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
A novel type of composite electrode based on nmltiwalled carbon nanotubes coated with sheet-like cobalt hydroxide particles was used in supercapacitors. Cobalt hydroxide cathodlcally deposited fiom Co（NO3）O2 solutio...A novel type of composite electrode based on nmltiwalled carbon nanotubes coated with sheet-like cobalt hydroxide particles was used in supercapacitors. Cobalt hydroxide cathodlcally deposited fiom Co（NO3）O2 solution with carbon nanotubes as matrix exhibited large pseudo-capacitance of 322 F/g in 1 mol/L KOH. To characterize the cobalt hydroxide nanocomposite electrode, a charge-discharge cycling test, cyclic voltammetry, and an impedance test were done. This cobalt hydroxide composite exhibiting excellent pseudo-capacitive behavior （i.c. high reversibility, high specific capacitance, low impedance）, was demonstrated to be a candidate for the application of electrochemical supercapacitors. A combined capacitor consisting of cobalt hydroxide composite as a cathode and activated carbon fiber as an anode was reported. The electrochemical pcrformance of the combined capacitor was characterized by cyclic voltammetry and a dc charge/discharge test. The combined capacitor showed ideal capacitor behavior with an extended operating voltage of 1.4 V. According to the extended operating voltage, the energy density of the combined capacitor at a current density of 100 mA/cm^2 was found to be 11 Wh/kg. The combined capacitor exhibited high-energy density and stable power characteristics,展开更多
Combining urea oxidation reaction(UOR) with hydrogen evolution reaction(HER) is an effective method for energy saving and highly efficient electrocatalytic hydrogen production. Herein, molybdenumincorporated cobalt ca...Combining urea oxidation reaction(UOR) with hydrogen evolution reaction(HER) is an effective method for energy saving and highly efficient electrocatalytic hydrogen production. Herein, molybdenumincorporated cobalt carbonate hydroxide nanoarrays(CoxMoyCH) are designed and synthesized as a bifunctional catalyst towards UOR and HER. Benefiting from the Mo doping, the dispersed nanoarray structure and redistributed electron density, the CoxMoyCH catalyst display outstanding catalytic performance and durability for both HER and UOR, affording the overpotential of 82 m V for HER and delivering a low potential of the 1.33 V for UOR(vs. reversible hydrogen electrode, RHE) to attain a current density of 10 m A cm^(-2), respectively. Remarkably, when CoxMoyCH was applied as bifunctional catalyst in a twoelectrode electrolyzer, a working voltage of 1.40 V is needed in urea-assisted water electrolysis at10 m A cm^(-2) and without apparent decline for 40 h, outperforming the working voltage of 1.51 V in conventional water electrolysis.展开更多
A new design route was presented to fabricate cobalt aluminum-layered double hydroxide(CoAl-LDH)thin layers whichgrow on carbon spheres(CSs)through a growth method.The CoAl-LDH thin layers consist of nanoflakes with a...A new design route was presented to fabricate cobalt aluminum-layered double hydroxide(CoAl-LDH)thin layers whichgrow on carbon spheres(CSs)through a growth method.The CoAl-LDH thin layers consist of nanoflakes with a thickness of20nm.The galvanostatic charge-discharge test of the CoAl-LDH/CSs composite shows a great specific capacitance of1198F/g at1A/g(based on the mass of the CoAl-LDH/CSs composite)in6mol/L KOH solution,and the composite displays an impressive specificcapacitance of920F/g even at a high current density of10A/g.Moreover,the composite remains a specific capacitance of928F/gafter1000cycles at2A/g,and the specific capacitance retention is84%,indicating that the composite has high specific capacitance,excellent rate capability and good cycling stability in comparison to pristine CoAl-LDH.展开更多
Two-dimensional layered double hydroxides(LDHs)have been identified as promising electrocatalysts for the oxygen evolution reaction(OER);however,the simple and effective synthesis of high-quality LDHs remains extremel...Two-dimensional layered double hydroxides(LDHs)have been identified as promising electrocatalysts for the oxygen evolution reaction(OER);however,the simple and effective synthesis of high-quality LDHs remains extremely challenging and the active sites have not been clarified.Herein,we report a facile solution-reaction method for preparing an ultrathin(thickness<2 nm)nonprecious CoFe-based LDH.Co_(1)Fe_(0.2) LDH delivers a current density of 10 mA cm^(-2) and a high turnover frequency of 0.082 s^(-1) per total 3d metal atoms at a low overpotential of 256 mV.Its mass activity is 277.9 A g^(-1) at an overpotential of 300 mV for the OER.Kinetic studies reveal the Co site as the main active center for the OER.The doped Fe lowers the reaction barrier by accelerating the charge-transfer process.Theoretical calculations reveal that the surface Co sites adjacent to Fe atoms are the active centers for the OER and the subsurface Fe dopants excessively weaken the OH^(*)adsorption,thus increasing the energy barrier of the rate-determining step.This study can guide the rational design of high-performance CoFe-based LDHs for water splitting.展开更多
Hollow microsphere structure cobalt hydroxide(h-Co(OH)2) was synthesized via an optimized solvothermal-hydrothermal process and applied to activate peroxymonosulfate(PMS) for degradation of a typical pharmaceutically ...Hollow microsphere structure cobalt hydroxide(h-Co(OH)2) was synthesized via an optimized solvothermal-hydrothermal process and applied to activate peroxymonosulfate(PMS) for degradation of a typical pharmaceutically active compound,ibuprofen(IBP).The material characterizations confirmed the presence of the microscale hollow spheres with thin nanosheets shell in h-Co(OH)2,and the crystalline phase was assigned to a-Co(OH)2.h-Co(OH)2 could efficiently activate PMS for radicals production,and 98.6% of IBP was degraded at 10 min.The activation of PMS by h-Co(OH)2 was a pHindependent process,and pH 7 was the optimum condition for the activation-degradation system.Scavenger quenching test indicated that the sulfate radical(SO4^·-) was the primary reactive oxygen species for IBP degradation,which contributed to 75.7%.Fukui index(f^-) based on density functional theory(DFT) calculation predicted the active sites of IBP molecule for SO4^·- attack,and then IBP degradation pathway was proposed by means of intermediates identification and theoretical calculation.The developed hollow Co(OH)2 used to efficiently activate PMS is promising and innovative alternative for organic contaminants removal from water and wastewater.展开更多
