Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construc...Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H2 and H2O2 production. Both H2 and H2O2 are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^-1 h^–1 (first 1 h) for H2 and H2O2, respectively, which is much higher than that of a commercial Pt/TiO2(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H2O2, compared with the four-electron oxidation of water to O2.展开更多
Efficient,stable,and noble‐metal‐free electrocatalysts for both the oxygen evolution reaction and the hydrogen evolution reaction are highly imperative for the realization of low‐cost commercial water‐splitting el...Efficient,stable,and noble‐metal‐free electrocatalysts for both the oxygen evolution reaction and the hydrogen evolution reaction are highly imperative for the realization of low‐cost commercial water‐splitting electrolyzers.Herein,a cost‐effective and ecofriendly strategy is reported to fabricate coral‐like FeNi(OH)x/Ni as a bifunctional electrocatalyst for overall water splitting in alkaline media.With the assistance of mild corrosion of Ni by Fe(NO3)3,in situ generated FeNi(OH)x nanosheets are intimately attached on metallic coral‐like Ni.Integration of these nanosheets with the electrodeposited coral‐like Ni skeleton and the supermacroporous Ni foam substrate forms a binder‐free hierarchical electrode,which is beneficial for exposing catalytic active sites,accelerating mass transport,and facilitating the release of gaseous species.In 1.0 mol L^-1 KOH solution,a symmetric electrolyzer constructed with FeNi(OH)x/Ni as both the anode and the cathode exhibits an excellent activity with an applied potential difference of 1.52 V at 10 mA cm^-2,which is superior to that of an asymmetric electrolyzer constructed with the state‐of‐the‐art RuO2‐PtC couple(applied potential difference of 1.55 V at 10 mA cm^-2).This work contributes a facile and reliable strategy for manufacturing affordable,practical,and promising water‐splitting devices.展开更多
Determination of probable mechanism function and kinetic parameters is important to hydrometallurgical kinetics.In this work,the most probable mechanism function and kinetic parameters of gibbsite dissolution in NaOH ...Determination of probable mechanism function and kinetic parameters is important to hydrometallurgical kinetics.In this work,the most probable mechanism function and kinetic parameters of gibbsite dissolution in NaOH solution are studied.The sample,the mixture of synthetic gibbsite and sodium hydroxide solution,was scanned in high-pressure differential scanning calorimetry(DSC) equipment with the heating rate of 10 K·min-1. Integral equation and differential equation of non-isothermal kinetics were solved to fit the data related to DSC curve.According to the calculation results,the most probable mechanism function for pure synthetic gibbsite dissolution in sodium hydroxide solution is presented based on the optimum procedure in the database of the mechanism function.The apparent activation energy obtained is(75±1) kJ·mol-1,the frequency factor is 10 8±1mol·s-1,and the reaction is a second order reaction.展开更多
Photocatalytic Z-scheme water splitting is considered as a promising approach to produce solar hydrogen.However,the forward hydrogen production reaction is often impeded by backward reactions.In the present study,in a...Photocatalytic Z-scheme water splitting is considered as a promising approach to produce solar hydrogen.However,the forward hydrogen production reaction is often impeded by backward reactions.In the present study,in a photosystem Ⅱ-integrated hybrid Z-scheme water splitting system,the backward hydrogen oxidation reaction was significantly suppressed by loading a PtCrOx cocatalyst on a ZrO2/TaON photocatalyst.Due to the weak chemisorption and activation of molecular hydrogen on PtCrOx,where Pt is stabilized in the oxidized forms,Pt^Ⅱ and Pt^Ⅳ,hydrogen oxidation is inhibited.However,it is remarkably well-catalyzed by the metallic Pt cocatalyst,thereby rapidly consuming the produced hydrogen.This work describes an approach to inhibit the backward reaction in the photosystem Ⅱ-integrated hybrid Z-scheme water splitting system using Fe(CN)6^3-/Fe(CN)6^4-redox couple as an electron shuttle.展开更多
