Due to the loss of organic amine cations and lead ions in the structure of the iodine-lead methylamine perovskite solar cell,there are a large number of defects within the film and the recombination loss caused by gra...Due to the loss of organic amine cations and lead ions in the structure of the iodine-lead methylamine perovskite solar cell,there are a large number of defects within the film and the recombination loss caused by grain boundaries,which seriously hinder the further improvement of power conversion efficiency and stability.Herein,a novel carbon nitride C_(3)N_(3) incorporated into the perovskite precursor solution is a multifunctional strategy,which not only increases the light absorption strength,grain size,and hydrophobicity of the perovskite film,but also effectively passivates the bulk and interfacial defects of perovskite and verified by the first-principles density functional theory calculations.As a result,the efficiency and stability of perovskite solar cells are improved.The device with 0.075 mg mL^(-1) C_(3)N_(3) additive delivers a champion power conversion efficiency of 19.91%with suppressed hysteresis,which is significantly higher than the 18.16% of the control device.In addition,the open-circuit voltage of the modified device with the maximum addition as high as 1.137 V is 90.96% of the Shockley–Queisser limit(1.25 V).Moreover,the power conversion efficiency of the modified device without encapsulation can maintain nearly 90% of its initial value after being stored at 25℃ and 60% relative humidity for 500 h.This work provides a new idea for developing additives to improve the power conversion efficiency and stability of perovskite solar cells.展开更多
Photocatalytic CO_(2)reduction provides a promising strategy for the alleviation of greenhouse effect and energy shortage problem.Metal single atom modification is an effective method to improve the CO_(2)reduction pe...Photocatalytic CO_(2)reduction provides a promising strategy for the alleviation of greenhouse effect and energy shortage problem.Metal single atom modification is an effective method to improve the CO_(2)reduction performance of covalent organic framework(COF)photocatalysts,while the intrinsic mechanism is not revealed in depth.Herein,a Pt-COF photocatalytic system was constructed by embedding Pt single atom in TFPT-TMT-COF(TFPT:1,3,5-tris(4-formylphenyl)-triazine,TMT:2,4,6-trimethyl-1,3,5-triazine).Based on density functional theory(DFT)calculation,the geometric structure and electronic property of Pt-COF were investigated,and the CO_(2)adsorption and reduction reaction process on Pt-COF were simulated.The results show that the Pt atom can be steadily anchored in COF via the formation of Pt-N and Pt-C bonds.Moreover,there is strong electronic interaction between Pt and COF.The incorporation of Pt atom benefits the CO_(2)reduction activity of COF from multiple aspects:(ⅰ)reducing the band gap and improving light absorption;(ⅱ)enhancing CO_(2)adsorption and activating the CO_(2)molecule;(ⅲ)decreasing the energy barrier in the hydrogenation step of CO_(2)→COOH,thus facilitating CO_(2)conversion to CO;(ⅳ)inhibiting the hydrogenation of CO,thereby increasing the selectivity of CO.This work brings a novel insight into the excellent CO_(2)reduction performance of Pt modified COF,and provides useful references for the design of single atom photocatalysts.展开更多
Preparation of efficient photocatalysts with ease of recovery in solar fuel generation is highly desired to achieve carbon neutralization in carbon dioxide(CO_(2))emissions.Inspired from the forest with superior light...Preparation of efficient photocatalysts with ease of recovery in solar fuel generation is highly desired to achieve carbon neutralization in carbon dioxide(CO_(2))emissions.Inspired from the forest with superior light penetration and fast gas transport,a TiO_(2)/g-C_(3)N_(4)composite nanowire arrays(NAs)film with maximized light utilization is devised.It is achieved by in-situ coating a thin layer of g-C_(3)N_(4)(as the leaf)on the vertically-oriented TiO_(2)arrays(as tree trunks)on Ti foil(as soil).Benefiting from the effective charge separation by S-scheme charge transfer,intimate contact by the in-situ growth as well as the ingenious structure,the composite,readily recyclable,displays exciting performance in photocatalytic CO_(2)reduction.It is beyond doubt that the combination of heterojunction construction and“nature-inspired biomimetic photocatalyst”design promises practical applications and industrial use.展开更多
Two-dimensional(2D)materials,especially transition metal carbides and/or nitrides(MXenes),have aroused extensive research interest in the field of photocatalysis.Specifically,the unique properties of high electrical c...Two-dimensional(2D)materials,especially transition metal carbides and/or nitrides(MXenes),have aroused extensive research interest in the field of photocatalysis.Specifically,the unique properties of high electrical conductivity,abundant surface functional groups,considerable specific surface area,and excellent photo-thermal effect allow MXenes to play versatile roles in photocatalysis.Herein,the latest and encouraging developments in MXenes-based composite materials for photocatalytic applications in recent two years are reviewed.We first briefly describe the roles of MXenes as a support and co-catalyst to promote the distribution of photocatalysts and facilitate the separation of the photogenerated charge carriers,respectively.Then,the design and fabrication of MXenes-based composite materials for various photocatalytic applications including H_(2) evolution,CO_(2) reduction,environmental remediation,and H_(2)O_(2) generation are comprehensively illustrated.Finally,we point out the challenges and prospects for the future development of MXenes-based composite materials.展开更多
Hydrogenation refers to the addition of hydrogen(H)atoms to unsaturated bonds.It is one of the most important transformation reactions in the organic synthesis of chemicals and pharmaceuticals[1].Based on different hy...Hydrogenation refers to the addition of hydrogen(H)atoms to unsaturated bonds.It is one of the most important transformation reactions in the organic synthesis of chemicals and pharmaceuticals[1].Based on different hydrogen sources,hydrogenation can be classified into direct hydrogenation(DH)and transfer hydrogenation(TH).展开更多
