Composites derived from metal-organic frameworks(MOFs)show promise as catalysts for the photocat-alytic reduction of CO_(2).However,their potential is hindered by constraints such as limited light absorp-tion and slug...Composites derived from metal-organic frameworks(MOFs)show promise as catalysts for the photocat-alytic reduction of CO_(2).However,their potential is hindered by constraints such as limited light absorp-tion and sluggish electron transfer and separation,impacting the overall efficiency of the photocatalytic process.In this study,TiO_(2)nanocrystals,modified with Ptx+,underwent laser etching were encapsulated within the traditional MOF-ZIF-8 framework.This enhanced the adsorption capabilities for CO_(2)reactants and solar light,while also facilitating directed electron transfer and the separation of photogenerated charges.The finely-tuned catalyst demonstrates impressive CH_(4) selectivity at 9.5%,with yields of 250.24μmol g^(-1)h^(-1)for CO and 25.43μmol g^(-1)h^(-1)for CH_(4),utilizing water as a hole trap and H^(+)source.This study demonstrates the viability of achieving characteristics related to the separation of photogen-erated charges in TiO_(2)nanocrystals through laser etching and MOF composite catalysts.It offers novel perspectives for designing MOF-based catalysts with enhanced performance in artificial photosynthesis.展开更多
Photocatalytic CO_(2)reduction into value-added chemicals holds significant promise for carbon-neutral recycling and solar-to-fuel conversion.Enhancing reaction efficiency by manipulating charge transfer is a key appr...Photocatalytic CO_(2)reduction into value-added chemicals holds significant promise for carbon-neutral recycling and solar-to-fuel conversion.Enhancing reaction efficiency by manipulating charge transfer is a key approach to unlocking this potential.In this work,we construct a two-dimensional/twodimensional(2D/2D)FeSe_(2)/protonated carbon nitride(FeSe_(2)/PCN)heterostructure to promote the interfacial charge transfer dynamics,leading to a four-fold improved conversion efficiency of photocatalytic CO_(2)reduction with near 100%CO selectivity.Combining in situ X-ray photoelectron spectroscopy,in situ soft X-ray absorption spectroscopy,and femtosecond transient absorption spectroscopy,it is revealed that FeSe_(2)acts as an electron acceptor upon photoexcitation,introducing an additional electron transfer pathway from PCN to FeSe_(2)that suppresses radiative recombination and promotes charge transfer.In situ X-ray absorption fine structure spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy,and density functional theory calculation further unravel that the electron-enriched FeSe_(2)functions as the active sites for CO_(2)activation and significantly reduces the energy barrier of key intermediate COOH*formation,which is the rate-determined step for CO generation.This work underscores the importance of regulating photocarrier relaxation pathways to achieve effective spatial charge separation for promoted photocatalytic CO_(2)reduction and demonstrates the powerful functions of in situ spectroscopies in in-depth understanding of the photocatalytic mechanism.展开更多
The interface modulation significantly affects the photocatalytic performances of supported metal phthalocyanines(MPc)-based systems.Herein,ZnPc was loaded on nanosized Au-modified TiO_(2)nanosheets(Au-T)to obtain wid...The interface modulation significantly affects the photocatalytic performances of supported metal phthalocyanines(MPc)-based systems.Herein,ZnPc was loaded on nanosized Au-modified TiO_(2)nanosheets(Au-T)to obtain wide-spectrum ZnPc/Au-T photocatalysts.Compared with large Au NP(8 nm)-mediated ZnPc/Au-T photocatalyst,ultrasmall Au NP(3 nm)-mediated one shows advantageous photoactivity,achieving 3-and 10-fold CO_(2)conversion rates compared with reference ZnPc/T and pristine TiO_(2)nanosheets,respectively.Employing monochromatic beam-assisted surface photovoltage and photocurrent action,etc.,the introduction of ultrasmall Au NPs more effectively facilitates intrinsic interfacial charge transfer.Moreover,ZnP c molecules are found more dispersed with the existence of small Au NPs hence exposing abundant Zn^(2+)sites as the catalytic center for CO_(2)reduction.This work provides a feasible design strategy and renewed recognition for supported MPc-based photocatalyst systems.展开更多
The highly photocatalytic conversion of CO_(2)into valuable products is a promising method for mitigating the global greenhouse effect and increasing the energy supply.However,the utilization of electron-deficient act...The highly photocatalytic conversion of CO_(2)into valuable products is a promising method for mitigating the global greenhouse effect and increasing the energy supply.However,the utilization of electron-deficient active sites to activate CO_(2)leads to lower photocatalytic efficiency and selectivity.One effective strategy to improve CO_(2)photoreduction performance is making precise adjustments to the electronic structure of the photocatalyst.Herein,the defective TiO_(2)modified with Cu,Ba,and CuBa metal sites is synthesized via a simple photo-deposition method and applied for photoreduction of CO_(2).Among the prepared catalysts,Cu1Ba_(3)/TiO_(2)-SBO(TiO_(2)-SBO:TiO_(2)with surface and bulk oxygen vacancies)has been demonstrated to possess excellent photocatalytic conversion of CO_(2),with the activity levels of the CO and CH_(4) that are 8 and 6 times higher than the bare TiO_(2)-SBO,and the electron selectivity of CO is up to 53%.The results reveal that oxygen vacancies and CuBa bimetallic sites have a synergistic ability to facilitate the separation of photogenerated carriers.Furthermore,the electron-donor Ba metal enables modulation of the electronic structure of Cu co-catalysts,generating electron-rich Cu metal sites that accelerate the activation of CO_(2).Meanwhile,the theoretical calculations prove that the Cu1Ba_(3)/TiO_(2)-SBO has the stronger CO_(2)adsorption energy,and its strengthened binding of^(*)COOH and the markedly reduced formation energy of CO and^(*)CO intermediates boost the conversion of COOH to CO and enhance the selectivity of CO.Thereby,the defective TiO_(2)modified with CuBa bimetal represents a more effective measure for CO_(2)reduction into valuable products.展开更多
Herein,PtO-supported GdFeO_(3)(PtO/GdFeO_(3))composite photocatalysts were synthesized by a solutionbased technique.Extensive analysis using various analytical instruments has shown that PtO plays a crucial function i...Herein,PtO-supported GdFeO_(3)(PtO/GdFeO_(3))composite photocatalysts were synthesized by a solutionbased technique.Extensive analysis using various analytical instruments has shown that PtO plays a crucial function in augmenting the visible light absorption capacity of composites.Better photogenerated charge carrier transport was credited with this improvement,which led to a decrease in bandgap energy as low as 2.14 eV.The PtO/GdFeO_(3) nanocomposites showed remarkable photocatalytic activity when exposed to visible light,especially in the conversion of CO_(2) into CH_(3)OH.After 9 h of light,a noteworthy yield of 1550μmol·g^(−1) of methanol was produced,demonstrating maximum efficiency at a dose of 2.0 g·L^(−1) and a concentration of 5.0%PtO/GdFeO_(3).This yield indicates the effectiveness of the heterostructure,which outperformed pristine GdFeO_(3) by a factor of 7.85.This significant enhancement highlights the potential advantages of the modified structure in improving performance.Most significantly,the photocatalyst's durability maintained 98.0%of its initial efficacy throughout five cycles.The success of PtO/GdFeO_(3) is largely due to the synergistic light absorption capabilities and enhanced photocharge carrier separation that the integration of PtO produced.It highlights the conversion of CO_(2) into valuable chemicals under visible light exposure,as well as the promise of mixed oxide nanostructures in ecologically responsible material creation.展开更多
