BiVO_(4)is one of the most promising photoanode materials for photoelectrochemical(PEC)solar energy conversion,but it still suffers from poor photocurrent density due to insufficient light‐harvesting efficiency(LHE),...BiVO_(4)is one of the most promising photoanode materials for photoelectrochemical(PEC)solar energy conversion,but it still suffers from poor photocurrent density due to insufficient light‐harvesting efficiency(LHE),weak photogenerated charge separation efficiency(Φ_(Sep)),and low water oxidation efficiency(Φ_(OX)).Herein,we tackle these challenges of the BiVO_(4)photoanodes using systematic engineering,including catalysis engineering,bandgap engineering,and morphology engineering.In particular,we deposit a NiCoO_(x)layer onto the BiVO_(4)photoanode as the oxygen evolution catalyst to enhance theΦ_(OX)of Fe‐g‐C_(3)N_(4)/BiVO_(4)for PEC water oxidation,and incorporate Fe‐doped graphite‐phase C_(3)N_(4)(Fe‐g‐C_(3)N_(4))into the BiVO_(4)photoanode to optimize the bandgap and surface areas to subsequently expand the light absorption range of the photoanode from 530 to 690 nm,increase the LHE andΦ_(Sep),and further improve the oxygen evolution reaction activity of the NiCoO_(x)catalytic layer.Consequently,the maximum photocurrent density of the as‐prepared NiCoO_(x)/Fe‐g‐C_(3)N_(4)/BiVO_(4)is remarkably boosted from 4.6 to 7.4 mA cm^(−2).This work suggests that the proposed systematic engineering strategy is exceptionally promising for improving LHE,Φ_(Sep),andΦ_(OX)of BiVO_(4)‐based photoanodes,which will substantially benefit the design,preparation,and large‐scale application of next‐generation high‐performance photoanodes.展开更多
Metal halide perovskite(MHP)has become one of the most promising materials for photocatalytic CO_(2)reduction owing to the wide light absorption range,negative conduction band position and high reduction ability.Howev...Metal halide perovskite(MHP)has become one of the most promising materials for photocatalytic CO_(2)reduction owing to the wide light absorption range,negative conduction band position and high reduction ability.However,photoreduction of CO_(2)by MHP remains a challenge because of the slow charge separation and transfer.Herein,a cobalt single-atom modified nitrogen-doped graphene(Co-NG)cocatalyst is prepared for enhanced photocatalytic CO_(2)reduction of bismuth-based MHP Cs_(3)Bi_(2)Br_(9).The optimal Cs_(3)Bi_(2)Br_(9)/Co-NG composite exhibits the CO production rate of 123.16μmol g-1 h-1,which is 17.3 times higher than that of Cs_(3)Bi_(2)Br_(9).Moreover,the Cs_(3)Bi_(2)Br_(9)/Co-NG composite photocatalyst exhibits nearly 100%CO selectivity as well as impressive long-term stability.Charge carrier dynamic characterizations such as Kelvin probe force microscopy(KPFM),single-particle PL microscope and transient absorption(TA)spectroscopy demonstrate the vital role of Co-NG cocatalyst in accelerating the transfer and separation of photogenerated charges and improving photocatalytic performance.The reaction mechanism has been demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy measurement.In addition,in situ X-ray photoelectron spectroscopy test and theoretical calculation reveal the reaction reactive sites and reaction energy barriers,demonstrating that the introduction of Co-NG promotes the formation of~(*)COOH intermediate,providing sufficient evidence for the highly selective generation of CO.This work provides an effective single-atom-based cocatalyst modification strategy for photocatalytic CO_(2)reduction and is expected to shed light on other photocatalytic applications.展开更多
The design and synthesis of novel photocatalyst with self-temperature control function is an important topic in the field of advanced environmental functional materials.In this work,submicron-sized magnetic phase chan...The design and synthesis of novel photocatalyst with self-temperature control function is an important topic in the field of advanced environmental functional materials.In this work,submicron-sized magnetic phase change microcapsules composed of paraffin core and Fe_(3)O_(4)-loaded silica shell are prepared,on which the Bi_(2)WO_(6)crystals is grown in situ through hydrothermal reaction to obtain novel magnetic phase-change-microcapsule-supported Bi_(2)WO_(6)catalyst(MP@FS/BWO).The MP@FS/BWO has a paraffin encapsulation ratio of 57.1%,and the phase change enthalpy of 105.1 J/g in a temperature range of 50–60℃,which endows the MP@FS/BWO with a certain self-temperature regulation ability.MP@FS/BWO shows excellent catalytic performance in the decomposition of rhodamine B under the simulated sunlight irradiation.After the light source is turned off,it still has good catalytic ability by maintaining high temperature due to its temperature control function based on the phase transition process.The MP@FS/BWO can be easily recycled by magnetic separation and shows good structural stability and reusability.This work provides a new idea for the development of long-effect and energy-saving outdoor photocatalysts.展开更多