We report a facile way to prepare sulfur(S) doped Ni4/5 Fe1/5-layered double hydroxide(LDH) electrocatalysts for oxygen evolution reaction(OER). The influence of S doping amount on the OER activity of the resulted Ni ...We report a facile way to prepare sulfur(S) doped Ni4/5 Fe1/5-layered double hydroxide(LDH) electrocatalysts for oxygen evolution reaction(OER). The influence of S doping amount on the OER activity of the resulted Ni Fe-LDHs was studied and the optimal surface S content was ca. 0.43 at%. The developed S-doped Ni Fe-LDH exhibits excellent OER catalyst activity in 1.0 M KOH with overpotential of only 257 m V at the current density of 10 m A cm^-2. Moreover, the catalyst could maintain high activity after 30 h stability test. The high activity of the S-doped Ni Fe-LDH catalysts may originate from the synergistic effect between S and the Fe sites. This work provides a simple but efficient way to improve the OER performance of transition metal oxides/(oxy)hydroxides.展开更多
Depositing a cocatalyst has proven to be an important strategy for improving the photoelectrochemical(PEC)water-splitting efficiency of photoanodes.In this study,Ni(OH)2 quantum dots(Ni(OH)2 QDs)were deposited in situ...Depositing a cocatalyst has proven to be an important strategy for improving the photoelectrochemical(PEC)water-splitting efficiency of photoanodes.In this study,Ni(OH)2 quantum dots(Ni(OH)2 QDs)were deposited in situ onto anα-Fe_(2)O_(3)photoanode via a chelation-mediated hydrolysis method.The photocurrent density of the Ni(OH)2 QDs/α-Fe_(2)O_(3)photoanode reached 1.93 mA·cm^(−2)at 1.23 V vs.RHE,which is 3.5 times that ofα-Fe_(2)O_(3),and an onset potential with a negative shift of ca.100 mV was achieved.More importantly,the Ni(OH)2 QDs exhibited excellent stability in maintaining PEC water oxidation at a high current density,which is attributed to the ultra-small crystalline size,allowing for the rapid acceptance of holes fromα-Fe_(2)O_(3)to Ni(OH)_(2)QDs,formation of active sites for water oxidation,and hole transfer from the active sites to water molecules.Further(photo)electrochemical analysis suggests that Ni(OH)_(2)QDs not only provide maximal active sites for water oxidation but also suppress charge recombination by passivating the surface states ofα-Fe_(2)O_(3),thereby significantly enhancing the water oxidation kinetics over theα-Fe_(2)O_(3)surface.展开更多
Catalytic water splitting potentially reduce the consumption of fossil fuels and has received intense research attention.Synergy effects in multi‐element transition metal‐based water splitting catalysts have evoked ...Catalytic water splitting potentially reduce the consumption of fossil fuels and has received intense research attention.Synergy effects in multi‐element transition metal‐based water splitting catalysts have evoked special interests.Studies on catalysts in interfacial structures are especially meaningful due to their pertinence in applications.In this study,we report the synergy effects in promoting catalytic power in the ternary transition metal Zn,Co,Ni alloy nanoparticles that embeds in the carbonized Ppy/CNT multilayered matrix.By comparison with a series of binary or single metal counterparts,the mechanism under the synergy effects are elucidated.Experimental and DFT calculation results indicate that the ternary transition metal catalysts in the N‐doped carbon matrix present special electronic structure,which benefits the reversible transition‐state adsorption in HER and OER and render the catalysts high conductivity in room temperature.We expect our findings inspire further development of efficient transition metal HER and OER catalysts.展开更多
Pretreatment is one of the most important steps in the production bioethanol from lignocellulose materials. Alkaline pretreatment is a common mean of pretreatment but microwave oven could assist its efficiency as it c...Pretreatment is one of the most important steps in the production bioethanol from lignocellulose materials. Alkaline pretreatment is a common mean of pretreatment but microwave oven could assist its efficiency as it can reduce the pretreatment time and improve the enzymatic activity during hydrolysis. The aim of this paper is to determine lignin removal from banana trunk using microwave-assisted alkaline (NaOH and NH4OH) pretreatments. The best pretreatment conditions were used for mass pretreatment before hydrolysis and fermentation. The result shows that, optimum lignin removal was with microwave-assisted NaOH pretreatment with the removal of up to 98% lignin at 2% (w/v (weight/volum)) sodium hydroxide, 170 W microwave power at 10 rain. Microwave-assisted ammonium hydroxide pretreatment achieved 97% lignin removal at 1% ammonium hydroxide concentration and 680 W microwave power at 5 min. Microwave- alkaline assisted pretreatment increased the yield and quality of fermentable sugar after enzyme hydrolysis with NH4OH and ammonium hydroxide yielding 40% and 39% of ethanol, respectively. This result reveals that, well controlled microwave- alkaline assisted pretreatment of banana trunk could effectively remove lignin and give high bioethanol yield.展开更多