In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe_(2)O_(3)).The route contains two steps of the adsorption of[Co-EDTA]...In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe_(2)O_(3)).The route contains two steps of the adsorption of[Co-EDTA]^(2-)species on Fe_(2)O_(3) nanorod array followed by the hydrolysis in alkaline solution.The resulting CoOOH/Fe_(2)O_(3) exhibits a remarkably improved photocurrent density of 2.10 mA cm^(-2) at 1.23 V vs.RHE,which is ca.2.8 times that of bare Fe_(2)O_(3).In addition,a negative shift of onset potential ca.200 mV is achieved.The structural characterizations reveal the chelate EDTA plays important roles that enhance the adsorption of Co species and the formation of contact between CoOOH and Fe_(2)O_(3).(Photo)electrochemical analysis suggests,besides providing active sites for water oxidation,CoOOH at large extent promotes the charge separation and the charge transfer via passivating surface states and suppressing charge recombination.It also found CoOOH possesses some oxygen vacancies,which could act as trapping centers for photogenerated holes and facilitate the charge separation.Intensity modulated photocurrent spectroscopy(IMPS)shows that,under low applied potential the water oxidation mainly occurs on CoOOH,while under high applied potential the water oxidation could occur on both CoOOH and Fe_(2)O_(3).The findings not only provide an efficient strategy for designing ultrathin(oxy)hydroxides on semiconductors for PEC applications but also put forward a new insight on the role of CoOOH during water oxidation.展开更多
The glassy carbon (GC) electrode modified with a monolayer nickel hydroxide (GC/Ni(OH) 2) was prepared by immersion of GC substrate in 1.0×10 -3 mol/L NiSO 4 solution, and then cyclic voltammetric scannin...The glassy carbon (GC) electrode modified with a monolayer nickel hydroxide (GC/Ni(OH) 2) was prepared by immersion of GC substrate in 1.0×10 -3 mol/L NiSO 4 solution, and then cyclic voltammetric scanning in 0.20 mol/L KOH. Similarly, GC/Co(OH) 2 electrode was prepared too. The experiments showed that the voltammetric behavior of GC/Ni(OH) 2 electrode in 0.20 mol/L KOH is more stable than that of GC/ Co(OH) 2. It was found that the GC/Ni(OH) 2 electrode acts as an effective electrocatalysis for the oxidation of hydrazine.展开更多
CoSn（OH）6 nanocubes were synthesized by a facile one-step co-precipitate method. Their supercapacitor performances were investigated via a traditional threeelectrode system and all solid-state flexible asymmetric su...CoSn（OH）6 nanocubes were synthesized by a facile one-step co-precipitate method. Their supercapacitor performances were investigated via a traditional threeelectrode system and all solid-state flexible asymmetric supercapacitor. The electrode shows a maximum specific capacitance up to 695 F·g^-1. The flexible all solid-state asymmetric supercapacitor was fabricated based on CoSn（OH）6 nanocubes and active carbon as positive and negative electrode. The assembled asymmetric supercapacitor exhibits a specific capacitance（97.3 mF·cm^-2）, good rate/mechanical stability and a long cycling stability（5000 cycles）, demonstrating great promise for applications in all solid-state flexible supercapacitors.展开更多
Double-exchange(DE) interaction plays an important role in electrocatalytic oxygen evolution reaction(OER).However,precise achievement of DE interaction often requires foreign dopants or vacancy engineering,leading to...Double-exchange(DE) interaction plays an important role in electrocatalytic oxygen evolution reaction(OER).However,precise achievement of DE interaction often requires foreign dopants or vacancy engineering,leading to destabilization of the catalysts and deterioration of performance.By contrast,the utilization of environmentally friendly,contactless,and continuously adjustable magnetic fields to study the OER process is profitable to avoid aforementioned interference factors and further elucidate the direct relationship_(0.5)between DE interaction and OER activity.Here,by using cobalt hydroxide carbonate(Co(OH)(CO_(3))·xH_(2)O,CoHC) nanostructures as a proof-of-concept study,external magnetic fields are carefully implemented to verify the role of DE interaction during water oxidation reaction.Detailed studies reveal that external magnetic fields effectively enhance the reaction rate of the catalyst,the overpotential decreases from 386 to 355 mV(100 mA·cm^(-2)),while Tafel slopes drastically decline from 93 to 67 mV·dec^(-1)(1.0 T).Moreover,magnetic field increment exhibits robust durability.Through in situ Raman and impedance measurements under external field,it can be found that magnetic field promotes the electron migration between Co^(2+) and Co^(3+) in the CoHC catalysts with the assistance of DE interactions,thus boosting the OER efficiency.展开更多