Although spatial charge separation between different facets of semiconductor crystals has been recognized as a general strategy in photocatalysis, the vital role of crystal morphology symmetry in charge separation pro...Although spatial charge separation between different facets of semiconductor crystals has been recognized as a general strategy in photocatalysis, the vital role of crystal morphology symmetry in charge separation properties still remains elusive. Herein,taking monoclinic bismuth vanadate(BiVO_(4)) as a platform, we found distinct charge separation difference via rationally tailoring the morphology symmetry from octahedral to truncated octahedral crystals. For octahedral BiVO_(4), photogenerated electrons and holes can be separated between edges and quasi-equivalent facets. However, as for truncated octahedral crystals,photogenerated electrons tend to transfer to {010} facets while photogenerated holes prefer to accumulate on {120} facets, thus realizing the spatial separation of photogenerated charge between different facets. Morphology tailoring of BiVO_(4) crystals leads to a significantly improved photogenerated charge separation efficiency and photocatalytic water oxidation activity. The built-in electric field for driving the separation of photogenerated electrons and holes is considered to be modulated by tuning the morphology symmetry of BiVO_(4) crystals. This work discloses the significant roles of morphology symmetry in photogenerated charge separation and facilitates the rational design of artificial photocatalysts.展开更多
Oxygen vacancy-rich bismuth oxysulfide(Bi_(2)O_(2)S)with layered structure was prepared for efficient photocatalytic CO_(2) reduction under visible light irradiation.The existence of rich oxygen vacancies in Bi_(2)O_(...Oxygen vacancy-rich bismuth oxysulfide(Bi_(2)O_(2)S)with layered structure was prepared for efficient photocatalytic CO_(2) reduction under visible light irradiation.The existence of rich oxygen vacancies in Bi_(2)O_(2)S,which was proven by sufficient characterization,can provide abundant active sites,improve CO_(2) adsorption and activation abilities and boost the separation efficiency of photogenerated carriers,as determined by theoretical and experimental analyses.As a result,Bi_(2)O_(2)S with rich oxygen vacancies achieves excellent CO_(2) conversion with a CH4 production of 65.8μmol g^(-1) under 90 min of visible light irradiation,which was 27-fold higher than the pristine Bi_(2)O_(2)S.The mechanism of photocatalytic conversion of CO_(2) to CH4 was also determined by in situ FT-IR analyses.This study provides an in-depth understanding of the development of Bi-O-S system photocatalysts through defect engineering for photocatalytic CO_(2) reduction.展开更多
Solar-driven water splitting is considered as a promising method to mitigate the energy crisis and various environmental issues.Bismuth vanadate(BiVO_(4))is photoanode material with tremendous potential for photoelect...Solar-driven water splitting is considered as a promising method to mitigate the energy crisis and various environmental issues.Bismuth vanadate(BiVO_(4))is photoanode material with tremendous potential for photoelectrochemical(PEC)water splitting.However,its PEC performance is severely hindered owing to poor surface charge transfer,surface recombination at the photoanode/electrolyte junction,and sluggish oxygen evolution reaction(OER)kinetics.In this regard,a novel solution was developed in this study to address these issues by decorating the surface of BiVO_(4)with cobalt sulfide,whose attractive features such as low cost,high conductivity,and rapid charge-transfer ability assisted in improving the PEC activity of the BiVO_(4)photoanode.The fabricated photoanode exhibited a significantly enhanced photocurrent density of 3.2 m A cm^(-2)under illumination at 1.23 V vs.a reversible hydrogen electrode,which is more than 2.5 times greater than that of pristine BiVO_(4).Moreover,the Co S/BiVO_(4)photoanode also exhibited considerable improvements in the charge injection yield(75.8%vs.36.7%for the bare BiVO_(4)film)and charge separation efficiency(79.8%vs.66.8%for the pristine BiVO_(4)film).These dramatic enhancements were primarily ascribed to rapid charge-transport kinetics and efficient reduction of the anodic overpotential for oxygen evolution enabled by the surface modification of BiVO_(4)by Co S.This study provides valuable suggestions for designing efficient photocatalysts via surface modification to improve the PEC performance.展开更多
