In order to avoid the formation ofηphase(W_(6)Co_(6)C or W_(3)Co_(3)C)that adversely affects the sintering process and its products in the preparation process of ultra-fine WC-Co powder,a technical route of prereduct...In order to avoid the formation ofηphase(W_(6)Co_(6)C or W_(3)Co_(3)C)that adversely affects the sintering process and its products in the preparation process of ultra-fine WC-Co powder,a technical route of prereduction of WO_(3)-Co_(3)O_(4)to WO_(2)-Co and then deep reduction carbonization to WC-Co powder has been proposed.This study mainly investigates the influence of gas partial pressure on the pre-reduction process of WO_(3)-Co_(3)O_(4)under a mixed atmosphere of H_(2)-C_(2)H_(4)-Ar at 600℃and establishes the kinetic equations of pre-reduction and carbon evolution.The results indicate that increasing the partial pressure of hydrogen is conducive to the rapid and complete conversion of WO_(3) to WO_(2).High carbon content can be generated by the deposition of C_(2)H_(4),and it hinders the diffusion of the reducing gas;WO_(3)still cannot be completely reduced to WO_(2)as the partial pressure of C_(2)H_(4) increases to 60%.For the carbon evolution of C_(2)H_(4),the carbon amount is positively related to the H_(2)partial pressure,but it shows the highest amount and evolution rate when the ethylene partial pressure is 20%.Based on the reduction rate curves of WO_(3) and carbon evolution rate curves of C_(2)H_(4),the rate equations of pre-reduction and carbon evolution of WO_(3)-Co_(3)O_(4)system at 600℃are established.The pre-reduction reaction belongs to the first-order reaction,and its equation is expressed as follows:r=-(dw_(WO_(3)))/dt=(9±0.15)×10^(-2)×P_(H_(2))^(0.44)P_(C_(2)H_(4))&(0.57)The carbon deposition rate equation of C_(2)H_(4) can be expressed as follows:r=-(dc_C)/dt=r_f-r_b≌7.35×10^(-2)×P_(C_(2)H_(4))^(0.31)展开更多
Heterojunction construction,especially S-scheme heterojunction,represents an efficient universal strategy to achieve high-performance photocatalytic materials.For further performance stimulation of these well-designed...Heterojunction construction,especially S-scheme heterojunction,represents an efficient universal strategy to achieve high-performance photocatalytic materials.For further performance stimulation of these well-designed heterojunctions,modulating the interfacial internal electric field(IEF)to steer dynamic charge transfer represents a promising approach.Herein,we realized the precise regulation of Fermi level(E_(F))of the oxidation semiconductor(mesoporous WO_(3-x))by tailoring the concentration of oxygen vacancies(V_(O)),maximizing the IEF intensity in Cs_(2)CuBr_(4)@WO_(3-x)(CCB@WO_(3-x))S-scheme heterojunction.The augmented IEF affords a robust driving force for directional electron delivery,leading to boosted charge separation.Hence,the developed CCB@WO_(3-x)S-scheme heterojunction demonstrated outstanding photocatalytic CO_(2)reduction performance,with the electron consumption rate(Relectron)up to 390.34μmol g^(-1)h^(-1),which is 3.28 folds higher than that of pure CCB.An in-depth analysis of the S-scheme electron transfer mode was presented via theoretical investigations,electron spin resonance(ESR),photo-irradiated Kelvin probe force microscopy(KPFM),and in-situ X-ray photoelectron spectroscopy(XPS).Finally,the CO_(2)photoconversion route was explored in detail using in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and DFT theoretical calculations.展开更多
Photocatalytic H_(2) evolution from seawater splitting presents a promising approach to tackle the fossil energy crisis and mitigate carbon emission due to the abundant source of seawater and sunlight on the earth.How...Photocatalytic H_(2) evolution from seawater splitting presents a promising approach to tackle the fossil energy crisis and mitigate carbon emission due to the abundant source of seawater and sunlight on the earth.However,the development of efficient photocatalysts for seawater splitting remains a formidable challenge.Herein,a 2D/2D ZnIn_(2)S_(4)/WO_(3)(ZIS/WO_(3))heterojunction nanostructure is fabricated to efficiently separate the photoinduced carriers by steering electron transfer from the conduction band minimum of WO_(3) to the valence band maximum of ZIS via constructing internal electric field.Subsequently,plasmonic Au nanoparticles(NPs)as a novel photosensitizer and a reduction cocatalyst are anchored on ZIS/WO_(3) surface to further enhance the optical absorption of ZIS/WO_(3) heterojunction and accelerate the catalytic conversion.The obtained Au/ZIS/WO_(3) photocatalyst exhibits an outstanding H_(2) evolution rate of 2610.6 or 3566.3μmol g^(-1)h~(-1)from seawater splitting under visible or full-spectrum light irradiation,respectively.These rates represent an impressive increase of approximately 7.3-and 6,6-fold compared to those of ZIS under the illumination of the same light source.The unique 2D/2D structure,internal electric field,and plasmonic metal modification together boost the photocatalytic H_(2) evolution rate of Au/ZIS/WO_(3),making it even comparable to H_(2) evolution from pure water splitting.The present work sheds light on the development of efficient photocatalysts for seawater splitting.展开更多