Layered hydroxide metal acetate Co2（OH）3（CH3COO）·H2O with an interlayer spacing of 1.282 nm has been synthesized by a novel method which is employed in ethanol-aqueous mixed solvents media. Experiment results...Layered hydroxide metal acetate Co2（OH）3（CH3COO）·H2O with an interlayer spacing of 1.282 nm has been synthesized by a novel method which is employed in ethanol-aqueous mixed solvents media. Experiment results show that the purity of the product by the modified method is higher compared with that by the previous methods. A complete characterization of the as-prepared samples was performed by means of X-ray powder diffraction, IR spectroscopy, scanning electron microscope, as well as magnetic measurement. The facile and effective approach for the preparation of this compound in this study is very interesting and important because it has wide application in the field of anionic exchange reaction for the synthesis of hybrid organic-inorganic compounds.展开更多
Electrocatalytic nitrate reduction reaction(NO_(3)RR)to ammonia provides a promising approach to environmental preservation and sustainable energy production,but suffers from a low yield rate and poor Faradic efficien...Electrocatalytic nitrate reduction reaction(NO_(3)RR)to ammonia provides a promising approach to environmental preservation and sustainable energy production,but suffers from a low yield rate and poor Faradic efficiency,ascribed to the sluggish active hydrogen(H^(*))generation via water dissociation.Herein,single Ru atoms anchored Co(OH)_(2)(Ru1/Co(OH)_(2))catalysts are synthesized for selective nitrate reduction to ammonia,which exhibits an excellent NH_(3)yield rate of 4200μg h^(-1)cm^(-2)and a high NH_(3)Faradic efficiency of 97%at-0.33 V versus reversible hydrogen electrode,outperforming the counterpart Co(OH)_(2)and the mostly reported electrocatalysts.Experimental and theoretical results reveal that the addition of Ru atoms can boost H^(*)generation and decrease the hydrogenation energy barrier on Ru1/Co(OH)_(2),leading to enhanced NO_(3)RR performance.An integrated system of electrochemical NO_(3)RR electrolyzer and in-situ NH_(3)recovery is present,where the electrochemical NO_(3)RR can be coupled with a hydrazine oxidation reaction to achieve a more highly efficient and electricity-saving system for NH_(3)recovery.This work provides guidance for the rational design of high-performance NO_(3)RR electrocatalysts by the effective regulation of H^(*)generation and holds great promise for simultaneous nitrate-containing wastewater treatment and resource recovery.展开更多
Novel three-dimensional （3D） concentration-gradient Ni-Co hydroxide nanostructures （3DCGNC） have been directly grown on nickel foam by a facile stepwise electrochemical deposition method and intensively investigat...Novel three-dimensional （3D） concentration-gradient Ni-Co hydroxide nanostructures （3DCGNC） have been directly grown on nickel foam by a facile stepwise electrochemical deposition method and intensively investigated as binder- and conductor-free electrode for supercapacitors. Based on a three- electrode electrochemical characterization technique, the obtained 3DCGNC electrodes demonstrated a high specific capacitance of 1,760 F·g^-1 and a remarkable rate capability whereby more than 62.5% capacitance was retained when the current density was raised from 1 to 100 A·g^-1. More importantly, asymmetric supercapacitors were assembled by using the obtained 3DCGNC as the cathode and Ketjenblack as a conventional activated carbon anode. The fabricated asymmetric supercapacitors exhibited very promising electrochemical performances with an excellent combination of high energy density of 103.0 Wh·kg^-1 at a power density of 3.0 kW·kg^-1, and excellent rate capability-energy densities of about 70.4 and 26.0 Wh·kg^-1 were achieved when the average power densities were increased to 26.2 and 133.4 kW·kg^-1, respectively. Moreover, an extremely stable cycling life with only 2.7% capacitance loss after 20,000 cycles at a current density of 5 A·g^-1 was achieved, which compares very well with the traditional doublelayer supercapacitors.展开更多
β-Co(OH)2 with three-dimensional(3-D)structures was prepared by a simple hydrothermal method.It was found that the amount of cetyltrimethylammonium bromide(CTAB),the pH value,and the reaction time all had an importan...β-Co(OH)2 with three-dimensional(3-D)structures was prepared by a simple hydrothermal method.It was found that the amount of cetyltrimethylammonium bromide(CTAB),the pH value,and the reaction time all had an important influence on the formation of this morphology.The products were characterized by X-ray diffraction,energy-dispersive X-ray analysis,and scanning electron microscopy.A possible mechanism of the formation of the 3-D microstructures ofβ-Co(OH)2 was proposed.展开更多
Layered α-cobalt hydroxides Co（OH1.65 Cl0.35.0.5H2O （1）, Co（OH）1.75（NO3）0.25.0.1H2O（2） with unique macro- and microscale morphologies have been synthesised by a low temperature, ammonia-controlled vapour-dif...Layered α-cobalt hydroxides Co（OH1.65 Cl0.35.0.5H2O （1）, Co（OH）1.75（NO3）0.25.0.1H2O（2） with unique macro- and microscale morphologies have been synthesised by a low temperature, ammonia-controlled vapour-diffusion method. The materials have thin film morphologies and were characterized by X-ray powder diffraction （XRD） and field emission scanning electron microscopy （FESEM）.展开更多
Cobalt ferrite CoxNi1-xFe2O4 （x = 0, 0.5, 1 ） particles with controllable magnetic properties have been prepared by calcination of co-substituted NiFe^2＋Fe^3＋ -layered double hydroxide （NiFe^2＋Fe^3＋-LDH） precu...Cobalt ferrite CoxNi1-xFe2O4 （x = 0, 0.5, 1 ） particles with controllable magnetic properties have been prepared by calcination of co-substituted NiFe^2＋Fe^3＋ -layered double hydroxide （NiFe^2＋Fe^3＋-LDH） precursors prepared via a scalable method involving separate nucleation and aging steps （SNAS）. Their structural and magnetic characteristics were investigated by powder X-ray diffraction （XRD）, scanning electron microscopy （SEM） and vibrating sample magnetometry （VSM）. Measurements of magnetic properties show that the saturation magnetization （Ms） and coercivity （He） of the calcined products increased with increasing cobalt content. The LDH precursor-based product obtained by calcination of a mixture of CoFe^2＋Fe3^＋-LDH and NiFe^2＋Fe^3＋ -LDH powders with a Co/Ni molar ratio of 1：1, exhibits a moderate value of Ms and an increased value of He compared to the corresponding values for an Ni0.5Co0.5Fe2O4 material prepared by calcination of a Co0.5Ni0.5Fe^2＋Fe^3＋-LDH precursor, and a physical mixture of CoFe2O4 and NiFe2O4 with a Co/Ni molar ratio of 1 ： 1. These results may provide a way to regulate magnetic anisotropy of ferrite spinels by varying the composition of the LDH precursors.展开更多