基金Natural Science Foundation of China,Grant/Award Number:22108042Guangzhou(202201020147)。
文摘BiVO_(4)is one of the most promising photoanode materials for photoelectrochemical(PEC)solar energy conversion,but it still suffers from poor photocurrent density due to insufficient light‐harvesting efficiency(LHE),weak photogenerated charge separation efficiency(Φ_(Sep)),and low water oxidation efficiency(Φ_(OX)).Herein,we tackle these challenges of the BiVO_(4)photoanodes using systematic engineering,including catalysis engineering,bandgap engineering,and morphology engineering.In particular,we deposit a NiCoO_(x)layer onto the BiVO_(4)photoanode as the oxygen evolution catalyst to enhance theΦ_(OX)of Fe‐g‐C_(3)N_(4)/BiVO_(4)for PEC water oxidation,and incorporate Fe‐doped graphite‐phase C_(3)N_(4)(Fe‐g‐C_(3)N_(4))into the BiVO_(4)photoanode to optimize the bandgap and surface areas to subsequently expand the light absorption range of the photoanode from 530 to 690 nm,increase the LHE andΦ_(Sep),and further improve the oxygen evolution reaction activity of the NiCoO_(x)catalytic layer.Consequently,the maximum photocurrent density of the as‐prepared NiCoO_(x)/Fe‐g‐C_(3)N_(4)/BiVO_(4)is remarkably boosted from 4.6 to 7.4 mA cm^(−2).This work suggests that the proposed systematic engineering strategy is exceptionally promising for improving LHE,Φ_(Sep),andΦ_(OX)of BiVO_(4)‐based photoanodes,which will substantially benefit the design,preparation,and large‐scale application of next‐generation high‐performance photoanodes.
文摘Metal halide perovskite(MHP)has become one of the most promising materials for photocatalytic CO_(2)reduction owing to the wide light absorption range,negative conduction band position and high reduction ability.However,photoreduction of CO_(2)by MHP remains a challenge because of the slow charge separation and transfer.Herein,a cobalt single-atom modified nitrogen-doped graphene(Co-NG)cocatalyst is prepared for enhanced photocatalytic CO_(2)reduction of bismuth-based MHP Cs_(3)Bi_(2)Br_(9).The optimal Cs_(3)Bi_(2)Br_(9)/Co-NG composite exhibits the CO production rate of 123.16μmol g-1 h-1,which is 17.3 times higher than that of Cs_(3)Bi_(2)Br_(9).Moreover,the Cs_(3)Bi_(2)Br_(9)/Co-NG composite photocatalyst exhibits nearly 100%CO selectivity as well as impressive long-term stability.Charge carrier dynamic characterizations such as Kelvin probe force microscopy(KPFM),single-particle PL microscope and transient absorption(TA)spectroscopy demonstrate the vital role of Co-NG cocatalyst in accelerating the transfer and separation of photogenerated charges and improving photocatalytic performance.The reaction mechanism has been demonstrated by in situ diffuse reflectance infrared Fourier-transform spectroscopy measurement.In addition,in situ X-ray photoelectron spectroscopy test and theoretical calculation reveal the reaction reactive sites and reaction energy barriers,demonstrating that the introduction of Co-NG promotes the formation of~(*)COOH intermediate,providing sufficient evidence for the highly selective generation of CO.This work provides an effective single-atom-based cocatalyst modification strategy for photocatalytic CO_(2)reduction and is expected to shed light on other photocatalytic applications.
基金supported by the National Natural Science Foundation of China(Nos.51973205 and 51773189)the Fundamental Research Funds for the Central Universities(Nos.WK9110000066,WK3450000005 and WK3450000006)。
文摘The design and synthesis of novel photocatalyst with self-temperature control function is an important topic in the field of advanced environmental functional materials.In this work,submicron-sized magnetic phase change microcapsules composed of paraffin core and Fe_(3)O_(4)-loaded silica shell are prepared,on which the Bi_(2)WO_(6)crystals is grown in situ through hydrothermal reaction to obtain novel magnetic phase-change-microcapsule-supported Bi_(2)WO_(6)catalyst(MP@FS/BWO).The MP@FS/BWO has a paraffin encapsulation ratio of 57.1%,and the phase change enthalpy of 105.1 J/g in a temperature range of 50–60℃,which endows the MP@FS/BWO with a certain self-temperature regulation ability.MP@FS/BWO shows excellent catalytic performance in the decomposition of rhodamine B under the simulated sunlight irradiation.After the light source is turned off,it still has good catalytic ability by maintaining high temperature due to its temperature control function based on the phase transition process.The MP@FS/BWO can be easily recycled by magnetic separation and shows good structural stability and reusability.This work provides a new idea for the development of long-effect and energy-saving outdoor photocatalysts.