Constructing step-scheme(S-scheme)heterojunctions has become a popular strategy for efficient pho-tocatalytic H_(2)O_(2) generation.Herein,we in situ grew BiOBr nanosheets(NSs)on a Schiff-base covalent organic framewo...Constructing step-scheme(S-scheme)heterojunctions has become a popular strategy for efficient pho-tocatalytic H_(2)O_(2) generation.Herein,we in situ grew BiOBr nanosheets(NSs)on a Schiff-base covalent organic framework(COF)with largeπ-conjugated structures to prepare S-scheme BiOBr/COF photocat-alysts for H_(2)O_(2) synthesis.The highest photocatalytic H_(2)O_(2) production performance of the composite sample constituting the S-scheme heterojunction is 3749μmol g−1 h−1,which was 1.85 and 27 times the rates of COF and BiOBr,respectively.The construction of S-scheme heterojunction contributed to ef-ficient carrier transfer and separation in space and enhanced redox power.Moreover,the lying-down O_(2)-adsorption configuration on the COF surface favors the concerted two-electron O_(2) reduction process,which greatly reduced the reduction potential requirement for O_(2)-to-H_(2)O_(2) conversion.The synergy be-tween the S-scheme heterojunction and the unique O_(2)-COF interaction boosted photocatalytic H_(2)O_(2) pro-duction activity.展开更多
Photocatalytic materials have attracted more and more attention in the world due to their great potential in solar energy conversion and environmental remediation.We were honored to host the 3rd Chinese Symposium on P...Photocatalytic materials have attracted more and more attention in the world due to their great potential in solar energy conversion and environmental remediation.We were honored to host the 3rd Chinese Symposium on Photocatalytic Materials(CSPM3)in Wuhan on December 11-14,2020,and hereby express our sincere thanks to all the guests and delegates attending this conference.展开更多
Sodium-ion batteries are promising candidates for large-scale grid storage systems and other applications.Their foremost advantage derives from superior environmental credentials,enhanced safety as well as lower raw m...Sodium-ion batteries are promising candidates for large-scale grid storage systems and other applications.Their foremost advantage derives from superior environmental credentials,enhanced safety as well as lower raw material costs than lithium-ion batteries.It is still challenging to explore desirable anode material.In this study,FeSe_(2)@CoSe_(2)/FeSe_(2),with a yolk-shell structure was prepared by ion exchange and selenisation.The FeSe_(2)@CoSe_(2)/FeSe_(2)prepared as anode material for sodiumion batteries exhibits excellent rate capability due to the synergistic effect of bimetallic selenides and the interfacial effect of the heterostructure.Moreover,it delivers high performance(510 mAh g^(-1)at 0.2 A g^(-1)),superior rate capa-bility(90%retention at 5 A g^(-1)),and good long-time cycling stability(78%capacity retention after 1800 cycles at a high current density of 2 A g^(-1)).The optimized sodiumion full cell with FeSe_(2)@CoSe_(2)/FeSe_(2)as the anode and Na 3 V 2(PO 4)3 as the cathode still demonstrates excellent performance.Namely,a ca-pacity of 272 mAh g^(-1)(at 1 A g^(-1))within the operating voltage from 1 to 3.8 V can be obtained.This work illustrates the potential of bimetallic selenides with heterostructures for performance enhancement of sodium-ion batteries.展开更多
To suppress the recombination of photogenerated electron and hole in single photocatalysts,an important method is to design heterojunction by combining two photocatalysts.This method has widely used to enhance the pho...To suppress the recombination of photogenerated electron and hole in single photocatalysts,an important method is to design heterojunction by combining two photocatalysts.This method has widely used to enhance the photocatalytic performance of the composites.At the begining,most people use type-Ⅱcharge carrier transfer mechanism to explain the emhanced activity of the composite semiconductors.展开更多
Photocatalytic Hproduction from water splitting has a promising prospect for alleviating energy and environmental issues.However,the fast recombination of photogenerated charge carriers limits the photocatalytic effic...Photocatalytic Hproduction from water splitting has a promising prospect for alleviating energy and environmental issues.However,the fast recombination of photogenerated charge carriers limits the photocatalytic efficiency and its practical application.Cocatalyst engineering is an effective strategy to spatially separate photogenerated charge carriers.In this work,noble-metal-free MoSand CoOcocatalysts are loaded on CdS nanorods by a two-step photodeposition method.The MoSfunctions as the reduction cocatalyst to trap electrons and Co Oas the oxidation cocatalyst to trap holes.Transmission electron microscopy(TEM),inductively coupled plasma(ICP),X-ray photoelectron spectroscopy(XPS)and MottSchottky results demonstrate the effectiveness of photodeposition for loading MoSand CoOdual cocatalysts on CdS and their impact on the photochemical properties.The optimized CdS-MoS-CoOcomposite exhibits a high photocatalytic H-production rate of 7.4 mmol g^(-1)h^(-1)and an apparent quantum efficiency(QE)of 7.6%at 420 nm.Further analysis on time-resolved photoluminescence(TRPL)indicates that the introduction of dual cocatalysts greatly prolongs the lifetime of photogenerated charge carriers and deceases the charge recombination rates,consequently leading to superior photocatalytic H-production performance.This work provides a facile and effective strategy for the construction of highly efficient dual-cocatalyst-modified CdS photocatalyst for high-performance photocatalytic Hproduction.展开更多
