Efficient photocatalytic reduction of CO_(2) to high-calorific-value CH4,an ideal target product,is a blueprint for C_(1)industry relevance and carbon neutrality,but it also faces great challenges.Herein,we demonstrat...Efficient photocatalytic reduction of CO_(2) to high-calorific-value CH4,an ideal target product,is a blueprint for C_(1)industry relevance and carbon neutrality,but it also faces great challenges.Herein,we demonstrate unprecedented hybrid SiC photocatalysts modified by Fe-based cocatalyst,which are prepared via a facile impregnation-reduction method,featuring an optimized local electronic structure.It exhibits a superior photocatalytic carbon-based products yield of 30.0μmol g^(−1) h^(−1) and achieves a record CH_(4) selectivity of up to 94.3%,which highlights the effectiveness of electron-rich Fe cocatalyst for boosting photocatalytic performance and selectivity.Specifically,the synergistic effects of directional migration of photogenerated electrons and strongπ-back bonding on low-valence Fe effectively strengthen the adsorption and activation of reactants and intermediates in the CO_(2)→CH_(4) pathway.This study inspires an effective strategy for enhancing the multielectron reduction capacity of semiconductor photocatalysts with low-cost Fe instead of noble metals as cocatalysts.展开更多
The integration of electrochemical CO_(2)reduction(CO_(2)RR) and photoelectrochemical water oxidation offers a sustainable access to valuable chemicals and fuels. Here, we develop a rapidly annealed hematite photoanod...The integration of electrochemical CO_(2)reduction(CO_(2)RR) and photoelectrochemical water oxidation offers a sustainable access to valuable chemicals and fuels. Here, we develop a rapidly annealed hematite photoanode with a photocurrent density of 2.83 mA cm^(-2)at 1.7 VRHEto drive the full-reaction. We also present Cu-alloys electrocatalysis extended from CuInSnS4, which are superior in both activity and selectivity for CO_(2)RR. Specifically, the screened CuInSn achieves a CO_(2)to HCOOH Faradaic efficiency of 93% at a cell voltage of-2.0 V by assembling into artificial photosynthesis cell. The stability test of IT exhibits less than 3% degradation over 24 h. Furthermore, in-situ Raman spectroscopy reveals that both CO_(3)^(-2)and CO_(2)are involved in CO_(2)RR as reactants. The preferential affinity of C for H in the ^(*)HCO_(2)intermediate enables an improved HCOOH-selectivity, highlighting the role of multifunctional Cu in reducing the cell voltage and enhancing the photocurrent density.展开更多
The ZnO sol well-crystallized was prepared by the sol-gel method. The ZnO films were coated on medical-grade PVC surface by the improved organic-inorganic interfacial adhesion method. The physical and photocatalytic p...The ZnO sol well-crystallized was prepared by the sol-gel method. The ZnO films were coated on medical-grade PVC surface by the improved organic-inorganic interfacial adhesion method. The physical and photocatalytic properties of the samples were characterized by XRD, SEM, DRS spectra and measured by the photodegradation reaction of Rho-damine B (RhB) and anti-bacteria for Escherichia coli (E. coli), respectively. The results show that pretreatment of PVC by the mix solution of THF-PVC helps to improve the amount and adhesion strength of ZnO suspension to PVC surface. The photocatalytic and antibacterial properties of the THF-ZnO/PVC film are better than that of the ZnO/PVC and neat PVC. Under UV irradiation, the THF-ZnO/PVC film shows the best antibacterial properties with 99% kill rate of bacteria.展开更多
Sunlight is the most abundant and inexhaustible energy source on earth.However,its low energy density,dispersibility and intermittent nature make its direct utilization with industrial relevance challenging,suggesting...Sunlight is the most abundant and inexhaustible energy source on earth.However,its low energy density,dispersibility and intermittent nature make its direct utilization with industrial relevance challenging,suggesting that converting sunlight into chemical energy and storing it is a valuable measure to achieve global sustainable development.Carbon–neutral,clean and secondary pollution-free solar-driven water splitting to produce hydrogen is one of the most attractive avenues among all the current options and is expected to realize the transformation from dependence on fossil fuels to zero-pollution hydrogen.Artificial photosynthetic systems(APSs)based on photoelectrochemical(PEC)devices appear to be an ideal avenue to efficiently achieve solar-to-hydrogen conversion.In this review,we comprehensively highlight the recent developments in photocathodes,including architectures,semiconductor photoabsorbers and performance optimization strategies.In particular,frontier research cases of organic semiconductors,dye sensitization and surface grafted molecular catalysts applied to APSs based on frontier(molecular)orbital theory and semiconductor energy band theory are discussed.Moreover,research advances in typical photoelectrodes with the metal–insulator–semiconductor(MIS)architecture based on quantum tunnelling are also introduced.Finally,we discuss the benchmarks and protocols for designing integrated tandem photoelectrodes and PEC systems that conform to the solar spectrum to achieve high-efficiency and cost-effective solar-to-hydrogen conversion at an industrial scale in the near future.展开更多
