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
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
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.
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.