Efficiently converting CO_(2)and H_(2)O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis.However,achieving artificial photocatalytic CO_(2)reduction us...Efficiently converting CO_(2)and H_(2)O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis.However,achieving artificial photocatalytic CO_(2)reduction using H_(2)O as the reductant poses challenges is due to the difficulty in efficient cooperation among multiple functional moieties.Metal-organic frameworks(MOFs)are promising candidates for overall CO_(2)photoreduction due to their large surface area,diverse active sites,and excellent tailorability.In this study,we designed a metal-organic framework photocatalyst,named PCN-224(Zn)-Bpy(Ru),by integrating photoactive Zn(Ⅱ)-porphyrin and Ru(Ⅱ)-bipyridyl moieties.In comparison,two isostructural MOFs just with either Zn(Ⅱ)-porphyrin or Ru(Ⅱ)-bipyridyl moiety,namely PCN-224-Bpy(Ru)and PCN-224(Zn)-Bpy were also synthesized.As a result,PCN-224(Zn)-Bpy(Ru)exhibited the highest photocatalytic conversion rate of CO_(2)to CO,with a production rate of 7.6μmol·g^(-1)·h^(-1)in a mixed solvent of CH_(3)CN and H_(2)O,without the need for co-catalysts,photosensitizers,or sacrificial agents.Mass spectrometer analysis detected the signals of^(13)CO(m/z=29),^(13)C^(18)O(m/z=31),^(16)O^(18)O(m/z=34),and^(18)O_(2)(m/z=36),confirming that CO_(2)and H_(2)O acted as the carbon and oxygen sources for CO and O_(2),respectively,thereby confirming the coupling of photocatalytic CO_(2)reduction with H_(2)O oxidation.In contrast,using PCN-224-Bpy(Ru)or PCN-224(Zn)-Bpy as catalysts under the same conditions resulted in significantly lower CO production rates of only 1.5 and 0μmol·g^(-1)·h^(-1),respectively.Mechanistic studies revealed that the lowest unoccupied molecular orbital(LUMO)potential of PCN-224(Zn)-Bpy(Ru)is more negative than the redox potentials of CO_(2)/CO,and the highest occupied molecular orbital(HOMO)potential is more positive than that of H_(2)O/O_(2),satisfying the thermodynamic requirements for overall photocatalytic CO_(2)reduction.In comparison,the HOMO potential of PCN-224(Zn)-Bpy without Ru(II)-bipyridyl moieties is less positive than that of H_(2)O/O_(2),indicating that the Ru(II)-bipyridyl moiety is thermodynamically necessary for CO_(2)reduction coupled with H_(2)O oxidation.Additionally,photoluminescence spectroscopy revealed that the fluorescence of PCN-224(Zn)-Bpy(Ru)was almost completely quenched,and a longer average photoluminescence lifetime compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru)was observed.These suggest a low recombination rate of photogenerated carriers in PCN-224(Zn)-Bpy(Ru),which also supported by the higher photocurrent observed in PCN-224(Zn)-Bpy(Ru)compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru).In summary,the integrated Zn(II)-porphyrin and Ru(II)-bipyridyl moieties in PCN-224(Zn)-Bpy(Ru)play important roles of a photosensitizer and CO_(2)reduction as well as H_(2)O oxidation sites,and their efficient cooperation optimizes the band structure,thereby facilitating the coupling of CO_(2)reduction with H_(2)O oxidation and resulting in highperformance artificial photocatalytic CO_(2)reduction.展开更多
The photoreduction of greenhouse gas CO_(2) using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of ...The photoreduction of greenhouse gas CO_(2) using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of CO_(2) photoreduction remains generally low due to the challenging activation of CO_(2) and the limited light absorption and separation of charge.Defect engineering of catalysts rep-resents a pivotal strategy to enhance the photocatalytic activity for CO_(2),with most research on met-al oxide catalysts focusing on the creation of anionic vacancies.The exploration of metal vacancies and their effects,however,is still underexplored.In this study,we prepared an In2O3 catalyst with indium vacancies(VIn)through defect engineering for CO_(2) photoreduction.Experimental and theo-retical calculations results demonstrate that VIn not only facilitate light absorption and charge sepa-ration in the catalyst but also enhance CO_(2) adsorption and reduce the energy barrier for the for-mation of the key intermediate*COOH during CO_(2) reduction.Through metal vacancy engineering,the activity of the catalyst was 7.4 times,reaching an outstanding rate of 841.32μmol g(-1)h^(-1).This work unveils the mechanism of metal vacancies in CO_(2) photoreduction and provides theoretical guidance for the development of novel CO_(2) photoreduction catalysts.展开更多
The insufficient active sites and slow interfacial charge trans-fer of photocatalysts restrict the efficiency of CO_(2) photoreduction.The synchronized modulation of the above key issues is demanding and chal-lenging....The insufficient active sites and slow interfacial charge trans-fer of photocatalysts restrict the efficiency of CO_(2) photoreduction.The synchronized modulation of the above key issues is demanding and chal-lenging.Herein,strain-induced strategy is developed to construct the Bi–O-bonded interface in Cu porphyrin-based monoatomic layer(PML-Cu)and Bi_(12)O_(17)Br_(2)(BOB),which triggers the surface interface dual polarization of PML-Cu/BOB(PBOB).In this multi-step polarization,the built-in electric field formed between the interfaces induces the electron transfer from con-duction band(CB)of BOB to CB of PML-Cu and suppresses its reverse migration.Moreover,the surface polarization of PML-Cu further promotes the electron converge in Cu atoms.The introduction of PML-Cu endows a high density of dispersed Cu active sites on the surface of PBOB,significantly promoting the adsorption and activation of CO_(2) and CO desorption.The conversion rate of CO_(2) photoreduction to CO for PBOB can reach 584.3μmol g-1,which is 7.83 times higher than BOB and 20.01 times than PML-Cu.This work offers valuable insights into multi-step polarization regulation and active site design for catalysts.展开更多
Ternary halo-sulfur bismuth compound Bi_(19)X_(3)S_(27)(X=Cl,Br,I)with distinct electronic structure and full-spectrum light-harvesting properties show great application potential in the CO_(2) photoreduction field.Ho...Ternary halo-sulfur bismuth compound Bi_(19)X_(3)S_(27)(X=Cl,Br,I)with distinct electronic structure and full-spectrum light-harvesting properties show great application potential in the CO_(2) photoreduction field.However,the relationship between photocatalytic CO_(2) reduction performance and the function of halogens in Bi_(19)X_(3)S_(27) is still poorly understood.Herein,a series of Bi_(19)X_(3)S_(27) nanorod photocatalysts with intrinsic X and S dual vacancies were developed,which showed significant near-infrared(NIR)light responses.The types and concentrations of intrinsic vacancies were confirmed and quantified by positron annihilation spectrometry and electron spin resonance spectroscopy.Experimental results showed that Br atoms and intrinsic vacancies(dual Br-S)in Bi_(19)Br_(3)S_(27) could greatly enhance the internal polarized electric field and improve the transfer and separation of photogenerated carriers compared with Bi19Cl3S27 and Bi19I3S27.Theoretical calculations revealed that Br atoms in Bi_(19)Br_(3)S_(27) could facilitate CO_(2) adsorption and activation and decrease the formation energy of reactive hydrogen.Among Bi_(19)X_(3)S_(27) nanorods,Bi_(19)Br_(3)S_(27) nanorods revealed the highest CO_(2) photoreduction activity with CO yield rate of 28.68 and 2.28μmol gcatalyst^(−1) h^(−1) with full-spectrum and NIR lights,respectively.This work presents an atomic understanding of the intrinsic vacancies and halogen-mediated CO_(2) photoreduction mechanism.展开更多