The promising S-scheme heterojunction photocatalysts are considered as a novel frontier due to their superiority in various solar-driven energy-related applications.Recently,a novel atom-specific tailoring strategy ha...The promising S-scheme heterojunction photocatalysts are considered as a novel frontier due to their superiority in various solar-driven energy-related applications.Recently,a novel atom-specific tailoring strategy has been introduced on the construction of S-scheme het-erojunction for promoting the electronic transferability.The S-scheme heterojunction is regulated by integrating high-crystalline carbon nitride with Co-doped CeO_(2).Specifically,this atom-specific regulation of S-scheme heterojunction boosts directional electron-driving effect towards functionalized Co sites,benefit-ing for effective photogenerated charge carrier transferability.Moreover,a series of tracking characterizations show that Co-embedded modification promotes CO_(2)photoreduction into hydrogenation steps,resulting in high performance towards CO_(2)-to-CH_(4)photoreduction,which provides new opportunities for the development of multifunctional cooperation in heterogeneous photocatalysis.展开更多
Single-atom catalysts have high catalytic activity due to their unique quantum size effects and optimal atom utilization.Herein,visi-ble-light-responsive photocatalysts were designed by coupling CdS with graphene quan...Single-atom catalysts have high catalytic activity due to their unique quantum size effects and optimal atom utilization.Herein,visi-ble-light-responsive photocatalysts were designed by coupling CdS with graphene quantum dots(GQDs)and platinum single atoms(PtSAs).GQDs and PtSAs were successively loaded on ultrathin CdS nanosheets through freeze-drying and in-situ photocatalytic reduction.The synergistic effect between PtSAs and GQDs results in superior photocatalytic activity with a hydrogen production rate of 13488μmol h^(-1)g^(-1)as well as the maximum apparent quantum efficiency(AQE)of 35.5%in lactic acid aqueous solution,which is 62 times higher than that of pristine CdS(213μmol g^(-1)h^(-1)).The energy conversion efficiency is ca.13.05%.As a photosensitizer and an electron reservoir,GQDs can not only extend the light response of CdS to the visible-light region(400-800 nm),but also promotes the separation of photoinduced electron-hole pairs.Meanwhile,PtSAs,with unique electronic and geometric features,can provide more efficient proton reduction sites.This finding provides an effective strategy to remarkably improve the photocatalytic H_(2) production performance.展开更多
CdS photocorrosion is one of the most important factors that greatly affect the photocatalytic H_(2)-production rate and long-time stability.However,the reported works about CdS photocorrosion are mainly focused on th...CdS photocorrosion is one of the most important factors that greatly affect the photocatalytic H_(2)-production rate and long-time stability.However,the reported works about CdS photocorrosion are mainly focused on the surface oxidation by photogenerated holes,while the possible reduction of lattice Cd^(2+) by photogenerated electrons is usually ignored.In this work,the lattice Cd^(2+) reduction by photogenerated electrons during CdS photocorrosion were carefully investigated to reveal its potential effect on the microstructure change and photocatalytic H_(2)-production performance of CdS photocatalyst based on the two typical Na_(2)S-Na_(2)SO_(3) and lactic acid H_(2)-evolution systems.It was found that many isolated metallic Cd nanoparticles(5–50 nm)were produced on the CdS surface in the Na_(2)S-Na_(2)SO_(3) system,causing its serious destroy of CdS surface and a gradually decreased photocatalytic activity,while only a metallic Cd layer(2-3 nm)is homogeneously coated on the CdS surface in the lactic acid system,leading to an increased H-evolution rate.In fact,once a certain amount of metallic Cd was produced on the CdS surface,the resulting CdS-Cd composites can present a stable photocatalytic H_(2)-production activity and excellent stability for the final CdS-Cd photocatalysts.Hence,a photoinduced self-stability mechanism of CdS photocatalyst has been proposed,namely,the spontaneously produced metallic Cd contributes to the transformation of unstable CdS into stable CdS-Cd structure,with the simultaneous realization of final stable H_(2)-evolution performance.展开更多
Solar energy is the most important clean and renewable energy in the world.However,the unpredictability,seasonal variation day and night,uneven distribution and low energy density limit its practical application.Photo...Solar energy is the most important clean and renewable energy in the world.However,the unpredictability,seasonal variation day and night,uneven distribution and low energy density limit its practical application.Photocatalysis technology has a very broad application prospect in solving energy and environmental problems.展开更多
Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a clean and cost-efficient alternative to the traditional anthraquinone oxidation approach.Herein,a step-scheme(S-scheme)heterojunction photocat-alyst is f...Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a clean and cost-efficient alternative to the traditional anthraquinone oxidation approach.Herein,a step-scheme(S-scheme)heterojunction photocat-alyst is fabricated by coupling TiO_(2)with three dimensionally ordered macroporous sulfur-doped graphitic carbon nitride(3DOM SCN/T)by electrostatic self-assembly.The optimized photocatalyst achieved a high photocatalytic H_(2)O_(2)production activity with a yield of 2128μmol h^(−1)g^(−1)without the addition of hole scavengers.The remarkable performance was attributed to the synergy between the 3DOM framework and the S-scheme heterojunction.The former enhances light harvesting and provides abundant active sites for surface reactions,while the latter promotes the spatial separation of photogenerated carriers and enhances the redox power.Finally,the mechanism of photocatalytic H_(2)O_(2)production over the 3DOM SCN/T S-scheme composite is proposed.This work provides novel insights into the development of effi-cient photocatalysts for H_(2)O_(2)production from water and O_(2).展开更多