An efficient and economical oxygen evolution reaction(OER)catalyst is critical to the widespread application of solar energy to fuel conversion.Among many potential OER catalysts,the metal oxyhydroxides,especially FeO...An efficient and economical oxygen evolution reaction(OER)catalyst is critical to the widespread application of solar energy to fuel conversion.Among many potential OER catalysts,the metal oxyhydroxides,especially FeOOH,show promising OER reactivity.In the present work,we performed a DFT+U study of the OER mechanism on theγ‐FeOOH(010)surface.In particular,we established the chemical potential of the OH?and hole pair and included the OH?anion in the reaction pathway,accounting to the alkaline conditions of anodic OER process.We then analyzed the OER pathways on the surface with OH‐,O‐and Fe‐terminations.On the surface with OH‐and O‐terminations,the O2molecule could form from either OH reacting with the surface oxygen species(-OH*and-O*)or the combination of two surface oxygen species.On the Fe‐terminated surface,O2can only form by adsorbing OH on the Fe sites first.The potential‐limiting step of the oxygen evolution with different surface terminations was determined by following the free‐energy change of the elementary steps along each pathway.Our results show that oxygen formation requires recreating the surface Fe sites,and consequently,the condition that favors the partially exposed Fe sites will promote oxygen formation.展开更多
Contrast degradation experiments between ethanol and polyvinyl alcohol (PVA) were conducted during H2O2, UV/H2O2, Fenton, and Photo-Fenton processes in this study. UV/VIS spectra showed' that complexes between Fe(...Contrast degradation experiments between ethanol and polyvinyl alcohol (PVA) were conducted during H2O2, UV/H2O2, Fenton, and Photo-Fenton processes in this study. UV/VIS spectra showed' that complexes between Fe(Ⅲ) and organics were easily formed and degraded within reaction time. Compared with ,the degradation of complex, hydroxyl radicals acted weakly in Fenton or Photo-Fenton process. Hydroxyl radi'cals involved in Photo-Fenton process were deemed to be generated from the split decomposition of H2O2, photolysis of Fe_aq^3+, and degradation of hydrated Fe(Ⅳ)-complex but not traditional Fenton reaction. Experimental evidence to support this point was presented in this paper.展开更多
The catalytic/electrocatalytic performance of platinum(Pt)nanostructures highly relates to their morphology.Herein,we propose a facile self-template pyrolysis strategy at high temperature to synthesize one-dimensional...The catalytic/electrocatalytic performance of platinum(Pt)nanostructures highly relates to their morphology.Herein,we propose a facile self-template pyrolysis strategy at high temperature to synthesize one-dimensionally holey Pt nanotubes(Pt-hNTs)using Pt^(Ⅱ)-dimethylglyoxime complex(Pt^(Ⅱ)-DMG)nanorods as the reaction precursor.The coordination capability of DMG results in the generation of Pt^(Ⅱ)-DMG nanorods,whereas the reducibility of DMG at high temperature leads to the reduction of Pt^(Ⅱ)species in Pt^(Ⅱ)-DMG nanorods.During the reaction process,the inside-out Ostwald ripening phenomenon leads to the hollow morphology of Pt-hNTs.Benefiting from the physical characteristics of hollow and holey structure,Pt-hNTs with clean surface show superior electroactivity and durability for catalyzing ethanol electrooxidation as well as hydrogen evolution reaction in alkaline media.Under optimized experimental conditions,the constructed symmetric Pt-hNTs||Pt-hNTs ethanol electrolyzer only requires an electrolysis voltage of 0.40 V to achieve the electrochemical hydrogen production,demonstrating a highly energy saving strategy relative to traditional water electrolysis.展开更多