Surface charge localization and inferior charge transfer efficiency seriously restrict the supply of reactive hydrogen and the reaction dynamics of CO_(2) photoreduction performance of photocatalysts.Herein,chemically...Surface charge localization and inferior charge transfer efficiency seriously restrict the supply of reactive hydrogen and the reaction dynamics of CO_(2) photoreduction performance of photocatalysts.Herein,chemically bonded BiVO_(4)/Bi_(19)Cl_(3)S_(27)(BVO/BCS)S-scheme heterojunction with a strong internal electric field is designed.Experimental and density function theory calculation results confirm that the elaborated heterojunction accelerates the vectorial migration of photogenerated charges from BiVO_(4) to Bi_(19)Cl_(3)S_(27) via the interfacial chemical bonding interactions(i.e.,Bi-O and Bi-S bonds)between Bi atoms of BVO and S atoms of BCS or Bi atoms of BCS and O atoms of BVO under light irradiation,breaking the interfacial barrier and surface charge localization of Bi_(19)Cl_(3)S_(27),and further decreasing the energy of reactive hydrogen generation,CO_(2) absorption and activation.The separation efficiency of photogenerated carriers is much more efficient than that counterpart individual in BVO/BCS S-scheme heterojunction system.As a result,BVO/BCS heterojunction exhibits a significantly improved continuous photocatalytic performance for CO_(2) reduction and the 24 h CO yield reaches 678.27μmol⋅g^(-1).This work provides an atomic-level insight into charge transfer kinetics and CO_(2) reduction mechanism in S-scheme heterojunction.展开更多
Modulating electronic structures of single-atom metal cocatalysts is vital for highly active photoreduction of CO_(2),and it's especially challenging to develop a facile method to modify the dispersion of atomical...Modulating electronic structures of single-atom metal cocatalysts is vital for highly active photoreduction of CO_(2),and it's especially challenging to develop a facile method to modify the dispersion of atomical photocatalytic sites.We herein report an ion-loading pyrolysis route to in-situ anchor Pd single atoms as well as twinned Pd nanoparticles on ultra-thin graphitic carbon nitride nanosheets(PdTP/Pd_(SA)-CN)for high-efficiency photoreduction of CO_(2).The anchored Pd twinned nanoparticles donate electrons to adjacent single Pd–N_(4) sites through the carbon nitride networks,and the optimized PdTP/Pd_(SA)-CN photocatalyst exhibits a CO evolution rate up to 46.5μmol g^(-1) h^(-1) with nearly 100%selectivity.As revealed by spectroscopic and theoretical analyses,the superior photocatalytic activity is attributed to the lowered desorption barrier of carbonyl species at electron-enriched Pd single atoms,together with the improved efficiencies of light-harvesting and charge separation/transport.This work has demonstrated the engineering of the electron density of single active sites with twinned metal nanoparticles assisted by strong electronic interaction with the support of the atomic metal,and unveiled the underlying mechanism for expedited photocatalytic efficiency.展开更多
The overall photocatalytic CO_(2) reduction reaction(OPCRR)that can directly convert CO_(2) and H_(2)O into fuels represents a promising renewable energy conversion technology.As a typical redox reaction,the OPCRR inv...The overall photocatalytic CO_(2) reduction reaction(OPCRR)that can directly convert CO_(2) and H_(2)O into fuels represents a promising renewable energy conversion technology.As a typical redox reaction,the OPCRR involves two half-reactions:the CO_(2) reduction half-reaction(CRHR)and the water oxidation half-reaction(WOHR).Generally,both half-reactions can be promoted by adjusting the wettability of catalysts.However,there is a contradiction in wettability requirements for the two half-reactions.Specifically,CRHR prefers a hydrophobic surface that can accumulate more CO_(2) molecules on the active sites,ensuring the appropriate ratio of gas-phase(CO_(2))to liquid-phase(H_(2)O)reactants.Conversely,the WOHR prefers a hydrophilic surface that can promote the departure of the gaseous product(O_(2))from the catalyst surface,preventing isolation between active sites and the reactant(H_(2)O).Here,we successfully reconciled the contradictory wettability requirements for the CRHR and WOHR by creating an alternately hydrophobic catalyst.This was achieved through a selectively hydrophobic modification method and a charge-transfer-control strategy.Consequently,the collaboratively promoted CRHR and WOHR led to a significantly enhanced OPCRR with a solar-to-fuel conversion efficiency of 0.186%.Notably,in ethanol production,the catalyst exhibited a 10.64-fold increase in generation rate(271.44μmol g^(-1)h~(-1))and a 4-fold increase in selectivity(55.77%)compared to the benchmark catalyst.This innovative approach holds great potential for application in universal overall reactions involving gas participation.展开更多
The stems of water convolvulus were employed as biotemplates for the replication of their optimized 3D hierarchical architecture to synthesize porous MgO-modified TiO2 . The photocatalytic reduction of CO2 with H2O va...The stems of water convolvulus were employed as biotemplates for the replication of their optimized 3D hierarchical architecture to synthesize porous MgO-modified TiO2 . The photocatalytic reduction of CO2 with H2O vapor into hydrocarbon fuel was studied with these MgO-TiO2 nanostructures as the photocatalysts with the benefits of improved CO2 adsorption and activation through incorporated MgO. Various factors involving CO2 adsorption capacity, migration of charge carriers to the surface, and the number of activity sites, which depend on the amount of added MgO, determine the photocatalytic conversion efficiency.展开更多
A series of highly dispersed platinum‐deposited porous g‐C3N4 (Pt/pg‐C3N4) were successfully fabricated by a simple in situ photoreduction strategy using chloroplatinic acid and porous g‐C3N4 as precursors. Porou...A series of highly dispersed platinum‐deposited porous g‐C3N4 (Pt/pg‐C3N4) were successfully fabricated by a simple in situ photoreduction strategy using chloroplatinic acid and porous g‐C3N4 as precursors. Porous g‐C3N4 was fabricated by a pretreatment strategy using melamine as a raw material.The morphology, porosity, phase, chemical structure, and optical and electronic properties ofas‐prepared Pt/pg‐C3N4 were characterized. The photocatalytic activity of as‐prepared Pt/pg‐C3N4was preliminarily evaluated by the degradation of aqueous azo dyes methyl orange under visible light irradiation. The as‐prepared Pt/pg‐C3N4 were further applied to the degradation and mineralization of aqueous 4‐fluorophenol. The recyclability of Pt/pg‐C3N4 was evaluated under four consecutive photocatalytic runs.展开更多