CdZnS solid solutions with strong light absorption are promising materials for solar-driven COreduction;however,their relatively weak redox ability and intrinsic photo-corrosion limit their further development as a ph...CdZnS solid solutions with strong light absorption are promising materials for solar-driven COreduction;however,their relatively weak redox ability and intrinsic photo-corrosion limit their further development as a photocatalyst.The addition of a second photocatalyst with a suitable band structure to construct a S-scheme photocatalytic system can solve both problems simultaneously.Here,we report a S-scheme photocatalyst based on the heterostructure of CoTiO_(3)/CdZnS(abbreviated as CoTiO_(3)/Cd_(9.51)Zn_(0.49)S_(10))that enables the efficient photocatalytic reduction of CO.Detailed physicochemical characterization resolves the S-scheme charge transfer mechanism in this composite photocatalyst.With the well-designed structure of particles and desirable band offsets,this hybrid system offers visible light absorption in a broad spectral region,large surface area,strong redox ability,and fast carrier separation and transportation.Under visible-light illumination,the CoTiO_(3)/Cd Zn S hybrid system displays a CO formation rate of about 11 mmol hgcombined with a long-term operational stability.Besides,a high apparent quantum efficiency(AQE)of 7.27%is realized for the CO_(2)-to-CO reduction reaction by the optimized Co TiO/Cd Zn S hybrid under 420 nm monochromatic light irradiation.展开更多
For a long time, there has been global concern over the environment and energy problems. Recently, the problems, which have brought about serious effect on the global living condition, have been in the ‘‘spotlight&q...For a long time, there has been global concern over the environment and energy problems. Recently, the problems, which have brought about serious effect on the global living condition, have been in the ‘‘spotlight" and given impetus to the universal's efforts to head for the same direction: stem the worst warming and strive for the renewable energy source. Hydrogen peroxide(H_2O_2) is undoubtedly a good choice,which holds the promise as a clean, efficient, safe and transferrable energy carrier. Octahedral coordination polymer, Cd_3(C_3N_3S_3)_2, was found to be a robust photocatalyst for H_2O_2 generation under visible light irradiation. To further improve the H_2O_2 generation efficiency, adhering the octahedron to reduced graphene(rGO) was applied as the strategy herein. The study shows that by adhering Cd_3(C_3N_3S_3)_2to rGO, the formation of H_2O_2 is 2.5-fold enhanced and its deformation is concurrently suppressed. This work not only demonstrates the effectiveness of adhering Cd_3(C_3N_3S_3)_2polymer to rGO for the improvement of the polymer's photocatalytic performance, but also proposes a general way for the fabrication of graphene/coordination compound hybrids for maximizing their synergy.展开更多
ZnIn_(2)S_(4) has emerged in water splitting and degradation of dyes due to its good stability and light absorption properties.However,there are still few reports of CO_(2) photoreduction.Herein,we successfully synthe...ZnIn_(2)S_(4) has emerged in water splitting and degradation of dyes due to its good stability and light absorption properties.However,there are still few reports of CO_(2) photoreduction.Herein,we successfully synthesized ZnIn_(2)S_(4) and obtained a series of ZnIn_(2)S_(4)-CdIn_(2)S_(4) heterostructured microspheres through the ion exchange method,and first used them in photocatalytic CO_(2) reduction in noble-metal-free systems.The activity results showed that these ZnIn_(2)S_(4)-CdIn_(2)S_(4) photocatalysts exhibit excellent catalytic activity under visible light,and the best CO yield is as high as 33.57μmol・h^(-1) with a selectivity of 91%.Furthermore,the stability and reusability of ZnIn_(2)S_(4)-CdIn_(2)S_(4) was firmly confirmed by diverse characterizations,including X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),energy-dispersive X-ray spectroscopy(EDX)and N2 adsorption measurements.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22072022)the Natural Science Foundation of Fujian Province(2021L3003)the Science Foundation of Shandong Province(ZR2019BB065).