Photocatalytic H_(2)O_(2)production provides a clean and sustainable strategy for artificial photosynthesis.Herein,an inorganic/organic composite photocatalyst was fabricated by in-situ growth of CdS nanoparticles on ...Photocatalytic H_(2)O_(2)production provides a clean and sustainable strategy for artificial photosynthesis.Herein,an inorganic/organic composite photocatalyst was fabricated by in-situ growth of CdS nanoparticles on the surface of resorcinol-formaldehyde(RF)resin spheres.RF spheres played multiple roles:(i)acting as a substrate for the growth of CdS and constructing a core-shell structure with seamless con-tact;(ⅱ)improving visible light absorption of CdS;(ⅲ)forming an S-scheme heterojunction with CdS and promoting the charge separation and transfer.Consequently,under visible light illumination,CdS/RF composite presented remarkably enhanced H_(2)O_(2)production activity.Its H_(2)O_(2)yield in 60 min was 801μmol L^(-1),which was 5.2 and 1.5 times higher than that of RF spheres and CdS hollow spheres,respectively.The charge migration between CdS and RF followed the S-scheme photocatalytic mechanism,which was verified by work function measurement,ex-situ and in-situ irradiated X-ray photoelectron spectroscopy.This work brings a novel insight into designing RF-based inorganic/organic S-scheme heterojunction pho-tocatalysts for efficient H_(2)O_(2)production.展开更多
Electron donors(EDs)are widely used to improve the H 2 production performance of Schottky junction photocatalysts,but the functions of EDs are still unknown from the perspective of electron transfer dy-namics.Herein,P...Electron donors(EDs)are widely used to improve the H 2 production performance of Schottky junction photocatalysts,but the functions of EDs are still unknown from the perspective of electron transfer dy-namics.Herein,Pt nanocluster-decorated CdS nanorod is successfully prepared to construct a typical CdS/Pt Schottky junction.Pt nanoclusters with a diameter of∼2 nm are deposited on the surface of CdS nanorods by in situ photoreduction at sub-zero temperature.The CdS/Pt photocatalyst using lactic acid shows a higher H_(2)production rate of 4762μmol g^(-1)h^(-1)compared to that using methanol,tri-ethanolamine,and glycerol.To understand the cause,the dynamics of photogenerated carriers in CdS/Pt photocatalysts during ED-assisted H_(2)production are revealed by femtosecond transient absorption spec-troscopy.Among the four organic EDs,lactic acid enables the fastest electron transfer rate of 1.8×10^(9)s^(-1)and the highest electron transfer efficiency of 76%at the CdS/Pt interface due to the most efficient hole consumption.This work sheds light on the importance of efficient interfacial electron transfer for im-proving the photocatalytic performance of Schottky junction photocatalysts.展开更多
Photocatalytic production of H_(2)O_(2) by polymeric carbon nitride has been regarded as a promising ap-proach for the conversion of solar energy into valuable chemicals.However,the efficiency of pristine car-bon nitr...Photocatalytic production of H_(2)O_(2) by polymeric carbon nitride has been regarded as a promising ap-proach for the conversion of solar energy into valuable chemicals.However,the efficiency of pristine car-bon nitride is limited by the rapid charge recombination and the lack of suitable active sites.Herein,we introduce single-atom Cu anchored on N-doped graphene(Cu-NG)as a cocatalyst coupled with carbon nitride via covalent bonding to enhance photocatalytic H_(2)O_(2) production.The Cu-NG/carbon nitride could broaden the light absorption from UV to near-infrared region,contributing to the photocatalytic process.Moreover,NG containing electron-rich N atoms could serve as anchoring sites for stabilizing single-atom Cu.Importantly,the single-atom Cu acts not only as an electron sink to steer the interfacial charge sep-aration but also as an active site for molecular oxygen adsorption and activation.With the synergistic effect of the enhanced interfacial charge separation and suitable active sites,Cu-NG/carbon nitride ex-hibits improved photocatalytic performance with an H_(2)O_(2) generation rate of 2856μmol g^(−1)h^(−1),which is 2.6 times that of pristine carbon nitride.This work provides a protocol for high-performance photocat-alytic H_(2)O_(2) production using a single-atom cocatalyst.展开更多
Photocatalytic production of hydrogen peroxide(H_(2)O_(2))is an ideal pathway for obtaining solar fuels.Herein,an S-scheme heterojunction is constructed in hybrid TiO_(2)/In_(2)S_(3)photocatalyst,which greatly promote...Photocatalytic production of hydrogen peroxide(H_(2)O_(2))is an ideal pathway for obtaining solar fuels.Herein,an S-scheme heterojunction is constructed in hybrid TiO_(2)/In_(2)S_(3)photocatalyst,which greatly promotes the separation of photogenerated carriers to foster efficient H_(2)O_(2)evolution.These composite photocatalysts show a high H_(2)O_(2)yield of 376μmol/(L·h).The mechanism of charge transfer and separation within the S-scheme heterojunction is well studied by computational methods and experiments.Density functional theory and in-situ irradiated X-ray photoelectron spectroscopy results reveal distinct features of the S-scheme heterojunction in the TiO_(2)/In_(2)S_(3)hybrids and demonstrate charge transfer mechanisms.The density functional theory calculation and electron paramagnetic resonance results suggest that O_(2)reduction to H_(2)O_(2)follows stepwise one-electron processes.In_(2)S_(3)shows a much stronger interaction with O_(2)than TiO_(2)as well as a higher reduction ability,serving as the active sites for H_(2)O_(2)generation.The work provides a novel design of S-scheme photocatalyst with high H_(2)O_(2)evolution efficiency and mechanistically demonstrates the improved separation of charge carriers.展开更多
基金This work was financially supported by National Natural Science Foundation of China(52002121,62004064,21873027,and 21905219)the Key Program for Inter-governmental S&T Innovation Cooperation Projects of National Key R&D Pro-gram of China(2019YFE0107100)+1 种基金Natural Science Foundation of Hubei Province(2020CFA091)Overseas Expertise Introduction Center for Discipline Innova-tion(D18025).
