,which is the predominant misorientation observed.Other statistically significant misorientation angles between hcp grains,including 32°,36°,38°,60°,71°and 86°−91°,are also identified.These newly observed misorientation angles are linked to the microstructure of the fcc matrix at elevated temperatures,with twin structures in the fcc matrix being the primary cause.Furthermore,a novel method is proposed for estimating the fraction of twins in the fcc grains based on misorientation angles between hcp variants,which is found to be consistent with experimental observations.In-situ EBSD observations validate the possible origin of fcc twins from the hcp→fcc transformation.
文摘Propane dehydrogenation(PDH)has emerged as a key on-purpose technology for the production of propylene,but it often depends on toxic chromium and expensive platinum catalysts,highlighting the need for environmentally friendly and cost-effective alternatives.In this study,we developed a facile impregnation method to fabricate unsaturated Co single-atoms with a tricoordinated Co_(1)O_(3)H_(x) structure by regulating silanol nests in purely siliceous Beta zeolites.Detailed PDH catalytic tests and characterizations revealed a positive correlation between the presence of silanol nests and enhanced catalytic activity.Additionally,the unsaturated Co single-atoms exhibited a carbon deposition rate more than an order of magnitude slower than that of Co nanoparticles.Notably,the optimized Co_(0.3%)/deAl-meso-Beta catalyst achieved a record-high propylene formation rate of 21.2 mmol_(C3H6) g_(cat)^(-1) h^(-1),with an exceptional propylene selectivity of 99.1%at 550℃.Moreover,the Co_(0.3%)/deAl-meso-Beta catalyst demonstrated excellent stability,with negligible deactivation after 5 consecutive regeneration cycles.This study emphasizes the pivotal role of silanol nests of zeolites in stabilizing and modulating the coordination environment of metallic active sites,providing valuable insights for the design of high-activity,high-stability,and low-cost PDH catalysts.
基金supported by the National Natural Science Foundation of China(No.52370168)the Program of Shanghai Outstanding Technology Leaders(No.20XD1433900)。
文摘Cobalt sulfide has received widespread attention in the advanced oxidation treatment of wastewater,and its catalytic activity is infiuenced by crystal structure and exposed active sites.This work successfully constructed three types of cobalt sulfides,namely Co_(9)S_(8),Co_(3)S_(4)and CoS_(2),by changing the molar ratio of cobalt to sulfur.The results showed that the degradation efficiency of Co_(9)S_(8),Co_(3)S_(4)and CoS_(2)on chloroxylenol by activated peroxomonosulfate(PMS)were 100%,88.70%and 67.73%,respectively.Combined with density functional theory(DFT),the structural properties and reaction energy barriers of different cobaltsulfur ratios were calculated.As the ratio of cobalt to sulfur increases,the sulfur vacancies realized a fuller exposure of active sites(Co_(surf.)^(2+))on the surface of the catalysts,with a highly linear relationship with the reaction rate constant(R^(2)=0.945).This work explores the structure-activity relationship between cobalt sulfur ratio and degradation efficiency,which can guide new catalyst synthesis.
基金supported by the National Natural Science Foundation of China(Nos.22076052 and 21976063)China Postdoctoral Science Foundation(No.2018M642850)the Research Funding of Wuhan Polytechnic University(No.2023RZ017).