The photoreduction of CO_(2)to achieve high-value-added hydrocarbons under simulated sunlight irradiation is advantageous,but challenging.In this study,a series of MgO and Au nanoparticle-co-modified g-C_(3)N_(4)photo...The photoreduction of CO_(2)to achieve high-value-added hydrocarbons under simulated sunlight irradiation is advantageous,but challenging.In this study,a series of MgO and Au nanoparticle-co-modified g-C_(3)N_(4)photocatalysts were synthesized and subsequently applied for the photocatalytic reduction of CO_(2)with H2O under simulated solar irradiation.The best photocatalytic performance was demonstrated by the Au and 3%MgO-co-modified g-C_(3)N_(4)photocatalysts with CO,CH_(4),CH3OH,and CH3CHO yields of 423.9,83.2,47.2,and 130.4μmol/g,respectively,in a 3-h reaction.We investigated the effects of MgO and Au as cocatalysts on photocatalytic behaviors,respectively.The characterizations and experimental results showed that the enhanced photocatalytic activity was due to the synergistic effect among the components of the ternary photocatalyst.The cocatalyst MgO can activate CO_(2)(adsorbed at the interface between the MgO and Au particles),and the Mg-N bonds formed in the MgO-CN nanosheets played an important role in the charge transfer.Meanwhile,the Au particles that were modified into MgO/g-C_(3)N_(4)can increase the absorption of visible light via the surface plasmon resonance effect and further reduce the activation energies of the photoreduction of CO_(2)using H2O.This study provided an effective method for the modification of traditional primary photocatalysts with promising performance for photocatalytic CO_(2)reduction.展开更多
Photocatalytic conversion of CO_(2) to high-value products plays a crucial role in the global pursuit of carbon–neutral economy.Junction photocatalysts,such as the isotype heterojunctions,offer an ideal paradigm to n...Photocatalytic conversion of CO_(2) to high-value products plays a crucial role in the global pursuit of carbon–neutral economy.Junction photocatalysts,such as the isotype heterojunctions,offer an ideal paradigm to navigate the photocatalytic CO_(2) reduction reaction(CRR).Herein,we elucidate the behaviors of isotype heterojunctions toward photocatalytic CRR over a representative photocatalyst,g-C_(3)N_(4).Impressively,the isotype heterojunctions possess a significantly higher efficiency for the spatial separation and transfer of photogenerated carriers than the single components.Along with the intrinsically outstanding stability,the isotype heterojunctions exhibit an exceptional and stable activity toward the CO_(2) photoreduction to CO.More importantly,by combining quantitative in situ technique with the first-principles modeling,we elucidate that the enhanced photoinduced charge dynamics promotes the production of key intermediates and thus the whole reaction kinetics.展开更多
Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high...Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.展开更多
Photoreduction characteristics of divalent inorganic mercury (Hg2+) in the presence of specific algae species are still not well known.Laboratory experiments were conducted in the present study to identify the effects...Photoreduction characteristics of divalent inorganic mercury (Hg2+) in the presence of specific algae species are still not well known.Laboratory experiments were conducted in the present study to identify the effects of different concentrations of living/dead algae species,including Aphanizomenon flosaquae (AF) and Microcystis aeruginosa (MA),on the photoreduction rate of Hg2+ under various light conditions.The experimental results showed that percentage reduction of Hg2+ was significantly influenced by radiation wavelengths,and dramatically decreased with the presence of algae.The highest percentage reduction of Hg2+ was induced by UV-A,followed by UV-B,visible light and dark for both living and dead AF,and the order was dark > UV-A > UV-B > visible light for both living and dead MA.There were two aspects,i.e.,energy and attenuation rate of light radiation and excrementitious generated from algae metabolisms,were involved in the processes of Hg2+ photoreduction with the presence of algae under different light conditions.The percentage reduction of Hg2+ decreased from 15% to 11% when living and dead AF concentrations increased by 10 times (from 106 to 105 cells/mL),and decreased from11% to ~9% in the case of living and dead MA increased.Algae can adsorb Hg2+ and decrease the concentration of free Hg2+,thus inhibiting Hg2+ photoreduction,especially under the conditions with high concentrations of algae.No significant differences were found in percentage reduction of Hg2+ between living and dead treatments of algae species.The results are of great importance for understanding the role of algae in Hg2+ photoreduction.展开更多
The BiOCl(BOC)synthesized by the water bath heating method was treated with sodium borohydride(NaBH_(4))to introduce oxygen vacancies(OVs).At the same time,Au nanoparticles were loaded to prepare a series of Au/BiOCl ...The BiOCl(BOC)synthesized by the water bath heating method was treated with sodium borohydride(NaBH_(4))to introduce oxygen vacancies(OVs).At the same time,Au nanoparticles were loaded to prepare a series of Au/BiOCl samples with different ratios.OVs and Au nanoparticles can promote the light absorption of host photocatalyst in the visible region.The calculated work function of BiOCl and Au can verify the existence of Ohmic contact between the interface of them,which is conducive to the separation of charge carriers.Through a series of photoelectric tests,it was verified experimentally that the separation of charge carriers is indeed enhanced.The high-energy hot electrons produced by Au under the surface plasmon resonance(SPR)effect can increase the counts of electrons to participate in the CO_(2)reduction reaction.Especially for 1.0%-Au/BOC,the yields of CO can reach 43.16μmol g^(−1)h^(−1),which is 6.6 times more than that of BOC.Therefore,loading precious metal on semiconductors is an effective strategy to promote the photocatalytic performance of CO_(2)reduction reactions.展开更多
The performance of CeO2-TiO2 photocatalyst for the photocatalytic reduction of CO2 into methanol was studied under visible light irradiation. The as-prepared catalysts were characterized for their structural, textural...The performance of CeO2-TiO2 photocatalyst for the photocatalytic reduction of CO2 into methanol was studied under visible light irradiation. The as-prepared catalysts were characterized for their structural, textural and optical properties using X-ray diffraction（XRD）, field emission scanning electron microscopy（FESEM）, X-ray photoelectron spectroscopy（XPS）, nitrogen physisorption analysis, UV-vis spectroscopy and photoluminescence（PL） spectroscopy. The characterization results indicated that the presence of CeO2 stabilized the anatase phase of TiO2, decreased its crystallite size, increased the surface area, reduced the band gap energy and lowered the rate of electron-hole pair recombination. The CeO2-TiO2 photocatalyst showed an increased methanol yield of 18.6 μmol/g under visible light irradiation, compared to the bare TiO2（6.0 μmol/g）.展开更多
文摘Composites derived from metal-organic frameworks(MOFs)show promise as catalysts for the photocat-alytic reduction of CO_(2).However,their potential is hindered by constraints such as limited light absorp-tion and sluggish electron transfer and separation,impacting the overall efficiency of the photocatalytic process.In this study,TiO_(2)nanocrystals,modified with Ptx+,underwent laser etching were encapsulated within the traditional MOF-ZIF-8 framework.This enhanced the adsorption capabilities for CO_(2)reactants and solar light,while also facilitating directed electron transfer and the separation of photogenerated charges.The finely-tuned catalyst demonstrates impressive CH_(4) selectivity at 9.5%,with yields of 250.24μmol g^(-1)h^(-1)for CO and 25.43μmol g^(-1)h^(-1)for CH_(4),utilizing water as a hole trap and H^(+)source.This study demonstrates the viability of achieving characteristics related to the separation of photogen-erated charges in TiO_(2)nanocrystals through laser etching and MOF composite catalysts.It offers novel perspectives for designing MOF-based catalysts with enhanced performance in artificial photosynthesis.