文摘Due to the loss of organic amine cations and lead ions in the structure of the iodine-lead methylamine perovskite solar cell,there are a large number of defects within the film and the recombination loss caused by grain boundaries,which seriously hinder the further improvement of power conversion efficiency and stability.Herein,a novel carbon nitride C_(3)N_(3) incorporated into the perovskite precursor solution is a multifunctional strategy,which not only increases the light absorption strength,grain size,and hydrophobicity of the perovskite film,but also effectively passivates the bulk and interfacial defects of perovskite and verified by the first-principles density functional theory calculations.As a result,the efficiency and stability of perovskite solar cells are improved.The device with 0.075 mg mL^(-1) C_(3)N_(3) additive delivers a champion power conversion efficiency of 19.91%with suppressed hysteresis,which is significantly higher than the 18.16% of the control device.In addition,the open-circuit voltage of the modified device with the maximum addition as high as 1.137 V is 90.96% of the Shockley–Queisser limit(1.25 V).Moreover,the power conversion efficiency of the modified device without encapsulation can maintain nearly 90% of its initial value after being stored at 25℃ and 60% relative humidity for 500 h.This work provides a new idea for developing additives to improve the power conversion efficiency and stability of perovskite solar cells.
基金supported by the National Key Research and Development Program of China(Nos.2022YFE0115900 and 2022YFB3803600)the National Natural Science Foundation of China(Nos.52173065,51932007,22261142666 and 22238009)the China Postdoctoral Science Foundation(No.2022M710137)and the Natural Science Foundation of Hubei Province of China(No.2022CFA001).
文摘Photocatalytic CO_(2)reduction provides a promising strategy for the alleviation of greenhouse effect and energy shortage problem.Metal single atom modification is an effective method to improve the CO_(2)reduction performance of covalent organic framework(COF)photocatalysts,while the intrinsic mechanism is not revealed in depth.Herein,a Pt-COF photocatalytic system was constructed by embedding Pt single atom in TFPT-TMT-COF(TFPT:1,3,5-tris(4-formylphenyl)-triazine,TMT:2,4,6-trimethyl-1,3,5-triazine).Based on density functional theory(DFT)calculation,the geometric structure and electronic property of Pt-COF were investigated,and the CO_(2)adsorption and reduction reaction process on Pt-COF were simulated.The results show that the Pt atom can be steadily anchored in COF via the formation of Pt-N and Pt-C bonds.Moreover,there is strong electronic interaction between Pt and COF.The incorporation of Pt atom benefits the CO_(2)reduction activity of COF from multiple aspects:(ⅰ)reducing the band gap and improving light absorption;(ⅱ)enhancing CO_(2)adsorption and activating the CO_(2)molecule;(ⅲ)decreasing the energy barrier in the hydrogenation step of CO_(2)→COOH,thus facilitating CO_(2)conversion to CO;(ⅳ)inhibiting the hydrogenation of CO,thereby increasing the selectivity of CO.This work brings a novel insight into the excellent CO_(2)reduction performance of Pt modified COF,and provides useful references for the design of single atom photocatalysts.
基金supported by the National Natural Science Foundation of China(NSFC)(Nos.51932007,51872220,51961135303,21871217,52073223,52063028,U1905215 and U1705251)。
文摘Preparation of efficient photocatalysts with ease of recovery in solar fuel generation is highly desired to achieve carbon neutralization in carbon dioxide(CO_(2))emissions.Inspired from the forest with superior light penetration and fast gas transport,a TiO_(2)/g-C_(3)N_(4)composite nanowire arrays(NAs)film with maximized light utilization is devised.It is achieved by in-situ coating a thin layer of g-C_(3)N_(4)(as the leaf)on the vertically-oriented TiO_(2)arrays(as tree trunks)on Ti foil(as soil).Benefiting from the effective charge separation by S-scheme charge transfer,intimate contact by the in-situ growth as well as the ingenious structure,the composite,readily recyclable,displays exciting performance in photocatalytic CO_(2)reduction.It is beyond doubt that the combination of heterojunction construction and“nature-inspired biomimetic photocatalyst”design promises practical applications and industrial use.
基金supported by the National Natural Science Foundation of China(51932007,U1705251,U1905215,51961135303,22005232,and 22150610467)the National Key Research and Development Program of China(2018YFB1502001).
文摘Two-dimensional(2D)materials,especially transition metal carbides and/or nitrides(MXenes),have aroused extensive research interest in the field of photocatalysis.Specifically,the unique properties of high electrical conductivity,abundant surface functional groups,considerable specific surface area,and excellent photo-thermal effect allow MXenes to play versatile roles in photocatalysis.Herein,the latest and encouraging developments in MXenes-based composite materials for photocatalytic applications in recent two years are reviewed.We first briefly describe the roles of MXenes as a support and co-catalyst to promote the distribution of photocatalysts and facilitate the separation of the photogenerated charge carriers,respectively.Then,the design and fabrication of MXenes-based composite materials for various photocatalytic applications including H_(2) evolution,CO_(2) reduction,environmental remediation,and H_(2)O_(2) generation are comprehensively illustrated.Finally,we point out the challenges and prospects for the future development of MXenes-based composite materials.
文摘Hydrogenation refers to the addition of hydrogen(H)atoms to unsaturated bonds.It is one of the most important transformation reactions in the organic synthesis of chemicals and pharmaceuticals[1].Based on different hydrogen sources,hydrogenation can be classified into direct hydrogenation(DH)and transfer hydrogenation(TH).