基金the National Natural Science Foundation of China(22078326,21878305,21908227)。
文摘In order to avoid the formation ofηphase(W_(6)Co_(6)C or W_(3)Co_(3)C)that adversely affects the sintering process and its products in the preparation process of ultra-fine WC-Co powder,a technical route of prereduction of WO_(3)-Co_(3)O_(4)to WO_(2)-Co and then deep reduction carbonization to WC-Co powder has been proposed.This study mainly investigates the influence of gas partial pressure on the pre-reduction process of WO_(3)-Co_(3)O_(4)under a mixed atmosphere of H_(2)-C_(2)H_(4)-Ar at 600℃and establishes the kinetic equations of pre-reduction and carbon evolution.The results indicate that increasing the partial pressure of hydrogen is conducive to the rapid and complete conversion of WO_(3) to WO_(2).High carbon content can be generated by the deposition of C_(2)H_(4),and it hinders the diffusion of the reducing gas;WO_(3)still cannot be completely reduced to WO_(2)as the partial pressure of C_(2)H_(4) increases to 60%.For the carbon evolution of C_(2)H_(4),the carbon amount is positively related to the H_(2)partial pressure,but it shows the highest amount and evolution rate when the ethylene partial pressure is 20%.Based on the reduction rate curves of WO_(3) and carbon evolution rate curves of C_(2)H_(4),the rate equations of pre-reduction and carbon evolution of WO_(3)-Co_(3)O_(4)system at 600℃are established.The pre-reduction reaction belongs to the first-order reaction,and its equation is expressed as follows:r=-(dw_(WO_(3)))/dt=(9±0.15)×10^(-2)×P_(H_(2))^(0.44)P_(C_(2)H_(4))&(0.57)The carbon deposition rate equation of C_(2)H_(4) can be expressed as follows:r=-(dc_C)/dt=r_f-r_b≌7.35×10^(-2)×P_(C_(2)H_(4))^(0.31)
基金This work was financially supported by the National Natural Science Foundation of China(51972213)Natural Science Foundation of Shanghai(22ZR1460700).
文摘Heterojunction construction,especially S-scheme heterojunction,represents an efficient universal strategy to achieve high-performance photocatalytic materials.For further performance stimulation of these well-designed heterojunctions,modulating the interfacial internal electric field(IEF)to steer dynamic charge transfer represents a promising approach.Herein,we realized the precise regulation of Fermi level(E_(F))of the oxidation semiconductor(mesoporous WO_(3-x))by tailoring the concentration of oxygen vacancies(V_(O)),maximizing the IEF intensity in Cs_(2)CuBr_(4)@WO_(3-x)(CCB@WO_(3-x))S-scheme heterojunction.The augmented IEF affords a robust driving force for directional electron delivery,leading to boosted charge separation.Hence,the developed CCB@WO_(3-x)S-scheme heterojunction demonstrated outstanding photocatalytic CO_(2)reduction performance,with the electron consumption rate(Relectron)up to 390.34μmol g^(-1)h^(-1),which is 3.28 folds higher than that of pure CCB.An in-depth analysis of the S-scheme electron transfer mode was presented via theoretical investigations,electron spin resonance(ESR),photo-irradiated Kelvin probe force microscopy(KPFM),and in-situ X-ray photoelectron spectroscopy(XPS).Finally,the CO_(2)photoconversion route was explored in detail using in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and DFT theoretical calculations.
基金supported by the National Natural Science Foundation of China(21872104,21501131,21978216 and 22272082)the Natural Science Foundation of Tianjin for Distinguished Young Scholar(20JCJQJC00150)the Analytical&Testing Center of Tiangong University for PL work。
文摘Photocatalytic H_(2) evolution from seawater splitting presents a promising approach to tackle the fossil energy crisis and mitigate carbon emission due to the abundant source of seawater and sunlight on the earth.However,the development of efficient photocatalysts for seawater splitting remains a formidable challenge.Herein,a 2D/2D ZnIn_(2)S_(4)/WO_(3)(ZIS/WO_(3))heterojunction nanostructure is fabricated to efficiently separate the photoinduced carriers by steering electron transfer from the conduction band minimum of WO_(3) to the valence band maximum of ZIS via constructing internal electric field.Subsequently,plasmonic Au nanoparticles(NPs)as a novel photosensitizer and a reduction cocatalyst are anchored on ZIS/WO_(3) surface to further enhance the optical absorption of ZIS/WO_(3) heterojunction and accelerate the catalytic conversion.The obtained Au/ZIS/WO_(3) photocatalyst exhibits an outstanding H_(2) evolution rate of 2610.6 or 3566.3μmol g^(-1)h~(-1)from seawater splitting under visible or full-spectrum light irradiation,respectively.These rates represent an impressive increase of approximately 7.3-and 6,6-fold compared to those of ZIS under the illumination of the same light source.The unique 2D/2D structure,internal electric field,and plasmonic metal modification together boost the photocatalytic H_(2) evolution rate of Au/ZIS/WO_(3),making it even comparable to H_(2) evolution from pure water splitting.The present work sheds light on the development of efficient photocatalysts for seawater splitting.