文摘An efficient catalytic system was developed to remove various organic pollutants by simultaneously using low-level cobalt ions,calcium carbonate micro-particles and peroxymonosulfate(PMS).A simple base-induced precipitation was used to successfully loaded Co-centered reactive sites onto the surface of CaCO_(3)microparticles.Under optimal conditions at 25°C,10 mg/L methylene blue(MB)could be completely degraded within 10 min with 480μg/L Co^(2+),0.4 g/L CaCO_(3)microparticles(or 0.4 g/L Co@CaCO_(3))and 0.1 g/L PMS.The MB degradation followed the pseudo first order kinetics with a rate constant of 0.583 min^(−1),being 8.3,11.5 and 53.0 times that by using Co-OH(0.07 min^(−1)),Co^(2+)(0.044 min^(−1))and CaCO_(3)(0.011 min^(−1))as the catalyst,respectively.It was confirmed that there was a synergistic effect in the catalytic activity between Co species and the CaCO_(3)particles but the major contributor was the highly dispersed Co species.When Co^(2+)-containing simulated electroplating wastewater was used as the Co^(2+)source,not only the added MB was also completely degraded within 5 min in this catalytic system,but also the coexisting heavy metal ions were substantially removed.The presently developed method was applied to simultaneously treat organic wastewater and heavy metals wastewater.The present method was also successfully used to efficiently degrade other organic pollutants including bisphenol A,sulfamethoxazole,rhodamine B,tetrabromobisphenol A,ofloxacin and benzoic acid.A catalytic mechanism was proposed for the PMS activation by Co@CaCO_(3).The surface of CaCO_(3)particles favors the adsorption of Co^(2+).More importantly,the surface of CaCO_(3)particles provides plentiful surface-OH and-CO_(3)^(2+),and these surface groups complex with Co^(2+)to producemore catalytically active species such as surface[CoOH]^(−),resulting in rapid Co^(2+)/Co^(3+)cycling and electron transfer.These interactions cause the observed synergistic effect between Co species and CaCO_(3)particles in PMS activation.Due to good cycle stability,strong anti-interference ability and wide universality,the new method will have broad application prospects.
基金supported by the National Basic Research Program of China(Grant No.2021YFA1401901)the National Natural Science Foundation of China(Grant No.12474138)。
文摘The Kitaev honeycomb model has received significant attention due to its exactly solvable quantum spin liquid ground states and fractionalized excitations.Layered cobalt oxides have been considered as a promising platform for realizing this model.However,in contrast to the conventional wisdom regarding the single-q zigzag magnetic order inferred from previous studies of the candidate materials Na_(2)IrO_(3) and α-RuCl_(3),recent experiments on two representative honeycomb cobalt oxides,hexagonal Na_(2)Co_(2)TeO_(6) and monoclinic Na_(3)Co_(2)SbO_(6),have uncovered evidence for more complex multi-q zigzag order variants.This review surveys the experimental strategies used to distinguish between single-and multi-q orders,along with the crystallographic symmetries of cobalt oxides,in comparison with previously studied systems.The general formation mechanism of multi-q order is also briefly discussed.The goal is to provide a solid ground for examining the relevance of multi-q order in honeycomb cobalt oxides and discuss its implications for the microscopic model of these intriguing quantum magnets.
基金supported by the National Natural Science Foundation of China(22278407,22001147,21922814,22138012,22178349)CAS Project for Young Scientists in Basic Research(YSBR-038)+2 种基金the Ministry of Science and Technology of China(2021YFC2901500)Excellent Member in Youth Innovation Promotion Association,Chinese Academy of Sciences(Y202014)Shandong Energy Institute(SEI U202306).
文摘Simultaneous recovery of Ni and Co from Fe(Ⅲ)and AI is a critical challenge in hydrometallurgical processes.Recognized solvent extraction systems often struggle with selectivity and effective performance in mixed metal ion environments.Herein,a new synergistic solvent extraction(SSX)system comprised of a novel pyridine analog,N,N-bis(pyridin-2-ylmethyl)dodecan-1-amine(BPMDA),and dinonylnaphthalene sulfonic acid(DNNSA)with tributyl phosphate as phase modifier is introduced.The SSX system demonstrates high extraction performance achieving>90%for Ni and>97%for Co in a singlestage extraction process,with high selectivity.Under optimal conditions,the selectivity sequence is observed as Co^(2+)(>97%)>Ni^(2+)(>90%)>Mn^(2+)(<20%)>Fe^(3+)(<10%)>Mg^(2+)(<5%)>Al^(3+)(<2%)>Ca^(2+)(<1%).Spectroscopic analysis evidences the preferential binding of BPMDA with Ni and Co in the presence of DNNSA,concurrently achieving a significant reduction in the co-extraction of Fe(Ⅲ)and Al.The selective complexation of Ni and Co using the SSX system offers a highly efficient and selective approach for their extraction,with promising potential for applications in recovery-based processes.