基金supported by the National Natural Science Foundation of China(12241502,92045301)Fundamental Research Funds for the Central Universities(20720220010)+7 种基金USTC Research Funds of the Double First-Class Initiative(YD2310002012)the Launching Special Funds of Scientific Research for Introduced Talents from University of Science and Technology of China(KY2310000060)National Key Research and Development Program of China(2019YFA0405602)Anhui Provincial Natural Science Foundation(2408085QB049)the Instruments Center for Physical Science and USTC Center for Micro and Nanoscale Research and Fabrication,University of Science and Technology of Chinathe solid supports from the BL03U,BL10B,and BL12B beamlines of the National Synchrotron Radiation Laboratory(NSRL,Hefei)the Shanghai Synchrotron Radiation Facility(SSRF,Shanghai)of BL11B(https://cstr.cn/31124.02.SSRF.BL11B)and BL14W1(https://cstr.cn/31124.02.SSRF.BL14W1)beamlines for the assistance on XAFS measurementsAnhui Chuangpu Instruments Co.,Ltd.for the assistance in the test of Table XAFS。
文摘Photocatalytic CO_(2)reduction into value-added chemicals holds significant promise for carbon-neutral recycling and solar-to-fuel conversion.Enhancing reaction efficiency by manipulating charge transfer is a key approach to unlocking this potential.In this work,we construct a two-dimensional/twodimensional(2D/2D)FeSe_(2)/protonated carbon nitride(FeSe_(2)/PCN)heterostructure to promote the interfacial charge transfer dynamics,leading to a four-fold improved conversion efficiency of photocatalytic CO_(2)reduction with near 100%CO selectivity.Combining in situ X-ray photoelectron spectroscopy,in situ soft X-ray absorption spectroscopy,and femtosecond transient absorption spectroscopy,it is revealed that FeSe_(2)acts as an electron acceptor upon photoexcitation,introducing an additional electron transfer pathway from PCN to FeSe_(2)that suppresses radiative recombination and promotes charge transfer.In situ X-ray absorption fine structure spectroscopy,in situ diffuse reflectance infrared Fourier transform spectroscopy,and density functional theory calculation further unravel that the electron-enriched FeSe_(2)functions as the active sites for CO_(2)activation and significantly reduces the energy barrier of key intermediate COOH*formation,which is the rate-determined step for CO generation.This work underscores the importance of regulating photocarrier relaxation pathways to achieve effective spatial charge separation for promoted photocatalytic CO_(2)reduction and demonstrates the powerful functions of in situ spectroscopies in in-depth understanding of the photocatalytic mechanism.
基金supported by the National Natural Science Foundation of China(Nos.U2102211 and 22378101)the Fundamental Research Foundation for Universities of Heilongjiang Province(No.2021-KYYWF-0004)the Science Fund for Distinguished Young Scholars of Heilongjiang University(No.JCL202102)。
文摘The interface modulation significantly affects the photocatalytic performances of supported metal phthalocyanines(MPc)-based systems.Herein,ZnPc was loaded on nanosized Au-modified TiO_(2)nanosheets(Au-T)to obtain wide-spectrum ZnPc/Au-T photocatalysts.Compared with large Au NP(8 nm)-mediated ZnPc/Au-T photocatalyst,ultrasmall Au NP(3 nm)-mediated one shows advantageous photoactivity,achieving 3-and 10-fold CO_(2)conversion rates compared with reference ZnPc/T and pristine TiO_(2)nanosheets,respectively.Employing monochromatic beam-assisted surface photovoltage and photocurrent action,etc.,the introduction of ultrasmall Au NPs more effectively facilitates intrinsic interfacial charge transfer.Moreover,ZnP c molecules are found more dispersed with the existence of small Au NPs hence exposing abundant Zn^(2+)sites as the catalytic center for CO_(2)reduction.This work provides a feasible design strategy and renewed recognition for supported MPc-based photocatalyst systems.
文摘The highly photocatalytic conversion of CO_(2)into valuable products is a promising method for mitigating the global greenhouse effect and increasing the energy supply.However,the utilization of electron-deficient active sites to activate CO_(2)leads to lower photocatalytic efficiency and selectivity.One effective strategy to improve CO_(2)photoreduction performance is making precise adjustments to the electronic structure of the photocatalyst.Herein,the defective TiO_(2)modified with Cu,Ba,and CuBa metal sites is synthesized via a simple photo-deposition method and applied for photoreduction of CO_(2).Among the prepared catalysts,Cu1Ba_(3)/TiO_(2)-SBO(TiO_(2)-SBO:TiO_(2)with surface and bulk oxygen vacancies)has been demonstrated to possess excellent photocatalytic conversion of CO_(2),with the activity levels of the CO and CH_(4) that are 8 and 6 times higher than the bare TiO_(2)-SBO,and the electron selectivity of CO is up to 53%.The results reveal that oxygen vacancies and CuBa bimetallic sites have a synergistic ability to facilitate the separation of photogenerated carriers.Furthermore,the electron-donor Ba metal enables modulation of the electronic structure of Cu co-catalysts,generating electron-rich Cu metal sites that accelerate the activation of CO_(2).Meanwhile,the theoretical calculations prove that the Cu1Ba_(3)/TiO_(2)-SBO has the stronger CO_(2)adsorption energy,and its strengthened binding of^(*)COOH and the markedly reduced formation energy of CO and^(*)CO intermediates boost the conversion of COOH to CO and enhance the selectivity of CO.Thereby,the defective TiO_(2)modified with CuBa bimetal represents a more effective measure for CO_(2)reduction into valuable products.
基金support from National Natural Science Foundation of China(21771047)Natural Science Foundation of Heilongjiang Province,China(YQ2020E029)Open Project of State Key Laboratory of Inorganic Synthesis&Preparative Chemistry,Jilin University(2023-17).
文摘Herein,PtO-supported GdFeO_(3)(PtO/GdFeO_(3))composite photocatalysts were synthesized by a solutionbased technique.Extensive analysis using various analytical instruments has shown that PtO plays a crucial function in augmenting the visible light absorption capacity of composites.Better photogenerated charge carrier transport was credited with this improvement,which led to a decrease in bandgap energy as low as 2.14 eV.The PtO/GdFeO_(3) nanocomposites showed remarkable photocatalytic activity when exposed to visible light,especially in the conversion of CO_(2) into CH_(3)OH.After 9 h of light,a noteworthy yield of 1550μmol·g^(−1) of methanol was produced,demonstrating maximum efficiency at a dose of 2.0 g·L^(−1) and a concentration of 5.0%PtO/GdFeO_(3).This yield indicates the effectiveness of the heterostructure,which outperformed pristine GdFeO_(3) by a factor of 7.85.This significant enhancement highlights the potential advantages of the modified structure in improving performance.Most significantly,the photocatalyst's durability maintained 98.0%of its initial efficacy throughout five cycles.The success of PtO/GdFeO_(3) is largely due to the synergistic light absorption capabilities and enhanced photocharge carrier separation that the integration of PtO produced.It highlights the conversion of CO_(2) into valuable chemicals under visible light exposure,as well as the promise of mixed oxide nanostructures in ecologically responsible material creation.