Development of highly active electrocatalysts for oxygen evolution reaction(OER)is one of the critical issues for water splitting,and most reported catalysts operate at overpotentials above 190 mV.Here we present a mu...Development of highly active electrocatalysts for oxygen evolution reaction(OER)is one of the critical issues for water splitting,and most reported catalysts operate at overpotentials above 190 mV.Here we present a multiphase nickel iron sulfide(MPS)hybrid electrode with a hierarchical structure of iron doped NiS and Ni3S2,possessing a benchmark OER activity in alkaline media with a potential as low as 1.33 V(vs.reversible hydrogen electrode)to drive an OER current density of 10 mA cm^-2.The Fe doped NiS,combined with highly conductive disulfide phase on porous Ni foam,is believed to be responsible for the ultrahigh activity.Furthermore,density functional theory simulation reveals that partially oxidized sulfur sites in Fe doped NiS could dramatically lower the energy barrier for the rate-determining elementary reaction,thus contributing to the active oxygen evolution.展开更多
Water electrolysis to produce H2 is a promising strategy for generating a renewable fuel.However,the sluggish-kinetics and low value-added anodic oxygen evolution reaction(OER)restricts the overall energy conversion e...Water electrolysis to produce H2 is a promising strategy for generating a renewable fuel.However,the sluggish-kinetics and low value-added anodic oxygen evolution reaction(OER)restricts the overall energy conversion efficiency.Herein we report a strategy of boosting H_(2)production at low voltages by replacing OER with a bioelectrochemical cascade reaction at a triphase bioanode.In the presence of oxygen,oxidase enzymes can convert biomass into valuable products,and concurrently generate H_(2)O_(2) that can be further electrooxidized at the bioanode.Benefiting from the efficient oxidase kinetics at an oxygen-rich triphase bioanode and the more favorable thermodynamics of H_(2)O_(2)oxidation than that of OER,the cell voltage and energy consumption are reduced by~0.70 V and~36%,respectively,relative to regular water electrolysis.This leads to an efficient H_(2)production at the cathode and valuable product generation at the bioanode.Integration of a bioelectrochemical cascade into the water splitting process provides an energy-efficient and promising pathway for achieving a renewable fuel.展开更多
Hydrolysis and oxidation of formamidine disulfide in acidic medium were investigated using high-performance liquid chro- matography (HPLC) and mass spectrometry (MS) at 25 ~C. By controlling the slow reaction rate...Hydrolysis and oxidation of formamidine disulfide in acidic medium were investigated using high-performance liquid chro- matography (HPLC) and mass spectrometry (MS) at 25 ~C. By controlling the slow reaction rate and choosing appropriate mobile phase, HPLC provides the unique advantages over other methods (UV-Vis, chemical separation) in species tracking and kinetic study. In addition to thiourea and formamidine sulfinic acid, two unreported products were also detected in the hy- drolysis reaction. Mass spectrometry measurement indicates these two products to be formamidine sulfenic acid and thiocyan- ogen with mass weights of 92.28 and 116,36, respectively. In the oxidation of formamidine disulfide by hydrogen peroxide, besides thiourea, formamidine sulfenic acid, formamidine sulfinic acid, thiocyanogen and urea, formamidine sulfonic acid and sulfate could be detected. The oxidation reaction was found to be first order in both forrnamidine disulfide and hydrogen per- oxide. The rate constants of hydrolysis and oxidation reactions were determined in the pH range of 1.5-3.0. It was found both rate constants are increased with the increasing of pH. Experimental curves of different species can be effectively simulated via a mechanism scheme for formamidine disulfide oxidation, including hydrolysis equilibrium of formamidine disulfide and irre- versible hydrolysis of formamidine sulfenic acid.展开更多
基金supported by the National Natural Science Foundation of China(21703046)the National Key R&D of China(2016YFF0203803 and 2016YFA0200902)~~
文摘Photocatalytic oxidation of water is a promising method to realize large-scale H2O2 production without a hazardous and energy-intensive process. In this study, we introduce a Pt/TiO2(anatase) photocatalyst to construct a simple and environmentally friendly system to achieve simultaneous H2 and H2O2 production. Both H2 and H2O2 are high-value chemicals, and their separation is automatic. Even without the assistance of a sacrificial agent, the system can reach an efficiency of 7410 and 5096 μmol g^-1 h^–1 (first 1 h) for H2 and H2O2, respectively, which is much higher than that of a commercial Pt/TiO2(anatase) system that has a similar morphology. This exceptional activity is attributed to the more favorable two-electron oxidation of water to H2O2, compared with the four-electron oxidation of water to O2.