基金This work was supported by the National Natural Science Foun-dation of China(Nos.22278324,51932007,22238009,U1905215,52073223,52073034,and 22208332)the Postdoctoral Science Foundation of China(No.2022M712946)the Natural Science Foundation of Hubei Province of China(No.2022CFA001).
文摘Constructing step-scheme(S-scheme)heterojunctions has become a popular strategy for efficient pho-tocatalytic H_(2)O_(2) generation.Herein,we in situ grew BiOBr nanosheets(NSs)on a Schiff-base covalent organic framework(COF)with largeπ-conjugated structures to prepare S-scheme BiOBr/COF photocat-alysts for H_(2)O_(2) synthesis.The highest photocatalytic H_(2)O_(2) production performance of the composite sample constituting the S-scheme heterojunction is 3749μmol g−1 h−1,which was 1.85 and 27 times the rates of COF and BiOBr,respectively.The construction of S-scheme heterojunction contributed to ef-ficient carrier transfer and separation in space and enhanced redox power.Moreover,the lying-down O_(2)-adsorption configuration on the COF surface favors the concerted two-electron O_(2) reduction process,which greatly reduced the reduction potential requirement for O_(2)-to-H_(2)O_(2) conversion.The synergy be-tween the S-scheme heterojunction and the unique O_(2)-COF interaction boosted photocatalytic H_(2)O_(2) pro-duction activity.
基金The CSPM3 meeting was supported by the National Key R&D Program of China(2018YFB1502001)NSFC 51961135303,51932007 and U1905215).
文摘Photocatalytic materials have attracted more and more attention in the world due to their great potential in solar energy conversion and environmental remediation.We were honored to host the 3rd Chinese Symposium on Photocatalytic Materials(CSPM3)in Wuhan on December 11-14,2020,and hereby express our sincere thanks to all the guests and delegates attending this conference.
基金supported by the National Natural Science Foundation of China(51972177,22372084)the Key Project of Zhejiang Province(2023C3016)the Natural Science Foundation of Ningbo City(2021J067)。
基金supported by the National Natural Science Foundation of China(Nos.21801200 and 22075217)the Open Project of Hunan Key Laboratory of Applied Environmental Photocatalysis(No.2114504)the Natural Science Foundation of Hubei Province of China(No.2022CFA001).
文摘Sodium-ion batteries are promising candidates for large-scale grid storage systems and other applications.Their foremost advantage derives from superior environmental credentials,enhanced safety as well as lower raw material costs than lithium-ion batteries.It is still challenging to explore desirable anode material.In this study,FeSe_(2)@CoSe_(2)/FeSe_(2),with a yolk-shell structure was prepared by ion exchange and selenisation.The FeSe_(2)@CoSe_(2)/FeSe_(2)prepared as anode material for sodiumion batteries exhibits excellent rate capability due to the synergistic effect of bimetallic selenides and the interfacial effect of the heterostructure.Moreover,it delivers high performance(510 mAh g^(-1)at 0.2 A g^(-1)),superior rate capa-bility(90%retention at 5 A g^(-1)),and good long-time cycling stability(78%capacity retention after 1800 cycles at a high current density of 2 A g^(-1)).The optimized sodiumion full cell with FeSe_(2)@CoSe_(2)/FeSe_(2)as the anode and Na 3 V 2(PO 4)3 as the cathode still demonstrates excellent performance.Namely,a ca-pacity of 272 mAh g^(-1)(at 1 A g^(-1))within the operating voltage from 1 to 3.8 V can be obtained.This work illustrates the potential of bimetallic selenides with heterostructures for performance enhancement of sodium-ion batteries.
文摘To suppress the recombination of photogenerated electron and hole in single photocatalysts,an important method is to design heterojunction by combining two photocatalysts.This method has widely used to enhance the photocatalytic performance of the composites.At the begining,most people use type-Ⅱcharge carrier transfer mechanism to explain the emhanced activity of the composite semiconductors.
基金the National Science Foundation of China(Nos.22005228 and 52063028)。
文摘Photocatalytic Hproduction from water splitting has a promising prospect for alleviating energy and environmental issues.However,the fast recombination of photogenerated charge carriers limits the photocatalytic efficiency and its practical application.Cocatalyst engineering is an effective strategy to spatially separate photogenerated charge carriers.In this work,noble-metal-free MoSand CoOcocatalysts are loaded on CdS nanorods by a two-step photodeposition method.The MoSfunctions as the reduction cocatalyst to trap electrons and Co Oas the oxidation cocatalyst to trap holes.Transmission electron microscopy(TEM),inductively coupled plasma(ICP),X-ray photoelectron spectroscopy(XPS)and MottSchottky results demonstrate the effectiveness of photodeposition for loading MoSand CoOdual cocatalysts on CdS and their impact on the photochemical properties.The optimized CdS-MoS-CoOcomposite exhibits a high photocatalytic H-production rate of 7.4 mmol g^(-1)h^(-1)and an apparent quantum efficiency(QE)of 7.6%at 420 nm.Further analysis on time-resolved photoluminescence(TRPL)indicates that the introduction of dual cocatalysts greatly prolongs the lifetime of photogenerated charge carriers and deceases the charge recombination rates,consequently leading to superior photocatalytic H-production performance.This work provides a facile and effective strategy for the construction of highly efficient dual-cocatalyst-modified CdS photocatalyst for high-performance photocatalytic Hproduction.