基金supported by the National Key Research and Development Program of China (2021YFA1502300)by the Fundamental Research Funds for the Central Universities (20720220011)+3 种基金conducted by the Fundamental Research Center of Artificial Photosynthesis (FReCAP)financially supported by the National Natural Science Foundation of China (22088102)the support from National Natural Science Foundation of China (22090033, 22272165)Youth Innovation Promotion Association of Chinese Academy of Sciences and the National Youth Talent Support Program。
文摘Although spatial charge separation between different facets of semiconductor crystals has been recognized as a general strategy in photocatalysis, the vital role of crystal morphology symmetry in charge separation properties still remains elusive. Herein,taking monoclinic bismuth vanadate(BiVO_(4)) as a platform, we found distinct charge separation difference via rationally tailoring the morphology symmetry from octahedral to truncated octahedral crystals. For octahedral BiVO_(4), photogenerated electrons and holes can be separated between edges and quasi-equivalent facets. However, as for truncated octahedral crystals,photogenerated electrons tend to transfer to {010} facets while photogenerated holes prefer to accumulate on {120} facets, thus realizing the spatial separation of photogenerated charge between different facets. Morphology tailoring of BiVO_(4) crystals leads to a significantly improved photogenerated charge separation efficiency and photocatalytic water oxidation activity. The built-in electric field for driving the separation of photogenerated electrons and holes is considered to be modulated by tuning the morphology symmetry of BiVO_(4) crystals. This work discloses the significant roles of morphology symmetry in photogenerated charge separation and facilitates the rational design of artificial photocatalysts.
基金supported by the Science and Technology Planning Project of Shenzhen Municipality(JCYJ20200109150225155)the Natural Science Foundation of Hubei Province (2016CFA078)+1 种基金the National Natural Science Foundation of China (51472194 and 21975193)the Fundamental Research Funds for the Central Universities (2020-YB-031)
文摘Oxygen vacancy-rich bismuth oxysulfide(Bi_(2)O_(2)S)with layered structure was prepared for efficient photocatalytic CO_(2) reduction under visible light irradiation.The existence of rich oxygen vacancies in Bi_(2)O_(2)S,which was proven by sufficient characterization,can provide abundant active sites,improve CO_(2) adsorption and activation abilities and boost the separation efficiency of photogenerated carriers,as determined by theoretical and experimental analyses.As a result,Bi_(2)O_(2)S with rich oxygen vacancies achieves excellent CO_(2) conversion with a CH4 production of 65.8μmol g^(-1) under 90 min of visible light irradiation,which was 27-fold higher than the pristine Bi_(2)O_(2)S.The mechanism of photocatalytic conversion of CO_(2) to CH4 was also determined by in situ FT-IR analyses.This study provides an in-depth understanding of the development of Bi-O-S system photocatalysts through defect engineering for photocatalytic CO_(2) reduction.
文摘Solar-driven water splitting is considered as a promising method to mitigate the energy crisis and various environmental issues.Bismuth vanadate(BiVO_(4))is photoanode material with tremendous potential for photoelectrochemical(PEC)water splitting.However,its PEC performance is severely hindered owing to poor surface charge transfer,surface recombination at the photoanode/electrolyte junction,and sluggish oxygen evolution reaction(OER)kinetics.In this regard,a novel solution was developed in this study to address these issues by decorating the surface of BiVO_(4)with cobalt sulfide,whose attractive features such as low cost,high conductivity,and rapid charge-transfer ability assisted in improving the PEC activity of the BiVO_(4)photoanode.The fabricated photoanode exhibited a significantly enhanced photocurrent density of 3.2 m A cm^(-2)under illumination at 1.23 V vs.a reversible hydrogen electrode,which is more than 2.5 times greater than that of pristine BiVO_(4).Moreover,the Co S/BiVO_(4)photoanode also exhibited considerable improvements in the charge injection yield(75.8%vs.36.7%for the bare BiVO_(4)film)and charge separation efficiency(79.8%vs.66.8%for the pristine BiVO_(4)film).These dramatic enhancements were primarily ascribed to rapid charge-transport kinetics and efficient reduction of the anodic overpotential for oxygen evolution enabled by the surface modification of BiVO_(4)by Co S.This study provides valuable suggestions for designing efficient photocatalysts via surface modification to improve the PEC performance.