文摘Efficient,stable,and noble‐metal‐free electrocatalysts for both the oxygen evolution reaction and the hydrogen evolution reaction are highly imperative for the realization of low‐cost commercial water‐splitting electrolyzers.Herein,a cost‐effective and ecofriendly strategy is reported to fabricate coral‐like FeNi(OH)x/Ni as a bifunctional electrocatalyst for overall water splitting in alkaline media.With the assistance of mild corrosion of Ni by Fe(NO3)3,in situ generated FeNi(OH)x nanosheets are intimately attached on metallic coral‐like Ni.Integration of these nanosheets with the electrodeposited coral‐like Ni skeleton and the supermacroporous Ni foam substrate forms a binder‐free hierarchical electrode,which is beneficial for exposing catalytic active sites,accelerating mass transport,and facilitating the release of gaseous species.In 1.0 mol L^-1 KOH solution,a symmetric electrolyzer constructed with FeNi(OH)x/Ni as both the anode and the cathode exhibits an excellent activity with an applied potential difference of 1.52 V at 10 mA cm^-2,which is superior to that of an asymmetric electrolyzer constructed with the state‐of‐the‐art RuO2‐PtC couple(applied potential difference of 1.55 V at 10 mA cm^-2).This work contributes a facile and reliable strategy for manufacturing affordable,practical,and promising water‐splitting devices.
基金Supported by the Research Fund for the Doctoral Program of Higher Education(20050145029)the Science and Technology Talents Fund for Excellent Youth of Liaoning Province(2005221012)
文摘Determination of probable mechanism function and kinetic parameters is important to hydrometallurgical kinetics.In this work,the most probable mechanism function and kinetic parameters of gibbsite dissolution in NaOH solution are studied.The sample,the mixture of synthetic gibbsite and sodium hydroxide solution,was scanned in high-pressure differential scanning calorimetry(DSC) equipment with the heating rate of 10 K·min-1. Integral equation and differential equation of non-isothermal kinetics were solved to fit the data related to DSC curve.According to the calculation results,the most probable mechanism function for pure synthetic gibbsite dissolution in sodium hydroxide solution is presented based on the optimum procedure in the database of the mechanism function.The apparent activation energy obtained is(75±1) kJ·mol-1,the frequency factor is 10 8±1mol·s-1,and the reaction is a second order reaction.
基金supported by the Strategic Priority Research Program of Chinese Academy of Sciences(XDB17000000)the Key Research Program of Frontier Sciences,CAS(QYZDY-SSW-JSC023)+1 种基金the National Natural Science Foundation of China(21603224,31470339)the National Key R&D Program of China(2017YFA0503700)~~
文摘Photocatalytic Z-scheme water splitting is considered as a promising approach to produce solar hydrogen.However,the forward hydrogen production reaction is often impeded by backward reactions.In the present study,in a photosystem Ⅱ-integrated hybrid Z-scheme water splitting system,the backward hydrogen oxidation reaction was significantly suppressed by loading a PtCrOx cocatalyst on a ZrO2/TaON photocatalyst.Due to the weak chemisorption and activation of molecular hydrogen on PtCrOx,where Pt is stabilized in the oxidized forms,Pt^Ⅱ and Pt^Ⅳ,hydrogen oxidation is inhibited.However,it is remarkably well-catalyzed by the metallic Pt cocatalyst,thereby rapidly consuming the produced hydrogen.This work describes an approach to inhibit the backward reaction in the photosystem Ⅱ-integrated hybrid Z-scheme water splitting system using Fe(CN)6^3-/Fe(CN)6^4-redox couple as an electron shuttle.