基金supported by the National Natural Science Foundation of China(Nos.51961135303 and 51932007)China Postdoctoral Science Foundation(No.2021TQ0310)。
文摘The promising S-scheme heterojunction photocatalysts are considered as a novel frontier due to their superiority in various solar-driven energy-related applications.Recently,a novel atom-specific tailoring strategy has been introduced on the construction of S-scheme het-erojunction for promoting the electronic transferability.The S-scheme heterojunction is regulated by integrating high-crystalline carbon nitride with Co-doped CeO_(2).Specifically,this atom-specific regulation of S-scheme heterojunction boosts directional electron-driving effect towards functionalized Co sites,benefit-ing for effective photogenerated charge carrier transferability.Moreover,a series of tracking characterizations show that Co-embedded modification promotes CO_(2)photoreduction into hydrogenation steps,resulting in high performance towards CO_(2)-to-CH_(4)photoreduction,which provides new opportunities for the development of multifunctional cooperation in heterogeneous photocatalysis.
基金supported by the National Key Research and Development Program of China(2018YFB1502001)National Natural Science Foundation of China(NSFC)(Nos.51872220,51961135303,51932007,U1905215,21871217 and 52073223)Deanship of Scientific Research(DSR)at King Abdulaziz University,Jeddah(No.RG-72-130-42)。
文摘Single-atom catalysts have high catalytic activity due to their unique quantum size effects and optimal atom utilization.Herein,visi-ble-light-responsive photocatalysts were designed by coupling CdS with graphene quantum dots(GQDs)and platinum single atoms(PtSAs).GQDs and PtSAs were successively loaded on ultrathin CdS nanosheets through freeze-drying and in-situ photocatalytic reduction.The synergistic effect between PtSAs and GQDs results in superior photocatalytic activity with a hydrogen production rate of 13488μmol h^(-1)g^(-1)as well as the maximum apparent quantum efficiency(AQE)of 35.5%in lactic acid aqueous solution,which is 62 times higher than that of pristine CdS(213μmol g^(-1)h^(-1)).The energy conversion efficiency is ca.13.05%.As a photosensitizer and an electron reservoir,GQDs can not only extend the light response of CdS to the visible-light region(400-800 nm),but also promotes the separation of photoinduced electron-hole pairs.Meanwhile,PtSAs,with unique electronic and geometric features,can provide more efficient proton reduction sites.This finding provides an effective strategy to remarkably improve the photocatalytic H_(2) production performance.
基金the National Natural Science Foundation of China(Nos.22075220 and 51872221)the 111 Project(No.B18038)。
文摘CdS photocorrosion is one of the most important factors that greatly affect the photocatalytic H_(2)-production rate and long-time stability.However,the reported works about CdS photocorrosion are mainly focused on the surface oxidation by photogenerated holes,while the possible reduction of lattice Cd^(2+) by photogenerated electrons is usually ignored.In this work,the lattice Cd^(2+) reduction by photogenerated electrons during CdS photocorrosion were carefully investigated to reveal its potential effect on the microstructure change and photocatalytic H_(2)-production performance of CdS photocatalyst based on the two typical Na_(2)S-Na_(2)SO_(3) and lactic acid H_(2)-evolution systems.It was found that many isolated metallic Cd nanoparticles(5–50 nm)were produced on the CdS surface in the Na_(2)S-Na_(2)SO_(3) system,causing its serious destroy of CdS surface and a gradually decreased photocatalytic activity,while only a metallic Cd layer(2-3 nm)is homogeneously coated on the CdS surface in the lactic acid system,leading to an increased H-evolution rate.In fact,once a certain amount of metallic Cd was produced on the CdS surface,the resulting CdS-Cd composites can present a stable photocatalytic H_(2)-production activity and excellent stability for the final CdS-Cd photocatalysts.Hence,a photoinduced self-stability mechanism of CdS photocatalyst has been proposed,namely,the spontaneously produced metallic Cd contributes to the transformation of unstable CdS into stable CdS-Cd structure,with the simultaneous realization of final stable H_(2)-evolution performance.
文摘Solar energy is the most important clean and renewable energy in the world.However,the unpredictability,seasonal variation day and night,uneven distribution and low energy density limit its practical application.Photocatalysis technology has a very broad application prospect in solving energy and environmental problems.
基金supported by the National Natural Science Foundation of China(Nos.22278324,51932007,22238009,U1905215,52073223,52073034,and 22208332)the Natural Science Foundation of Hubei Province of China(No.2022CFA001)the Innovative Research Funds of SKLWUT(No.2022-CL-A1-01).
文摘Photocatalytic hydrogen peroxide(H_(2)O_(2))production offers a clean and cost-efficient alternative to the traditional anthraquinone oxidation approach.Herein,a step-scheme(S-scheme)heterojunction photocat-alyst is fabricated by coupling TiO_(2)with three dimensionally ordered macroporous sulfur-doped graphitic carbon nitride(3DOM SCN/T)by electrostatic self-assembly.The optimized photocatalyst achieved a high photocatalytic H_(2)O_(2)production activity with a yield of 2128μmol h^(−1)g^(−1)without the addition of hole scavengers.The remarkable performance was attributed to the synergy between the 3DOM framework and the S-scheme heterojunction.The former enhances light harvesting and provides abundant active sites for surface reactions,while the latter promotes the spatial separation of photogenerated carriers and enhances the redox power.Finally,the mechanism of photocatalytic H_(2)O_(2)production over the 3DOM SCN/T S-scheme composite is proposed.This work provides novel insights into the development of effi-cient photocatalysts for H_(2)O_(2)production from water and O_(2).
基金supported by the National Natural Science Foundation of China(Nos.52173065,51932007,22278324,52073223,22262012 and U1905215)China Postdoctoral Science Foundation(No.2022M710137)the Natural Science Foundation of Hubei Province of China(No.2022CFA001).