文摘Efficient photocatalytic reduction of CO_(2) to high-calorific-value CH4,an ideal target product,is a blueprint for C_(1)industry relevance and carbon neutrality,but it also faces great challenges.Herein,we demonstrate unprecedented hybrid SiC photocatalysts modified by Fe-based cocatalyst,which are prepared via a facile impregnation-reduction method,featuring an optimized local electronic structure.It exhibits a superior photocatalytic carbon-based products yield of 30.0μmol g^(−1) h^(−1) and achieves a record CH_(4) selectivity of up to 94.3%,which highlights the effectiveness of electron-rich Fe cocatalyst for boosting photocatalytic performance and selectivity.Specifically,the synergistic effects of directional migration of photogenerated electrons and strongπ-back bonding on low-valence Fe effectively strengthen the adsorption and activation of reactants and intermediates in the CO_(2)→CH_(4) pathway.This study inspires an effective strategy for enhancing the multielectron reduction capacity of semiconductor photocatalysts with low-cost Fe instead of noble metals as cocatalysts.
基金financially supported by the National Key R&D Program of China (2018YFE0208500)the National Natural Science Foundation of China (Grants No. 22072022)funded by King Abdullah University of Science and Technology (KAUST) through the baseline funding (BAS/1/1413-01-01)。
文摘The integration of electrochemical CO_(2)reduction(CO_(2)RR) and photoelectrochemical water oxidation offers a sustainable access to valuable chemicals and fuels. Here, we develop a rapidly annealed hematite photoanode with a photocurrent density of 2.83 mA cm^(-2)at 1.7 VRHEto drive the full-reaction. We also present Cu-alloys electrocatalysis extended from CuInSnS4, which are superior in both activity and selectivity for CO_(2)RR. Specifically, the screened CuInSn achieves a CO_(2)to HCOOH Faradaic efficiency of 93% at a cell voltage of-2.0 V by assembling into artificial photosynthesis cell. The stability test of IT exhibits less than 3% degradation over 24 h. Furthermore, in-situ Raman spectroscopy reveals that both CO_(3)^(-2)and CO_(2)are involved in CO_(2)RR as reactants. The preferential affinity of C for H in the ^(*)HCO_(2)intermediate enables an improved HCOOH-selectivity, highlighting the role of multifunctional Cu in reducing the cell voltage and enhancing the photocurrent density.
文摘The ZnO sol well-crystallized was prepared by the sol-gel method. The ZnO films were coated on medical-grade PVC surface by the improved organic-inorganic interfacial adhesion method. The physical and photocatalytic properties of the samples were characterized by XRD, SEM, DRS spectra and measured by the photodegradation reaction of Rho-damine B (RhB) and anti-bacteria for Escherichia coli (E. coli), respectively. The results show that pretreatment of PVC by the mix solution of THF-PVC helps to improve the amount and adhesion strength of ZnO suspension to PVC surface. The photocatalytic and antibacterial properties of the THF-ZnO/PVC film are better than that of the ZnO/PVC and neat PVC. Under UV irradiation, the THF-ZnO/PVC film shows the best antibacterial properties with 99% kill rate of bacteria.
基金supported by the National Key R&D Program of China(2018YFE0208500)the National Natural Science Foundation of China(Grant Nos.22072022,21773031,22011530144).
文摘Sunlight is the most abundant and inexhaustible energy source on earth.However,its low energy density,dispersibility and intermittent nature make its direct utilization with industrial relevance challenging,suggesting that converting sunlight into chemical energy and storing it is a valuable measure to achieve global sustainable development.Carbon–neutral,clean and secondary pollution-free solar-driven water splitting to produce hydrogen is one of the most attractive avenues among all the current options and is expected to realize the transformation from dependence on fossil fuels to zero-pollution hydrogen.Artificial photosynthetic systems(APSs)based on photoelectrochemical(PEC)devices appear to be an ideal avenue to efficiently achieve solar-to-hydrogen conversion.In this review,we comprehensively highlight the recent developments in photocathodes,including architectures,semiconductor photoabsorbers and performance optimization strategies.In particular,frontier research cases of organic semiconductors,dye sensitization and surface grafted molecular catalysts applied to APSs based on frontier(molecular)orbital theory and semiconductor energy band theory are discussed.Moreover,research advances in typical photoelectrodes with the metal–insulator–semiconductor(MIS)architecture based on quantum tunnelling are also introduced.Finally,we discuss the benchmarks and protocols for designing integrated tandem photoelectrodes and PEC systems that conform to the solar spectrum to achieve high-efficiency and cost-effective solar-to-hydrogen conversion at an industrial scale in the near future.