Cobalt hydroxide has been emerging as a promising catalyst for the electrocatalytic oxidation reactions,including the oxygen evolution reaction(OER)and glucose oxidation reaction(GOR).Herein,we prepared cobalt hydroxi...Cobalt hydroxide has been emerging as a promising catalyst for the electrocatalytic oxidation reactions,including the oxygen evolution reaction(OER)and glucose oxidation reaction(GOR).Herein,we prepared cobalt hydroxide nanoparticles(CoHP)and cobalt hydroxide nanosheets(CoHS)on nickel foam.In the electrocatalytic OER,CoHS shows an overpotential of 306 mV at a current density of 10 mA·cm^-2.This is enhanced as compared with that of CoHP(367 mV at 10 mA·cm^-2).In addition,CoHS also exhibits an improved performance in the electrocatalytic GOR.The improved electrocatalytic performance of CoHS could be due to the higher ability of the two-dimensional nanosheets on CoHS in electron transfer.These results are useful for fabricating efficient catalysts for electrocatalytic oxidation reactions.展开更多
The hybrid material based on polyelectrolyte complexes of chitosan with oxycompounds of cobalt and nickel was electrodeposited on a stainless steel plate using the method of non-stationary electrolysis.The hybrid mate...The hybrid material based on polyelectrolyte complexes of chitosan with oxycompounds of cobalt and nickel was electrodeposited on a stainless steel plate using the method of non-stationary electrolysis.The hybrid material layer was investigated by scanning electron microscopy,atomic force microscopy,transmission elec-tron microscopy,X-ray diffraction,X-ray photoelectron spectroscopy,Brunauer-Emmett-Teller method,Fourier transform infrared spectroscopy,and Raman spectroscopy.The electrocatalytic properties of the hybrid material were studied in the hydrogen evolution reaction in alkaline electrolyte(1 mol·L−1 NaOH).It was determined that during the initial four-hour period of the hydrogen evolution process,the overpotential underwent a substan-tial decline,remaining constant for a minimum of 17 h thereafter,from 289 up to 210 mV at−10 mA·cm^(−2).After a long-term hydrogen evolution,the activity of the hybrid material electrode exceeded hydrogen evolution reaction activity by 20%Pt/C commercial catalyst at a high current density of−100 mA·cm−2.展开更多
Developing efficient and low-cost electrocatalysts for oxygen evolution reaction(OER)with high electrochemical activity and durability for diverse renewable and sustainable energy technologies remains challenging.Here...Developing efficient and low-cost electrocatalysts for oxygen evolution reaction(OER)with high electrochemical activity and durability for diverse renewable and sustainable energy technologies remains challenging.Herein,an ultrasonic-assisted and coordination modulation strategy is developed to construct sandwich-like metal-organic framework(MOF)derived hydroxide nanosheet(NS)arrays/graphene oxide(GO)composite via one-step self-transformation route.Inducing from unsteady state,the dodecahedral ZIF-67 with Co^2+in tetrahedral coordination auto-converts into defect-rich ultrathin layered hydroxides with the interlayered ion NO3-.The self-transforming a-Co(OH)2/GO nanosheet arrays from ZIF-67(Co(OH)2-GNS)change the coordination mode of Co^2+and bring about the exposure of more metal active sites,thereby enhancing the spatial utilization ratio within the framework.As monometal-based electrocatalyst,the optimized Co(OH)2-GNS exhibits remarkable OER catalytic performance evidenced by a low overpotential of 259 mV to achieve a current density of 10 mA·cm-2 in alkaline medium,even exceeding commercial RuO2.During the oxygen evolution process,electron migration can be accelerated by the interfacial/in-plane charge polarization and local electric field,corroborated by the off-axis electron holography.Density functional theory(DFT)calculations further studied the collaboration between ultrathin Co(OH)2 NS and GO,which leads to lower energy barriers of intermediate products and greatly promotes electrocatalytic property.展开更多
A two-step approach was reported to fabricate cobaltous hydroxide/y- nickel oxide hydroxide/reduced graphene oxide （Co（OH）217-NiOOHIRGO） nanocompo- sites on nickel foam by combining the reduction of graphene oxide...A two-step approach was reported to fabricate cobaltous hydroxide/y- nickel oxide hydroxide/reduced graphene oxide （Co（OH）217-NiOOHIRGO） nanocompo- sites on nickel foam by combining the reduction of graphene oxide with the help of refux condensation and the subsequent hydrothermal of Co（OH）2 on RGO. The microstructural, surface morphology and electrochemical properties of the Co（OH）2/γ-NiOOH/RGO nanocomposite were investigated. The results showed that the surface of the first-step fabricated γ-NiOOH/RGO nanocomposites was uniformly coated by Co（OH）2 nanoflakes with lateral size of tens of nm and thickness of several nm. Co（OH）2/γ-NiOOHIRGO nanocomposite demonstrated a high specific capacitance （745 mF/cm= at 0.5 mAJcm2） and a cycling stability of 69.8% after 1000 cycles at 30 mV/cm2· γ-NiOOH/RGO//Co（OH）2/γ- NiOOH/RGO asymmetric supercapacitor was assembled, and maximum gravimetric energy density of 57.3 W.h/kg and power density of 66.1 kW/kg were achieved. The synergistic effect between the highly conductive graphene and the nanoflake Co（OH）2 structure was responsible for the high electrochemical performance of the hybrid electrode. It is expected that this research could offer a simple method to prepare graphene-based electrode materials.展开更多
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.