基金supported by the National Key R&D Program of China(Grant No.2022YFA1506000)Gusu Innovation and Entrepreneurship Leading Talents Program(ZXL2022497)+5 种基金Jiangsu Distinguished Professor programfinancial support by National Natural Science Foundation of China(Grant No.22301057)Natural Science Foundation of Hebei Province(Grant No.B2023201065)Science Research Project of Hebei Education Department(Grant No.BJK2024103)supported by the Open Research Fund of Shanghai Key Laboratory of High-resolution Electron MicroscopyOpen Project of State Key Laboratory of Supramolecular Structure and Materials(sklssm2024019),ShanghaiTech University。
文摘The dehydrogenation of alkanes has emerged as a vital complementary process to address the increasing global demand for olefins.A key challenge remains in the construction of novel active centers that offer superior activity,stability,and cost-effectiveness.Herein,tricoordinated cobalt atoms were successfully fabricated through an in-situ ligand-protected synthesis by introducing tungsten atoms into zeolite frameworks.These unsaturated Co species efficiently activate C-H bonds while suppressing C-C bond cleavage,resulting in exceptional catalytic activity and olefin selectivity in both propane and ethane dehydrogenation reactions.The optimized Co_(0.2%)@0.01W-S-1 catalyst demonstrated an impressive propylene formation rate of 15.2 molC_(3H6)gcC h^(-1)at 823 K and an ethylene formation rate of 240.3mol_(C2H4)g_(Co)^(-1)h^(-1)at 913 K,with propylene and ethylene selectivities of 99.0%and 97.5%,respectively.These results not only significantly surpass conventional tetracoordinated Co catalysts but also rival some Pt-based catalysts under similar conditions.Importantly,the catalyst exhibited excellent stability in dehydrogenation reactions,with no significant loss in catalytic activity after five consecutive regeneration cycles.This work offers valuable insights into the design of zeolite-supported non-precious metal catalysts with high activity and durability for efficient alkane dehydrogenation.
基金supported by the Central Government Guiding Local Science and Technology Development Fund Projects(No.236Z4108G)China Scholarship Council,the National Natu-ral Science Foundation of China(No.51874115)+2 种基金the Open Project of State Key Laboratory of Environment-friendly Energy Materials(No.22kfhg09)the Open Project of Key Laboratory of Solid Waste Treatment and Resource Recycle of Ministry of Education(No.22kfgk01)the Youth Talent Support Program of Hebei Province,the Giant Plan Innovation Team Project of Hebei Province,and the Excellent Young Scientist Foundation of Hebei province,China(No.E2018202241).
文摘The oxygen evolution reaction(OER)is regarded as the bottleneck of electrolytic water splitting.Thus,developing robust earth-abundant electrocatalysts for efficient OER has received a great deal of attention and it is an ongoing scientific challenge.Herein,hierarchical hollow nanorods assembled with ultrathin mesoporous cobalt silicate hydroxide nanosheets(denoted as CoSi)were successfully fabricated,using the silica nanotube derived from halloysite as a sacrificial template,via a simple hydrothermal method.The resulting cobalt silicate hydroxide nanosheets stack with thicknesses∼10 nm,as confirmed by transmis-sion electron microscopy.The elaborated nanoarchitecture possesses a high specific surface area(SSA)al-lowing good exposure to the cobalt active centers exhibiting superior catalytic activity vs analogs synthe-sized using sodium silicate.Among all as-prepared CoSi samples,those synthesized at 150℃(CoSi-150)exhibited the minimum overpotential of∼347 mV at a current density of 10 mA cm^(-2).In addition,CoSi-150 also exhibited superior performance against typical cobalt-based catalysts,and its surface hydroxyl groups were beneficial for the enhancement of OER performance.Furthermore,the CoSi-150 showed ex-cellent durability and stability after the 105 s chronopotentiometry test in 1 M KOH.This design concept provides a new strategy for the low-cost preparation of high-quality cobalt water splitting electrocata-lysts.