文摘Efficiently converting CO_(2)and H_(2)O into value-added chemicals using solar energy is a viable approach to address global warming and the energy crisis.However,achieving artificial photocatalytic CO_(2)reduction using H_(2)O as the reductant poses challenges is due to the difficulty in efficient cooperation among multiple functional moieties.Metal-organic frameworks(MOFs)are promising candidates for overall CO_(2)photoreduction due to their large surface area,diverse active sites,and excellent tailorability.In this study,we designed a metal-organic framework photocatalyst,named PCN-224(Zn)-Bpy(Ru),by integrating photoactive Zn(Ⅱ)-porphyrin and Ru(Ⅱ)-bipyridyl moieties.In comparison,two isostructural MOFs just with either Zn(Ⅱ)-porphyrin or Ru(Ⅱ)-bipyridyl moiety,namely PCN-224-Bpy(Ru)and PCN-224(Zn)-Bpy were also synthesized.As a result,PCN-224(Zn)-Bpy(Ru)exhibited the highest photocatalytic conversion rate of CO_(2)to CO,with a production rate of 7.6μmol·g^(-1)·h^(-1)in a mixed solvent of CH_(3)CN and H_(2)O,without the need for co-catalysts,photosensitizers,or sacrificial agents.Mass spectrometer analysis detected the signals of^(13)CO(m/z=29),^(13)C^(18)O(m/z=31),^(16)O^(18)O(m/z=34),and^(18)O_(2)(m/z=36),confirming that CO_(2)and H_(2)O acted as the carbon and oxygen sources for CO and O_(2),respectively,thereby confirming the coupling of photocatalytic CO_(2)reduction with H_(2)O oxidation.In contrast,using PCN-224-Bpy(Ru)or PCN-224(Zn)-Bpy as catalysts under the same conditions resulted in significantly lower CO production rates of only 1.5 and 0μmol·g^(-1)·h^(-1),respectively.Mechanistic studies revealed that the lowest unoccupied molecular orbital(LUMO)potential of PCN-224(Zn)-Bpy(Ru)is more negative than the redox potentials of CO_(2)/CO,and the highest occupied molecular orbital(HOMO)potential is more positive than that of H_(2)O/O_(2),satisfying the thermodynamic requirements for overall photocatalytic CO_(2)reduction.In comparison,the HOMO potential of PCN-224(Zn)-Bpy without Ru(II)-bipyridyl moieties is less positive than that of H_(2)O/O_(2),indicating that the Ru(II)-bipyridyl moiety is thermodynamically necessary for CO_(2)reduction coupled with H_(2)O oxidation.Additionally,photoluminescence spectroscopy revealed that the fluorescence of PCN-224(Zn)-Bpy(Ru)was almost completely quenched,and a longer average photoluminescence lifetime compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru)was observed.These suggest a low recombination rate of photogenerated carriers in PCN-224(Zn)-Bpy(Ru),which also supported by the higher photocurrent observed in PCN-224(Zn)-Bpy(Ru)compared to PCN-224(Zn)-Bpy and PCN-224-Bpy(Ru).In summary,the integrated Zn(II)-porphyrin and Ru(II)-bipyridyl moieties in PCN-224(Zn)-Bpy(Ru)play important roles of a photosensitizer and CO_(2)reduction as well as H_(2)O oxidation sites,and their efficient cooperation optimizes the band structure,thereby facilitating the coupling of CO_(2)reduction with H_(2)O oxidation and resulting in highperformance artificial photocatalytic CO_(2)reduction.
文摘The photoreduction of greenhouse gas CO_(2) using photocatalytic technologies not only benefits en-vironmental remediation but also facilitates the production of raw materials for chemicals.Howev-er,the efficiency of CO_(2) photoreduction remains generally low due to the challenging activation of CO_(2) and the limited light absorption and separation of charge.Defect engineering of catalysts rep-resents a pivotal strategy to enhance the photocatalytic activity for CO_(2),with most research on met-al oxide catalysts focusing on the creation of anionic vacancies.The exploration of metal vacancies and their effects,however,is still underexplored.In this study,we prepared an In2O3 catalyst with indium vacancies(VIn)through defect engineering for CO_(2) photoreduction.Experimental and theo-retical calculations results demonstrate that VIn not only facilitate light absorption and charge sepa-ration in the catalyst but also enhance CO_(2) adsorption and reduce the energy barrier for the for-mation of the key intermediate*COOH during CO_(2) reduction.Through metal vacancy engineering,the activity of the catalyst was 7.4 times,reaching an outstanding rate of 841.32μmol g(-1)h^(-1).This work unveils the mechanism of metal vacancies in CO_(2) photoreduction and provides theoretical guidance for the development of novel CO_(2) photoreduction catalysts.
基金This work was supported by the National Natural Science Foundation of China(Nos.22138011,22205108,22378206)Open Research Fund of Key Laboratory of the Ministry of Education for Advanced Catalysis Materials and Zhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces(KLMEACM 202201),Zhejiang Normal University.
文摘The insufficient active sites and slow interfacial charge trans-fer of photocatalysts restrict the efficiency of CO_(2) photoreduction.The synchronized modulation of the above key issues is demanding and chal-lenging.Herein,strain-induced strategy is developed to construct the Bi–O-bonded interface in Cu porphyrin-based monoatomic layer(PML-Cu)and Bi_(12)O_(17)Br_(2)(BOB),which triggers the surface interface dual polarization of PML-Cu/BOB(PBOB).In this multi-step polarization,the built-in electric field formed between the interfaces induces the electron transfer from con-duction band(CB)of BOB to CB of PML-Cu and suppresses its reverse migration.Moreover,the surface polarization of PML-Cu further promotes the electron converge in Cu atoms.The introduction of PML-Cu endows a high density of dispersed Cu active sites on the surface of PBOB,significantly promoting the adsorption and activation of CO_(2) and CO desorption.The conversion rate of CO_(2) photoreduction to CO for PBOB can reach 584.3μmol g-1,which is 7.83 times higher than BOB and 20.01 times than PML-Cu.This work offers valuable insights into multi-step polarization regulation and active site design for catalysts.
基金Cooperation between industry and education project of Ministry of Education,Grant/Award Number:220601318235513Zhejiang Provincial Natural Science Foundation,Grant/Award Number:LQ23E020002+4 种基金Wenzhou Key Scientific and Technological Innovation Research Projects,Grant/Award Number:ZG2023053Wenzhou Natural Science Foundation,Grant/Award Numbers:G20220019,G20220021Wenzhou Science and Technology Association Serves Scientific and Technological Innovation Projects,Grant/Award Number:KJFW0201National Natural Science Foundation of China,Grant/Award Numbers:22308336,52202284City University of Hong Kong startup fund.
文摘Ternary halo-sulfur bismuth compound Bi_(19)X_(3)S_(27)(X=Cl,Br,I)with distinct electronic structure and full-spectrum light-harvesting properties show great application potential in the CO_(2) photoreduction field.However,the relationship between photocatalytic CO_(2) reduction performance and the function of halogens in Bi_(19)X_(3)S_(27) is still poorly understood.Herein,a series of Bi_(19)X_(3)S_(27) nanorod photocatalysts with intrinsic X and S dual vacancies were developed,which showed significant near-infrared(NIR)light responses.The types and concentrations of intrinsic vacancies were confirmed and quantified by positron annihilation spectrometry and electron spin resonance spectroscopy.Experimental results showed that Br atoms and intrinsic vacancies(dual Br-S)in Bi_(19)Br_(3)S_(27) could greatly enhance the internal polarized electric field and improve the transfer and separation of photogenerated carriers compared with Bi19Cl3S27 and Bi19I3S27.Theoretical calculations revealed that Br atoms in Bi_(19)Br_(3)S_(27) could facilitate CO_(2) adsorption and activation and decrease the formation energy of reactive hydrogen.Among Bi_(19)X_(3)S_(27) nanorods,Bi_(19)Br_(3)S_(27) nanorods revealed the highest CO_(2) photoreduction activity with CO yield rate of 28.68 and 2.28μmol gcatalyst^(−1) h^(−1) with full-spectrum and NIR lights,respectively.This work presents an atomic understanding of the intrinsic vacancies and halogen-mediated CO_(2) photoreduction mechanism.