文摘A novel type of composite electrode based on nmltiwalled carbon nanotubes coated with sheet-like cobalt hydroxide particles was used in supercapacitors. Cobalt hydroxide cathodlcally deposited fiom Co（NO3）O2 solution with carbon nanotubes as matrix exhibited large pseudo-capacitance of 322 F/g in 1 mol/L KOH. To characterize the cobalt hydroxide nanocomposite electrode, a charge-discharge cycling test, cyclic voltammetry, and an impedance test were done. This cobalt hydroxide composite exhibiting excellent pseudo-capacitive behavior （i.c. high reversibility, high specific capacitance, low impedance）, was demonstrated to be a candidate for the application of electrochemical supercapacitors. A combined capacitor consisting of cobalt hydroxide composite as a cathode and activated carbon fiber as an anode was reported. The electrochemical pcrformance of the combined capacitor was characterized by cyclic voltammetry and a dc charge/discharge test. The combined capacitor showed ideal capacitor behavior with an extended operating voltage of 1.4 V. According to the extended operating voltage, the energy density of the combined capacitor at a current density of 100 mA/cm^2 was found to be 11 Wh/kg. The combined capacitor exhibited high-energy density and stable power characteristics,
基金financially supported by the National Natural Science Foundation of China(52025013,22121005)the 111 Project(B12015)+1 种基金Haihe Laboratory of Sustainable Chemical Transformationsthe Fundamental Research Funds for the Central Universities。
文摘Combining urea oxidation reaction(UOR) with hydrogen evolution reaction(HER) is an effective method for energy saving and highly efficient electrocatalytic hydrogen production. Herein, molybdenumincorporated cobalt carbonate hydroxide nanoarrays(CoxMoyCH) are designed and synthesized as a bifunctional catalyst towards UOR and HER. Benefiting from the Mo doping, the dispersed nanoarray structure and redistributed electron density, the CoxMoyCH catalyst display outstanding catalytic performance and durability for both HER and UOR, affording the overpotential of 82 m V for HER and delivering a low potential of the 1.33 V for UOR(vs. reversible hydrogen electrode, RHE) to attain a current density of 10 m A cm^(-2), respectively. Remarkably, when CoxMoyCH was applied as bifunctional catalyst in a twoelectrode electrolyzer, a working voltage of 1.40 V is needed in urea-assisted water electrolysis at10 m A cm^(-2) and without apparent decline for 40 h, outperforming the working voltage of 1.51 V in conventional water electrolysis.
基金Project(21471162) supported by the National Natural Science Foundation of ChinaProject(2015H6016) supported by the Science and Technology Project of Fujian Province,China
文摘A new design route was presented to fabricate cobalt aluminum-layered double hydroxide(CoAl-LDH)thin layers whichgrow on carbon spheres(CSs)through a growth method.The CoAl-LDH thin layers consist of nanoflakes with a thickness of20nm.The galvanostatic charge-discharge test of the CoAl-LDH/CSs composite shows a great specific capacitance of1198F/g at1A/g(based on the mass of the CoAl-LDH/CSs composite)in6mol/L KOH solution,and the composite displays an impressive specificcapacitance of920F/g even at a high current density of10A/g.Moreover,the composite remains a specific capacitance of928F/gafter1000cycles at2A/g,and the specific capacitance retention is84%,indicating that the composite has high specific capacitance,excellent rate capability and good cycling stability in comparison to pristine CoAl-LDH.
文摘Two-dimensional layered double hydroxides(LDHs)have been identified as promising electrocatalysts for the oxygen evolution reaction(OER);however,the simple and effective synthesis of high-quality LDHs remains extremely challenging and the active sites have not been clarified.Herein,we report a facile solution-reaction method for preparing an ultrathin(thickness<2 nm)nonprecious CoFe-based LDH.Co_(1)Fe_(0.2) LDH delivers a current density of 10 mA cm^(-2) and a high turnover frequency of 0.082 s^(-1) per total 3d metal atoms at a low overpotential of 256 mV.Its mass activity is 277.9 A g^(-1) at an overpotential of 300 mV for the OER.Kinetic studies reveal the Co site as the main active center for the OER.The doped Fe lowers the reaction barrier by accelerating the charge-transfer process.Theoretical calculations reveal that the surface Co sites adjacent to Fe atoms are the active centers for the OER and the subsurface Fe dopants excessively weaken the OH^(*)adsorption,thus increasing the energy barrier of the rate-determining step.This study can guide the rational design of high-performance CoFe-based LDHs for water splitting.
基金partially supported by the National Natural Science Foundation of China(Nos.21906001 and 51721006)supported by MOE Key Laboratory of Resources and Environmental Systems Optimization(NCEPU)
文摘Hollow microsphere structure cobalt hydroxide(h-Co(OH)2) was synthesized via an optimized solvothermal-hydrothermal process and applied to activate peroxymonosulfate(PMS) for degradation of a typical pharmaceutically active compound,ibuprofen(IBP).The material characterizations confirmed the presence of the microscale hollow spheres with thin nanosheets shell in h-Co(OH)2,and the crystalline phase was assigned to a-Co(OH)2.h-Co(OH)2 could efficiently activate PMS for radicals production,and 98.6% of IBP was degraded at 10 min.The activation of PMS by h-Co(OH)2 was a pHindependent process,and pH 7 was the optimum condition for the activation-degradation system.Scavenger quenching test indicated that the sulfate radical(SO4^·-) was the primary reactive oxygen species for IBP degradation,which contributed to 75.7%.Fukui index(f^-) based on density functional theory(DFT) calculation predicted the active sites of IBP molecule for SO4^·- attack,and then IBP degradation pathway was proposed by means of intermediates identification and theoretical calculation.The developed hollow Co(OH)2 used to efficiently activate PMS is promising and innovative alternative for organic contaminants removal from water and wastewater.