文摘We report a facile way to prepare sulfur(S) doped Ni4/5 Fe1/5-layered double hydroxide(LDH) electrocatalysts for oxygen evolution reaction(OER). The influence of S doping amount on the OER activity of the resulted Ni Fe-LDHs was studied and the optimal surface S content was ca. 0.43 at%. The developed S-doped Ni Fe-LDH exhibits excellent OER catalyst activity in 1.0 M KOH with overpotential of only 257 m V at the current density of 10 m A cm^-2. Moreover, the catalyst could maintain high activity after 30 h stability test. The high activity of the S-doped Ni Fe-LDH catalysts may originate from the synergistic effect between S and the Fe sites. This work provides a simple but efficient way to improve the OER performance of transition metal oxides/(oxy)hydroxides.
文摘Depositing a cocatalyst has proven to be an important strategy for improving the photoelectrochemical(PEC)water-splitting efficiency of photoanodes.In this study,Ni(OH)2 quantum dots(Ni(OH)2 QDs)were deposited in situ onto anα-Fe_(2)O_(3)photoanode via a chelation-mediated hydrolysis method.The photocurrent density of the Ni(OH)2 QDs/α-Fe_(2)O_(3)photoanode reached 1.93 mA·cm^(−2)at 1.23 V vs.RHE,which is 3.5 times that ofα-Fe_(2)O_(3),and an onset potential with a negative shift of ca.100 mV was achieved.More importantly,the Ni(OH)2 QDs exhibited excellent stability in maintaining PEC water oxidation at a high current density,which is attributed to the ultra-small crystalline size,allowing for the rapid acceptance of holes fromα-Fe_(2)O_(3)to Ni(OH)_(2)QDs,formation of active sites for water oxidation,and hole transfer from the active sites to water molecules.Further(photo)electrochemical analysis suggests that Ni(OH)_(2)QDs not only provide maximal active sites for water oxidation but also suppress charge recombination by passivating the surface states ofα-Fe_(2)O_(3),thereby significantly enhancing the water oxidation kinetics over theα-Fe_(2)O_(3)surface.
文摘Catalytic water splitting potentially reduce the consumption of fossil fuels and has received intense research attention.Synergy effects in multi‐element transition metal‐based water splitting catalysts have evoked special interests.Studies on catalysts in interfacial structures are especially meaningful due to their pertinence in applications.In this study,we report the synergy effects in promoting catalytic power in the ternary transition metal Zn,Co,Ni alloy nanoparticles that embeds in the carbonized Ppy/CNT multilayered matrix.By comparison with a series of binary or single metal counterparts,the mechanism under the synergy effects are elucidated.Experimental and DFT calculation results indicate that the ternary transition metal catalysts in the N‐doped carbon matrix present special electronic structure,which benefits the reversible transition‐state adsorption in HER and OER and render the catalysts high conductivity in room temperature.We expect our findings inspire further development of efficient transition metal HER and OER catalysts.
文摘Pretreatment is one of the most important steps in the production bioethanol from lignocellulose materials. Alkaline pretreatment is a common mean of pretreatment but microwave oven could assist its efficiency as it can reduce the pretreatment time and improve the enzymatic activity during hydrolysis. The aim of this paper is to determine lignin removal from banana trunk using microwave-assisted alkaline (NaOH and NH4OH) pretreatments. The best pretreatment conditions were used for mass pretreatment before hydrolysis and fermentation. The result shows that, optimum lignin removal was with microwave-assisted NaOH pretreatment with the removal of up to 98% lignin at 2% (w/v (weight/volum)) sodium hydroxide, 170 W microwave power at 10 rain. Microwave-assisted ammonium hydroxide pretreatment achieved 97% lignin removal at 1% ammonium hydroxide concentration and 680 W microwave power at 5 min. Microwave- alkaline assisted pretreatment increased the yield and quality of fermentable sugar after enzyme hydrolysis with NH4OH and ammonium hydroxide yielding 40% and 39% of ethanol, respectively. This result reveals that, well controlled microwave- alkaline assisted pretreatment of banana trunk could effectively remove lignin and give high bioethanol yield.