基金financially supported by Outstanding Talent Research Fund of Zhengzhou University,China Postdoc toral Science Foundation(2020TQ0277,2020M682328)Central Plains Science and Technology Innovation Leader Project(214200510006)+1 种基金China Scholarship Council(No.202108410356)Postdoctoral Science Foundation of Henan province(202002010).
文摘Surface charge localization and inferior charge transfer efficiency seriously restrict the supply of reactive hydrogen and the reaction dynamics of CO_(2) photoreduction performance of photocatalysts.Herein,chemically bonded BiVO_(4)/Bi_(19)Cl_(3)S_(27)(BVO/BCS)S-scheme heterojunction with a strong internal electric field is designed.Experimental and density function theory calculation results confirm that the elaborated heterojunction accelerates the vectorial migration of photogenerated charges from BiVO_(4) to Bi_(19)Cl_(3)S_(27) via the interfacial chemical bonding interactions(i.e.,Bi-O and Bi-S bonds)between Bi atoms of BVO and S atoms of BCS or Bi atoms of BCS and O atoms of BVO under light irradiation,breaking the interfacial barrier and surface charge localization of Bi_(19)Cl_(3)S_(27),and further decreasing the energy of reactive hydrogen generation,CO_(2) absorption and activation.The separation efficiency of photogenerated carriers is much more efficient than that counterpart individual in BVO/BCS S-scheme heterojunction system.As a result,BVO/BCS heterojunction exhibits a significantly improved continuous photocatalytic performance for CO_(2) reduction and the 24 h CO yield reaches 678.27μmol⋅g^(-1).This work provides an atomic-level insight into charge transfer kinetics and CO_(2) reduction mechanism in S-scheme heterojunction.
基金We appreciate the financial support from the National Natural Science Foundation of China(22272150,22102145)the Major Program of Zhejiang Provincial Natural Science Foundation(LD22B030002)+3 种基金Zhejiang Provincial Ten Thousand Talent Program(2021R51009)Zhejiang Provincial Natural Science Foundation of China(LQ23B030006,LY22B030012)Shandong Provincial Natural Science Foundation of China(2020MB053)the Fundamental Research Funds for the Central Universities(DUT22RC(3)084).
文摘Modulating electronic structures of single-atom metal cocatalysts is vital for highly active photoreduction of CO_(2),and it's especially challenging to develop a facile method to modify the dispersion of atomical photocatalytic sites.We herein report an ion-loading pyrolysis route to in-situ anchor Pd single atoms as well as twinned Pd nanoparticles on ultra-thin graphitic carbon nitride nanosheets(PdTP/Pd_(SA)-CN)for high-efficiency photoreduction of CO_(2).The anchored Pd twinned nanoparticles donate electrons to adjacent single Pd–N_(4) sites through the carbon nitride networks,and the optimized PdTP/Pd_(SA)-CN photocatalyst exhibits a CO evolution rate up to 46.5μmol g^(-1) h^(-1) with nearly 100%selectivity.As revealed by spectroscopic and theoretical analyses,the superior photocatalytic activity is attributed to the lowered desorption barrier of carbonyl species at electron-enriched Pd single atoms,together with the improved efficiencies of light-harvesting and charge separation/transport.This work has demonstrated the engineering of the electron density of single active sites with twinned metal nanoparticles assisted by strong electronic interaction with the support of the atomic metal,and unveiled the underlying mechanism for expedited photocatalytic efficiency.
基金financially supported by the National Natural Science Foundation of China(22378204,22008121,51790492)the National Outstanding Youth Science Fund Project of National Natural Science Foundation of China(T2125004)+1 种基金the Funding of NJUST(No.TSXK2022D002)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23_0454)。
文摘The overall photocatalytic CO_(2) reduction reaction(OPCRR)that can directly convert CO_(2) and H_(2)O into fuels represents a promising renewable energy conversion technology.As a typical redox reaction,the OPCRR involves two half-reactions:the CO_(2) reduction half-reaction(CRHR)and the water oxidation half-reaction(WOHR).Generally,both half-reactions can be promoted by adjusting the wettability of catalysts.However,there is a contradiction in wettability requirements for the two half-reactions.Specifically,CRHR prefers a hydrophobic surface that can accumulate more CO_(2) molecules on the active sites,ensuring the appropriate ratio of gas-phase(CO_(2))to liquid-phase(H_(2)O)reactants.Conversely,the WOHR prefers a hydrophilic surface that can promote the departure of the gaseous product(O_(2))from the catalyst surface,preventing isolation between active sites and the reactant(H_(2)O).Here,we successfully reconciled the contradictory wettability requirements for the CRHR and WOHR by creating an alternately hydrophobic catalyst.This was achieved through a selectively hydrophobic modification method and a charge-transfer-control strategy.Consequently,the collaboratively promoted CRHR and WOHR led to a significantly enhanced OPCRR with a solar-to-fuel conversion efficiency of 0.186%.Notably,in ethanol production,the catalyst exhibited a 10.64-fold increase in generation rate(271.44μmol g^(-1)h~(-1))and a 4-fold increase in selectivity(55.77%)compared to the benchmark catalyst.This innovative approach holds great potential for application in universal overall reactions involving gas participation.
基金supported by the National Basic Research Program of China(973 Program,2014CB239302,2013CB632404)the Natural Science Foundation of Jiangsu Province(BK20130053)the National Natural Science Foundation of China(51272101,51202005,21473091)
文摘The stems of water convolvulus were employed as biotemplates for the replication of their optimized 3D hierarchical architecture to synthesize porous MgO-modified TiO2 . The photocatalytic reduction of CO2 with H2O vapor into hydrocarbon fuel was studied with these MgO-TiO2 nanostructures as the photocatalysts with the benefits of improved CO2 adsorption and activation through incorporated MgO. Various factors involving CO2 adsorption capacity, migration of charge carriers to the surface, and the number of activity sites, which depend on the amount of added MgO, determine the photocatalytic conversion efficiency.
基金supported by the National Natural Science Foundation of China (51568049, 51208248, 51468043, 21366024)the National Science Fund for Excellent Young Scholars (51422807)+1 种基金the Natural Science Foundation of Jiangxi Province, China (20161BAB206118, 20114BAB213015)the Natural Science Foundation of Jiangxi Provincial Department of Education, China (GJJ14515, GJJ12456)~~
文摘A series of highly dispersed platinum‐deposited porous g‐C3N4 (Pt/pg‐C3N4) were successfully fabricated by a simple in situ photoreduction strategy using chloroplatinic acid and porous g‐C3N4 as precursors. Porous g‐C3N4 was fabricated by a pretreatment strategy using melamine as a raw material.The morphology, porosity, phase, chemical structure, and optical and electronic properties ofas‐prepared Pt/pg‐C3N4 were characterized. The photocatalytic activity of as‐prepared Pt/pg‐C3N4was preliminarily evaluated by the degradation of aqueous azo dyes methyl orange under visible light irradiation. The as‐prepared Pt/pg‐C3N4 were further applied to the degradation and mineralization of aqueous 4‐fluorophenol. The recyclability of Pt/pg‐C3N4 was evaluated under four consecutive photocatalytic runs.