基金supported by the National Natural Science Foundation of China(51502078)the Major Project of Science and Technology,Education Department of Henan Province(19A150019 and 19A150018)+2 种基金the Science and Technology Research Project of Henan Province(192102310490 and 182102410090)the program for Science&Technology Innovation Team in Universities of Henan Province(19IRTSTHN029)supported by the U.S.Department of Energy,Office of Science,Office of Basic Energy Sciences,Chemical Sciences,Geosciences,and Biosciences Division,Catalysis Science program。
文摘In this work,a facile chelation-mediated route was developed to fabricate ultrathin cobalt(oxy)hydroxides(CoOOH)nanosheets on hematite photoanode(Fe_(2)O_(3)).The route contains two steps of the adsorption of[Co-EDTA]^(2-)species on Fe_(2)O_(3) nanorod array followed by the hydrolysis in alkaline solution.The resulting CoOOH/Fe_(2)O_(3) exhibits a remarkably improved photocurrent density of 2.10 mA cm^(-2) at 1.23 V vs.RHE,which is ca.2.8 times that of bare Fe_(2)O_(3).In addition,a negative shift of onset potential ca.200 mV is achieved.The structural characterizations reveal the chelate EDTA plays important roles that enhance the adsorption of Co species and the formation of contact between CoOOH and Fe_(2)O_(3).(Photo)electrochemical analysis suggests,besides providing active sites for water oxidation,CoOOH at large extent promotes the charge separation and the charge transfer via passivating surface states and suppressing charge recombination.It also found CoOOH possesses some oxygen vacancies,which could act as trapping centers for photogenerated holes and facilitate the charge separation.Intensity modulated photocurrent spectroscopy(IMPS)shows that,under low applied potential the water oxidation mainly occurs on CoOOH,while under high applied potential the water oxidation could occur on both CoOOH and Fe_(2)O_(3).The findings not only provide an efficient strategy for designing ultrathin(oxy)hydroxides on semiconductors for PEC applications but also put forward a new insight on the role of CoOOH during water oxidation.
文摘The glassy carbon (GC) electrode modified with a monolayer nickel hydroxide (GC/Ni(OH) 2) was prepared by immersion of GC substrate in 1.0×10 -3 mol/L NiSO 4 solution, and then cyclic voltammetric scanning in 0.20 mol/L KOH. Similarly, GC/Co(OH) 2 electrode was prepared too. The experiments showed that the voltammetric behavior of GC/Ni(OH) 2 electrode in 0.20 mol/L KOH is more stable than that of GC/ Co(OH) 2. It was found that the GC/Ni(OH) 2 electrode acts as an effective electrocatalysis for the oxidation of hydrazine.
基金financially supported by the Program for New Century Excellent Talents of the University in China (No. NCET-13-0645)the National Natural Science Foundation of China (Nos. 21201010, 21671170 and 21673203)+3 种基金the Innovation Scientists and Technicians Troop Construction Projects of Henan Province (No. 164200510018)the Program for Innovative Research Team (in Science and Technology) in University of Henan Province (No. 14IRTSTHN004)the Six Talent Plan (No. 2015-XCL-030)Qinglan Project
文摘CoSn（OH）6 nanocubes were synthesized by a facile one-step co-precipitate method. Their supercapacitor performances were investigated via a traditional threeelectrode system and all solid-state flexible asymmetric supercapacitor. The electrode shows a maximum specific capacitance up to 695 F·g^-1. The flexible all solid-state asymmetric supercapacitor was fabricated based on CoSn（OH）6 nanocubes and active carbon as positive and negative electrode. The assembled asymmetric supercapacitor exhibits a specific capacitance（97.3 mF·cm^-2）, good rate/mechanical stability and a long cycling stability（5000 cycles）, demonstrating great promise for applications in all solid-state flexible supercapacitors.
基金financially supported by the Program B for Outstanding PhD Candidate of Nanjing University(No.201801B067)。
文摘Double-exchange(DE) interaction plays an important role in electrocatalytic oxygen evolution reaction(OER).However,precise achievement of DE interaction often requires foreign dopants or vacancy engineering,leading to destabilization of the catalysts and deterioration of performance.By contrast,the utilization of environmentally friendly,contactless,and continuously adjustable magnetic fields to study the OER process is profitable to avoid aforementioned interference factors and further elucidate the direct relationship_(0.5)between DE interaction and OER activity.Here,by using cobalt hydroxide carbonate(Co(OH)(CO_(3))·xH_(2)O,CoHC) nanostructures as a proof-of-concept study,external magnetic fields are carefully implemented to verify the role of DE interaction during water oxidation reaction.Detailed studies reveal that external magnetic fields effectively enhance the reaction rate of the catalyst,the overpotential decreases from 386 to 355 mV(100 mA·cm^(-2)),while Tafel slopes drastically decline from 93 to 67 mV·dec^(-1)(1.0 T).Moreover,magnetic field increment exhibits robust durability.Through in situ Raman and impedance measurements under external field,it can be found that magnetic field promotes the electron migration between Co^(2+) and Co^(3+) in the CoHC catalysts with the assistance of DE interactions,thus boosting the OER efficiency.
基金Supported by the President Fund of Xi'an Technological University,China(No.XAGDXJJ1009)
文摘Layered hydroxide metal acetate Co2（OH）3（CH3COO）·H2O with an interlayer spacing of 1.282 nm has been synthesized by a novel method which is employed in ethanol-aqueous mixed solvents media. Experiment results show that the purity of the product by the modified method is higher compared with that by the previous methods. A complete characterization of the as-prepared samples was performed by means of X-ray powder diffraction, IR spectroscopy, scanning electron microscope, as well as magnetic measurement. The facile and effective approach for the preparation of this compound in this study is very interesting and important because it has wide application in the field of anionic exchange reaction for the synthesis of hybrid organic-inorganic compounds.