基金the National Key R&D Program of China(2021YFA1502100)NSFC(Grants Nos.21773031,22011530144,U1805255)+3 种基金Natural Science Foundation of Fujian Province of China(2018J01686)the State Key Laboratory of NBC Protection for Civilian(SKLNBC2020-18)Graphene Powder&Composite Research Center of Fujian Province(2017H2001)financial support from the Research Foundation,Flanders(FWO Grant No.VS052320N)。
文摘CdZnS solid solutions with strong light absorption are promising materials for solar-driven COreduction;however,their relatively weak redox ability and intrinsic photo-corrosion limit their further development as a photocatalyst.The addition of a second photocatalyst with a suitable band structure to construct a S-scheme photocatalytic system can solve both problems simultaneously.Here,we report a S-scheme photocatalyst based on the heterostructure of CoTiO_(3)/CdZnS(abbreviated as CoTiO_(3)/Cd_(9.51)Zn_(0.49)S_(10))that enables the efficient photocatalytic reduction of CO.Detailed physicochemical characterization resolves the S-scheme charge transfer mechanism in this composite photocatalyst.With the well-designed structure of particles and desirable band offsets,this hybrid system offers visible light absorption in a broad spectral region,large surface area,strong redox ability,and fast carrier separation and transportation.Under visible-light illumination,the CoTiO_(3)/Cd Zn S hybrid system displays a CO formation rate of about 11 mmol hgcombined with a long-term operational stability.Besides,a high apparent quantum efficiency(AQE)of 7.27%is realized for the CO_(2)-to-CO reduction reaction by the optimized Co TiO/Cd Zn S hybrid under 420 nm monochromatic light irradiation.
基金financially supported by the National Natural Science Foundation of China(21003021 and 21373051)
文摘For a long time, there has been global concern over the environment and energy problems. Recently, the problems, which have brought about serious effect on the global living condition, have been in the ‘‘spotlight" and given impetus to the universal's efforts to head for the same direction: stem the worst warming and strive for the renewable energy source. Hydrogen peroxide(H_2O_2) is undoubtedly a good choice,which holds the promise as a clean, efficient, safe and transferrable energy carrier. Octahedral coordination polymer, Cd_3(C_3N_3S_3)_2, was found to be a robust photocatalyst for H_2O_2 generation under visible light irradiation. To further improve the H_2O_2 generation efficiency, adhering the octahedron to reduced graphene(rGO) was applied as the strategy herein. The study shows that by adhering Cd_3(C_3N_3S_3)_2to rGO, the formation of H_2O_2 is 2.5-fold enhanced and its deformation is concurrently suppressed. This work not only demonstrates the effectiveness of adhering Cd_3(C_3N_3S_3)_2polymer to rGO for the improvement of the polymer's photocatalytic performance, but also proposes a general way for the fabrication of graphene/coordination compound hybrids for maximizing their synergy.
基金This work is supported by National Natural Science Foundation of China(FZUL 21876204 and 22072022)the State Key Laboratory of NBC Protection(SKLNBC2019-14 and SKLNBC2020-18).
文摘ZnIn_(2)S_(4) has emerged in water splitting and degradation of dyes due to its good stability and light absorption properties.However,there are still few reports of CO_(2) photoreduction.Herein,we successfully synthesized ZnIn_(2)S_(4) and obtained a series of ZnIn_(2)S_(4)-CdIn_(2)S_(4) heterostructured microspheres through the ion exchange method,and first used them in photocatalytic CO_(2) reduction in noble-metal-free systems.The activity results showed that these ZnIn_(2)S_(4)-CdIn_(2)S_(4) photocatalysts exhibit excellent catalytic activity under visible light,and the best CO yield is as high as 33.57μmol・h^(-1) with a selectivity of 91%.Furthermore,the stability and reusability of ZnIn_(2)S_(4)-CdIn_(2)S_(4) was firmly confirmed by diverse characterizations,including X-ray diffraction(XRD),scanning electron microscopy(SEM),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),energy-dispersive X-ray spectroscopy(EDX)and N2 adsorption measurements.