文摘Photocatalytic H_(2)O_(2)production provides a clean and sustainable strategy for artificial photosynthesis.Herein,an inorganic/organic composite photocatalyst was fabricated by in-situ growth of CdS nanoparticles on the surface of resorcinol-formaldehyde(RF)resin spheres.RF spheres played multiple roles:(i)acting as a substrate for the growth of CdS and constructing a core-shell structure with seamless con-tact;(ⅱ)improving visible light absorption of CdS;(ⅲ)forming an S-scheme heterojunction with CdS and promoting the charge separation and transfer.Consequently,under visible light illumination,CdS/RF composite presented remarkably enhanced H_(2)O_(2)production activity.Its H_(2)O_(2)yield in 60 min was 801μmol L^(-1),which was 5.2 and 1.5 times higher than that of RF spheres and CdS hollow spheres,respectively.The charge migration between CdS and RF followed the S-scheme photocatalytic mechanism,which was verified by work function measurement,ex-situ and in-situ irradiated X-ray photoelectron spectroscopy.This work brings a novel insight into designing RF-based inorganic/organic S-scheme heterojunction pho-tocatalysts for efficient H_(2)O_(2)production.
基金the National Key Research and Development Program of China(Nos.2022YFB3803600 and 2018YFB1502001)National Natural Science Foundation of China(Nos.22238009,51932007,U1905215,52073223,52173065,and 52202375)+2 种基金the Natural Science Foundation of Hubei Province of China(No.2022CFA001)China Postdoctoral Science Foundation(Nos.2021TQ0311 and 2021M702990)International Postdoc-toral Exchange Fellowship Program(No.PC2022051).
文摘Electron donors(EDs)are widely used to improve the H 2 production performance of Schottky junction photocatalysts,but the functions of EDs are still unknown from the perspective of electron transfer dy-namics.Herein,Pt nanocluster-decorated CdS nanorod is successfully prepared to construct a typical CdS/Pt Schottky junction.Pt nanoclusters with a diameter of∼2 nm are deposited on the surface of CdS nanorods by in situ photoreduction at sub-zero temperature.The CdS/Pt photocatalyst using lactic acid shows a higher H_(2)production rate of 4762μmol g^(-1)h^(-1)compared to that using methanol,tri-ethanolamine,and glycerol.To understand the cause,the dynamics of photogenerated carriers in CdS/Pt photocatalysts during ED-assisted H_(2)production are revealed by femtosecond transient absorption spec-troscopy.Among the four organic EDs,lactic acid enables the fastest electron transfer rate of 1.8×10^(9)s^(-1)and the highest electron transfer efficiency of 76%at the CdS/Pt interface due to the most efficient hole consumption.This work sheds light on the importance of efficient interfacial electron transfer for im-proving the photocatalytic performance of Schottky junction photocatalysts.
基金This work was financially supported by the National Key R&D Program of China(No.2022YFE0114800)the National Natural Science Foundation of China(Grant Nos.51922081,22278324,52073223,and U1905215)+1 种基金the Natural Science Foundation of Hubei Province of China(No.2022CFA001)the Fundamental Research Funds for the Central Universities(Grant No.WUT:2020-YB-010).
文摘Photocatalytic production of H_(2)O_(2) by polymeric carbon nitride has been regarded as a promising ap-proach for the conversion of solar energy into valuable chemicals.However,the efficiency of pristine car-bon nitride is limited by the rapid charge recombination and the lack of suitable active sites.Herein,we introduce single-atom Cu anchored on N-doped graphene(Cu-NG)as a cocatalyst coupled with carbon nitride via covalent bonding to enhance photocatalytic H_(2)O_(2) production.The Cu-NG/carbon nitride could broaden the light absorption from UV to near-infrared region,contributing to the photocatalytic process.Moreover,NG containing electron-rich N atoms could serve as anchoring sites for stabilizing single-atom Cu.Importantly,the single-atom Cu acts not only as an electron sink to steer the interfacial charge sep-aration but also as an active site for molecular oxygen adsorption and activation.With the synergistic effect of the enhanced interfacial charge separation and suitable active sites,Cu-NG/carbon nitride ex-hibits improved photocatalytic performance with an H_(2)O_(2) generation rate of 2856μmol g^(−1)h^(−1),which is 2.6 times that of pristine carbon nitride.This work provides a protocol for high-performance photocat-alytic H_(2)O_(2) production using a single-atom cocatalyst.
基金supported by the National Natural Science Foundation of China(Nos.52073223,51932007,51961135303,21871217,U1905215 and U1705251).
文摘Photocatalytic production of hydrogen peroxide(H_(2)O_(2))is an ideal pathway for obtaining solar fuels.Herein,an S-scheme heterojunction is constructed in hybrid TiO_(2)/In_(2)S_(3)photocatalyst,which greatly promotes the separation of photogenerated carriers to foster efficient H_(2)O_(2)evolution.These composite photocatalysts show a high H_(2)O_(2)yield of 376μmol/(L·h).The mechanism of charge transfer and separation within the S-scheme heterojunction is well studied by computational methods and experiments.Density functional theory and in-situ irradiated X-ray photoelectron spectroscopy results reveal distinct features of the S-scheme heterojunction in the TiO_(2)/In_(2)S_(3)hybrids and demonstrate charge transfer mechanisms.The density functional theory calculation and electron paramagnetic resonance results suggest that O_(2)reduction to H_(2)O_(2)follows stepwise one-electron processes.In_(2)S_(3)shows a much stronger interaction with O_(2)than TiO_(2)as well as a higher reduction ability,serving as the active sites for H_(2)O_(2)generation.The work provides a novel design of S-scheme photocatalyst with high H_(2)O_(2)evolution efficiency and mechanistically demonstrates the improved separation of charge carriers.