基金supported by the National Natural Science Foundation of China(grant nos.22206054,U21A20286,and 22478310)the Fundamental Research Funds for the Central China Normal University.
文摘Electrocatalytic nitrate reduction reaction(NO_(3)RR)to ammonia provides a promising approach to environmental preservation and sustainable energy production,but suffers from a low yield rate and poor Faradic efficiency,ascribed to the sluggish active hydrogen(H^(*))generation via water dissociation.Herein,single Ru atoms anchored Co(OH)_(2)(Ru1/Co(OH)_(2))catalysts are synthesized for selective nitrate reduction to ammonia,which exhibits an excellent NH_(3)yield rate of 4200μg h^(-1)cm^(-2)and a high NH_(3)Faradic efficiency of 97%at-0.33 V versus reversible hydrogen electrode,outperforming the counterpart Co(OH)_(2)and the mostly reported electrocatalysts.Experimental and theoretical results reveal that the addition of Ru atoms can boost H^(*)generation and decrease the hydrogenation energy barrier on Ru1/Co(OH)_(2),leading to enhanced NO_(3)RR performance.An integrated system of electrochemical NO_(3)RR electrolyzer and in-situ NH_(3)recovery is present,where the electrochemical NO_(3)RR can be coupled with a hydrazine oxidation reaction to achieve a more highly efficient and electricity-saving system for NH_(3)recovery.This work provides guidance for the rational design of high-performance NO_(3)RR electrocatalysts by the effective regulation of H^(*)generation and holds great promise for simultaneous nitrate-containing wastewater treatment and resource recovery.
基金This work was supported by the National Natural Science Foundation of China （No. 21001117）, the Shenzhen Peacock Plan （No. KQCX20140522150815065）, and the Starting-Up Funds of South University of Science and Technology of China （SUSTC） through the Talent Plan of the Shenzhen Government. H. T. L. acknowledges the support from a Key Project of the Hunan Provincial Science and Technology Plan （No. 2014FJ2007）.
文摘Novel three-dimensional （3D） concentration-gradient Ni-Co hydroxide nanostructures （3DCGNC） have been directly grown on nickel foam by a facile stepwise electrochemical deposition method and intensively investigated as binder- and conductor-free electrode for supercapacitors. Based on a three- electrode electrochemical characterization technique, the obtained 3DCGNC electrodes demonstrated a high specific capacitance of 1,760 F·g^-1 and a remarkable rate capability whereby more than 62.5% capacitance was retained when the current density was raised from 1 to 100 A·g^-1. More importantly, asymmetric supercapacitors were assembled by using the obtained 3DCGNC as the cathode and Ketjenblack as a conventional activated carbon anode. The fabricated asymmetric supercapacitors exhibited very promising electrochemical performances with an excellent combination of high energy density of 103.0 Wh·kg^-1 at a power density of 3.0 kW·kg^-1, and excellent rate capability-energy densities of about 70.4 and 26.0 Wh·kg^-1 were achieved when the average power densities were increased to 26.2 and 133.4 kW·kg^-1, respectively. Moreover, an extremely stable cycling life with only 2.7% capacitance loss after 20,000 cycles at a current density of 5 A·g^-1 was achieved, which compares very well with the traditional doublelayer supercapacitors.
基金supported by the National Natural Science Foundation of China(Grant No.20873020)
文摘β-Co(OH)2 with three-dimensional(3-D)structures was prepared by a simple hydrothermal method.It was found that the amount of cetyltrimethylammonium bromide(CTAB),the pH value,and the reaction time all had an important influence on the formation of this morphology.The products were characterized by X-ray diffraction,energy-dispersive X-ray analysis,and scanning electron microscopy.A possible mechanism of the formation of the 3-D microstructures ofβ-Co(OH)2 was proposed.
文摘Layered α-cobalt hydroxides Co（OH1.65 Cl0.35.0.5H2O （1）, Co（OH）1.75（NO3）0.25.0.1H2O（2） with unique macro- and microscale morphologies have been synthesised by a low temperature, ammonia-controlled vapour-diffusion method. The materials have thin film morphologies and were characterized by X-ray powder diffraction （XRD） and field emission scanning electron microscopy （FESEM）.
基金supported by the National Natural Science Foundation of China, the 111 Project (B07004)the Program for New Century Excellent Talents in Universities, the Beijing Nova Program (2007B021)the Natural Science Foundation for Young Teachers of Beijing University of Chemical Technology
文摘Cobalt ferrite CoxNi1-xFe2O4 （x = 0, 0.5, 1 ） particles with controllable magnetic properties have been prepared by calcination of co-substituted NiFe^2＋Fe^3＋ -layered double hydroxide （NiFe^2＋Fe^3＋-LDH） precursors prepared via a scalable method involving separate nucleation and aging steps （SNAS）. Their structural and magnetic characteristics were investigated by powder X-ray diffraction （XRD）, scanning electron microscopy （SEM） and vibrating sample magnetometry （VSM）. Measurements of magnetic properties show that the saturation magnetization （Ms） and coercivity （He） of the calcined products increased with increasing cobalt content. The LDH precursor-based product obtained by calcination of a mixture of CoFe^2＋Fe3^＋-LDH and NiFe^2＋Fe^3＋ -LDH powders with a Co/Ni molar ratio of 1：1, exhibits a moderate value of Ms and an increased value of He compared to the corresponding values for an Ni0.5Co0.5Fe2O4 material prepared by calcination of a Co0.5Ni0.5Fe^2＋Fe^3＋-LDH precursor, and a physical mixture of CoFe2O4 and NiFe2O4 with a Co/Ni molar ratio of 1 ： 1. These results may provide a way to regulate magnetic anisotropy of ferrite spinels by varying the composition of the LDH precursors.