基金supported by the Chemical,Biological,Environmental,and Transport Systems(CBET)program of US National Science Foundation(CBET-1438440)~~
文摘An efficient and economical oxygen evolution reaction(OER)catalyst is critical to the widespread application of solar energy to fuel conversion.Among many potential OER catalysts,the metal oxyhydroxides,especially FeOOH,show promising OER reactivity.In the present work,we performed a DFT+U study of the OER mechanism on theγ‐FeOOH(010)surface.In particular,we established the chemical potential of the OH?and hole pair and included the OH?anion in the reaction pathway,accounting to the alkaline conditions of anodic OER process.We then analyzed the OER pathways on the surface with OH‐,O‐and Fe‐terminations.On the surface with OH‐and O‐terminations,the O2molecule could form from either OH reacting with the surface oxygen species(-OH*and-O*)or the combination of two surface oxygen species.On the Fe‐terminated surface,O2can only form by adsorbing OH on the Fe sites first.The potential‐limiting step of the oxygen evolution with different surface terminations was determined by following the free‐energy change of the elementary steps along each pathway.Our results show that oxygen formation requires recreating the surface Fe sites,and consequently,the condition that favors the partially exposed Fe sites will promote oxygen formation.
基金National Natural Science Foundation of China(No.20176053)
文摘Contrast degradation experiments between ethanol and polyvinyl alcohol (PVA) were conducted during H2O2, UV/H2O2, Fenton, and Photo-Fenton processes in this study. UV/VIS spectra showed' that complexes between Fe(Ⅲ) and organics were easily formed and degraded within reaction time. Compared with ,the degradation of complex, hydroxyl radicals acted weakly in Fenton or Photo-Fenton process. Hydroxyl radi'cals involved in Photo-Fenton process were deemed to be generated from the split decomposition of H2O2, photolysis of Fe_aq^3+, and degradation of hydrated Fe(Ⅳ)-complex but not traditional Fenton reaction. Experimental evidence to support this point was presented in this paper.
基金supported by the Natural Science Foundation of Hainan Province(2019RC007)Key Research and Development Project of Hainan Province(ZDYF2020037)+5 种基金the National Natural Science Foundation of China(21875133 and 51873100)Natural Science Foundation of Shaanxi Province(2020JZ-23)Fundamental Research Funds for the Central Universities(GK202101005,GK201901002,2019TS007,2021CBLZ004,and 2020CSLZ012)the Innovation Team Project for Graduate Students at Shaanxi Normal University(TD2020048Y)Open Foundation of Guangxi Key Laboratory of Processing for Non-ferrous Metals and Featured Materials at Guangxi University(2021GXYSOF02)the 111 Project(B14041)。
文摘The catalytic/electrocatalytic performance of platinum(Pt)nanostructures highly relates to their morphology.Herein,we propose a facile self-template pyrolysis strategy at high temperature to synthesize one-dimensionally holey Pt nanotubes(Pt-hNTs)using Pt^(Ⅱ)-dimethylglyoxime complex(Pt^(Ⅱ)-DMG)nanorods as the reaction precursor.The coordination capability of DMG results in the generation of Pt^(Ⅱ)-DMG nanorods,whereas the reducibility of DMG at high temperature leads to the reduction of Pt^(Ⅱ)species in Pt^(Ⅱ)-DMG nanorods.During the reaction process,the inside-out Ostwald ripening phenomenon leads to the hollow morphology of Pt-hNTs.Benefiting from the physical characteristics of hollow and holey structure,Pt-hNTs with clean surface show superior electroactivity and durability for catalyzing ethanol electrooxidation as well as hydrogen evolution reaction in alkaline media.Under optimized experimental conditions,the constructed symmetric Pt-hNTs||Pt-hNTs ethanol electrolyzer only requires an electrolysis voltage of 0.40 V to achieve the electrochemical hydrogen production,demonstrating a highly energy saving strategy relative to traditional water electrolysis.