文摘The photoreduction of CO_(2)to achieve high-value-added hydrocarbons under simulated sunlight irradiation is advantageous,but challenging.In this study,a series of MgO and Au nanoparticle-co-modified g-C_(3)N_(4)photocatalysts were synthesized and subsequently applied for the photocatalytic reduction of CO_(2)with H2O under simulated solar irradiation.The best photocatalytic performance was demonstrated by the Au and 3%MgO-co-modified g-C_(3)N_(4)photocatalysts with CO,CH_(4),CH3OH,and CH3CHO yields of 423.9,83.2,47.2,and 130.4μmol/g,respectively,in a 3-h reaction.We investigated the effects of MgO and Au as cocatalysts on photocatalytic behaviors,respectively.The characterizations and experimental results showed that the enhanced photocatalytic activity was due to the synergistic effect among the components of the ternary photocatalyst.The cocatalyst MgO can activate CO_(2)(adsorbed at the interface between the MgO and Au particles),and the Mg-N bonds formed in the MgO-CN nanosheets played an important role in the charge transfer.Meanwhile,the Au particles that were modified into MgO/g-C_(3)N_(4)can increase the absorption of visible light via the surface plasmon resonance effect and further reduce the activation energies of the photoreduction of CO_(2)using H2O.This study provided an effective method for the modification of traditional primary photocatalysts with promising performance for photocatalytic CO_(2)reduction.
基金This work was financially supported in part by the National Natural Science Foundation of China(Grant Nos.12047564,52071041,12074048)the Project for Fundamental and Frontier Research in Chongqing(cstc2020jcyj-msxmX0777 and cstc2020jcyj-msxmX0796)+1 种基金the Fundamental Research Funds for the Central Universities(cqu2018CDHB1A09,106112016CDJZR308808)Open access funding provided by Shanghai Jiao Tong University
文摘Photocatalytic conversion of CO_(2) to high-value products plays a crucial role in the global pursuit of carbon–neutral economy.Junction photocatalysts,such as the isotype heterojunctions,offer an ideal paradigm to navigate the photocatalytic CO_(2) reduction reaction(CRR).Herein,we elucidate the behaviors of isotype heterojunctions toward photocatalytic CRR over a representative photocatalyst,g-C_(3)N_(4).Impressively,the isotype heterojunctions possess a significantly higher efficiency for the spatial separation and transfer of photogenerated carriers than the single components.Along with the intrinsically outstanding stability,the isotype heterojunctions exhibit an exceptional and stable activity toward the CO_(2) photoreduction to CO.More importantly,by combining quantitative in situ technique with the first-principles modeling,we elucidate that the enhanced photoinduced charge dynamics promotes the production of key intermediates and thus the whole reaction kinetics.
文摘Reducing CO_(2) to hydrocarbon fuels by solar irradiation provides a feasible channel for mitigating excessive CO_(2) emissions and addressing resource depletion.Nevertheless,severe charge recombi‐nation and the high energy barrier for CO_(2) photoreduction on the surface of photocatalysts com‐promise the catalytic performance.Herein,a 2D/2D Bi_(2)MoO_(6)/BiOI composite was fabricated to achieve improved CO_(2) photoreduction efficiency.Charge transfer in the composite was facilitated by the van der Waals heterojunction with a large‐area interface.Work function calculation demon‐strated that S‐scheme charge transfer is operative in the composite,and effective charge separation and strong redox capability were revealed by time‐resolved photoluminescence and electron para‐magnetic resonance spectroscopy.Moreover,the intermediates of CO_(2) photoreduction were identi‐fied based on the in situ diffuse reflectance infrared Fourier‐transform spectra.Density functional theory calculations showed that CO_(2) hydrogenation is the rate‐determining step for yielding CH_(4) and CO.Introducing Bi_(2)MoO_(6) into the composite further decreased the energy barrier for CO_(2) photoreduction on BiOI by 0.35 eV.This study verifies the synergistic effect of the S‐scheme heterojunction and van der Waals heterojunction in the 2D/2D composite.
基金supported by the Science and Technology Department of Guizhou Province(No.Qiankehe LH zi [2017]7334hao)the China Postdoctoral Science Foundation(No.2017M613005)+2 种基金Foundation of Guizhou Educational Committee(No.Qian jiao he KY[2016]135)the National Natural Science Foundation of China(No.41563012)the Doctoral Scientific Research Foundation of Guizhou Normal University for 2014
文摘Photoreduction characteristics of divalent inorganic mercury (Hg2+) in the presence of specific algae species are still not well known.Laboratory experiments were conducted in the present study to identify the effects of different concentrations of living/dead algae species,including Aphanizomenon flosaquae (AF) and Microcystis aeruginosa (MA),on the photoreduction rate of Hg2+ under various light conditions.The experimental results showed that percentage reduction of Hg2+ was significantly influenced by radiation wavelengths,and dramatically decreased with the presence of algae.The highest percentage reduction of Hg2+ was induced by UV-A,followed by UV-B,visible light and dark for both living and dead AF,and the order was dark > UV-A > UV-B > visible light for both living and dead MA.There were two aspects,i.e.,energy and attenuation rate of light radiation and excrementitious generated from algae metabolisms,were involved in the processes of Hg2+ photoreduction with the presence of algae under different light conditions.The percentage reduction of Hg2+ decreased from 15% to 11% when living and dead AF concentrations increased by 10 times (from 106 to 105 cells/mL),and decreased from11% to ~9% in the case of living and dead MA increased.Algae can adsorb Hg2+ and decrease the concentration of free Hg2+,thus inhibiting Hg2+ photoreduction,especially under the conditions with high concentrations of algae.No significant differences were found in percentage reduction of Hg2+ between living and dead treatments of algae species.The results are of great importance for understanding the role of algae in Hg2+ photoreduction.
基金supported by the National Natural Science Foundation of China(Nos.51772183.52072230)the Yulin Science and Technology Project(No.CXY-2020-040)。
文摘The BiOCl(BOC)synthesized by the water bath heating method was treated with sodium borohydride(NaBH_(4))to introduce oxygen vacancies(OVs).At the same time,Au nanoparticles were loaded to prepare a series of Au/BiOCl samples with different ratios.OVs and Au nanoparticles can promote the light absorption of host photocatalyst in the visible region.The calculated work function of BiOCl and Au can verify the existence of Ohmic contact between the interface of them,which is conducive to the separation of charge carriers.Through a series of photoelectric tests,it was verified experimentally that the separation of charge carriers is indeed enhanced.The high-energy hot electrons produced by Au under the surface plasmon resonance(SPR)effect can increase the counts of electrons to participate in the CO_(2)reduction reaction.Especially for 1.0%-Au/BOC,the yields of CO can reach 43.16μmol g^(−1)h^(−1),which is 6.6 times more than that of BOC.Therefore,loading precious metal on semiconductors is an effective strategy to promote the photocatalytic performance of CO_(2)reduction reactions.
基金the Ministry of Education (MOE), Universiti Kebangsaan Malaysia and Universiti Malaysia Pahang for financial support of this research under RAGS (RDU131418) and FRGS (RDU120112)
文摘The performance of CeO2-TiO2 photocatalyst for the photocatalytic reduction of CO2 into methanol was studied under visible light irradiation. The as-prepared catalysts were characterized for their structural, textural and optical properties using X-ray diffraction（XRD）, field emission scanning electron microscopy（FESEM）, X-ray photoelectron spectroscopy（XPS）, nitrogen physisorption analysis, UV-vis spectroscopy and photoluminescence（PL） spectroscopy. The characterization results indicated that the presence of CeO2 stabilized the anatase phase of TiO2, decreased its crystallite size, increased the surface area, reduced the band gap energy and lowered the rate of electron-hole pair recombination. The CeO2-TiO2 photocatalyst showed an increased methanol yield of 18.6 μmol/g under visible light irradiation, compared to the bare TiO2（6.0 μmol/g）.