基金the financial support from the National Natural Science Foundation of China(Grant Nos.11761141006,81822024 and 21605102)the National Key Research and Development Program of China(Grant No.2017YFC1200904).
文摘Cobalt hydroxide has been emerging as a promising catalyst for the electrocatalytic oxidation reactions,including the oxygen evolution reaction(OER)and glucose oxidation reaction(GOR).Herein,we prepared cobalt hydroxide nanoparticles(CoHP)and cobalt hydroxide nanosheets(CoHS)on nickel foam.In the electrocatalytic OER,CoHS shows an overpotential of 306 mV at a current density of 10 mA·cm^-2.This is enhanced as compared with that of CoHP(367 mV at 10 mA·cm^-2).In addition,CoHS also exhibits an improved performance in the electrocatalytic GOR.The improved electrocatalytic performance of CoHS could be due to the higher ability of the two-dimensional nanosheets on CoHS in electron transfer.These results are useful for fabricating efficient catalysts for electrocatalytic oxidation reactions.
基金supported by the Ministry of Science and Higher Education of the Russian Federation within the governmental assignment for Boreskov Institute of Catalysis(Project No.FWUR-2024-0036)(A.N.Kuznetsov)supported by the Ministry of Science and Higher Education of the Russian Federation(Project No.121031700314-5)(K.M.Popov).
文摘The hybrid material based on polyelectrolyte complexes of chitosan with oxycompounds of cobalt and nickel was electrodeposited on a stainless steel plate using the method of non-stationary electrolysis.The hybrid material layer was investigated by scanning electron microscopy,atomic force microscopy,transmission elec-tron microscopy,X-ray diffraction,X-ray photoelectron spectroscopy,Brunauer-Emmett-Teller method,Fourier transform infrared spectroscopy,and Raman spectroscopy.The electrocatalytic properties of the hybrid material were studied in the hydrogen evolution reaction in alkaline electrolyte(1 mol·L−1 NaOH).It was determined that during the initial four-hour period of the hydrogen evolution process,the overpotential underwent a substan-tial decline,remaining constant for a minimum of 17 h thereafter,from 289 up to 210 mV at−10 mA·cm^(−2).After a long-term hydrogen evolution,the activity of the hybrid material electrode exceeded hydrogen evolution reaction activity by 20%Pt/C commercial catalyst at a high current density of−100 mA·cm−2.
基金This work was supported by the National Basic Research Program of China(No.2018YFA209102)the National Natural Science Foundation of China(Nos.11727807,51725101,51672050,and 61790581).
文摘Developing efficient and low-cost electrocatalysts for oxygen evolution reaction(OER)with high electrochemical activity and durability for diverse renewable and sustainable energy technologies remains challenging.Herein,an ultrasonic-assisted and coordination modulation strategy is developed to construct sandwich-like metal-organic framework(MOF)derived hydroxide nanosheet(NS)arrays/graphene oxide(GO)composite via one-step self-transformation route.Inducing from unsteady state,the dodecahedral ZIF-67 with Co^2+in tetrahedral coordination auto-converts into defect-rich ultrathin layered hydroxides with the interlayered ion NO3-.The self-transforming a-Co(OH)2/GO nanosheet arrays from ZIF-67(Co(OH)2-GNS)change the coordination mode of Co^2+and bring about the exposure of more metal active sites,thereby enhancing the spatial utilization ratio within the framework.As monometal-based electrocatalyst,the optimized Co(OH)2-GNS exhibits remarkable OER catalytic performance evidenced by a low overpotential of 259 mV to achieve a current density of 10 mA·cm-2 in alkaline medium,even exceeding commercial RuO2.During the oxygen evolution process,electron migration can be accelerated by the interfacial/in-plane charge polarization and local electric field,corroborated by the off-axis electron holography.Density functional theory(DFT)calculations further studied the collaboration between ultrathin Co(OH)2 NS and GO,which leads to lower energy barriers of intermediate products and greatly promotes electrocatalytic property.
基金This work was financially supported by the National Natural Science Foundation of China （Grant Nos. 51605293 and 51702213） and the Natural Science Foundation of Shanghai （16ZR1423500）. The authors also acknowledge financial support from the Program for Associate Professor of Special Appointment （Young Eastern Scholar） at Shanghai Institutions of Higher Learning （QD2016013）.
文摘A two-step approach was reported to fabricate cobaltous hydroxide/y- nickel oxide hydroxide/reduced graphene oxide （Co（OH）217-NiOOHIRGO） nanocompo- sites on nickel foam by combining the reduction of graphene oxide with the help of refux condensation and the subsequent hydrothermal of Co（OH）2 on RGO. The microstructural, surface morphology and electrochemical properties of the Co（OH）2/γ-NiOOH/RGO nanocomposite were investigated. The results showed that the surface of the first-step fabricated γ-NiOOH/RGO nanocomposites was uniformly coated by Co（OH）2 nanoflakes with lateral size of tens of nm and thickness of several nm. Co（OH）2/γ-NiOOHIRGO nanocomposite demonstrated a high specific capacitance （745 mF/cm= at 0.5 mAJcm2） and a cycling stability of 69.8% after 1000 cycles at 30 mV/cm2· γ-NiOOH/RGO//Co（OH）2/γ- NiOOH/RGO asymmetric supercapacitor was assembled, and maximum gravimetric energy density of 57.3 W.h/kg and power density of 66.1 kW/kg were achieved. The synergistic effect between the highly conductive graphene and the nanoflake Co（OH）2 structure was responsible for the high electrochemical performance of the hybrid electrode. It is expected that this research could offer a simple method to prepare graphene-based electrode materials.