基金supported by the National Natural Science Foundation of Chinathe National Key Research and Development Project (2018YFB1502401)+4 种基金the Royal Society and Newton Fund through Newton Advanced Fellowship award (NAF\R1\191294)the Program for Changjiang Scholars and Innovative Research Team in the Universitythe Fundamental Research Funds for the Central Universitiesthe Longterm Subsidy Mechanism from the Ministry of Finance and the Ministry of Education of Chinathe financial support from China Scholarships Council (CSC)
文摘Development of highly active electrocatalysts for oxygen evolution reaction(OER)is one of the critical issues for water splitting,and most reported catalysts operate at overpotentials above 190 mV.Here we present a multiphase nickel iron sulfide(MPS)hybrid electrode with a hierarchical structure of iron doped NiS and Ni3S2,possessing a benchmark OER activity in alkaline media with a potential as low as 1.33 V(vs.reversible hydrogen electrode)to drive an OER current density of 10 mA cm^-2.The Fe doped NiS,combined with highly conductive disulfide phase on porous Ni foam,is believed to be responsible for the ultrahigh activity.Furthermore,density functional theory simulation reveals that partially oxidized sulfur sites in Fe doped NiS could dramatically lower the energy barrier for the rate-determining elementary reaction,thus contributing to the active oxygen evolution.
基金supported by the National Key R&D Program of China(2019YFA0709200)the National Natural Science Foundation of China(21988102,51772198 and 21975171)。
文摘Water electrolysis to produce H2 is a promising strategy for generating a renewable fuel.However,the sluggish-kinetics and low value-added anodic oxygen evolution reaction(OER)restricts the overall energy conversion efficiency.Herein we report a strategy of boosting H_(2)production at low voltages by replacing OER with a bioelectrochemical cascade reaction at a triphase bioanode.In the presence of oxygen,oxidase enzymes can convert biomass into valuable products,and concurrently generate H_(2)O_(2) that can be further electrooxidized at the bioanode.Benefiting from the efficient oxidase kinetics at an oxygen-rich triphase bioanode and the more favorable thermodynamics of H_(2)O_(2)oxidation than that of OER,the cell voltage and energy consumption are reduced by~0.70 V and~36%,respectively,relative to regular water electrolysis.This leads to an efficient H_(2)production at the cathode and valuable product generation at the bioanode.Integration of a bioelectrochemical cascade into the water splitting process provides an energy-efficient and promising pathway for achieving a renewable fuel.
基金supported by the National Natural Science Foundation of China (21073232 & 50921002)the Fundamental Research Fund from the Chinese Central University (2010LKHX02)
文摘Hydrolysis and oxidation of formamidine disulfide in acidic medium were investigated using high-performance liquid chro- matography (HPLC) and mass spectrometry (MS) at 25 ~C. By controlling the slow reaction rate and choosing appropriate mobile phase, HPLC provides the unique advantages over other methods (UV-Vis, chemical separation) in species tracking and kinetic study. In addition to thiourea and formamidine sulfinic acid, two unreported products were also detected in the hy- drolysis reaction. Mass spectrometry measurement indicates these two products to be formamidine sulfenic acid and thiocyan- ogen with mass weights of 92.28 and 116,36, respectively. In the oxidation of formamidine disulfide by hydrogen peroxide, besides thiourea, formamidine sulfenic acid, formamidine sulfinic acid, thiocyanogen and urea, formamidine sulfonic acid and sulfate could be detected. The oxidation reaction was found to be first order in both forrnamidine disulfide and hydrogen per- oxide. The rate constants of hydrolysis and oxidation reactions were determined in the pH range of 1.5-3.0. It was found both rate constants are increased with the increasing of pH. Experimental curves of different species can be effectively simulated via a mechanism scheme for formamidine disulfide oxidation, including hydrolysis equilibrium of formamidine disulfide and irre- versible hydrolysis of formamidine sulfenic acid.