Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology r...Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.展开更多
Direct-Z-scheme g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)photocatalyst with giant internal electric field was prepared by onestep aqueous sonication self-assembly method using g-C_(3)N_(4)and MXene of Ti_(3)C_(2)as the source ...Direct-Z-scheme g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)photocatalyst with giant internal electric field was prepared by onestep aqueous sonication self-assembly method using g-C_(3)N_(4)and MXene of Ti_(3)C_(2)as the source materials.The chemical composition and structure of the catalysts was characterized by FT-IR,XRD,SEM,TEM,and XPS.The XPS characterization indicated that Ti_(3)C_(2)was partially oxidized to TiO_(2)during the composite process.As a result,an efficient direct-Z-scheme heterojunction structure consisting of the g-C_(3)N_(4)and TiO_(2)with Ti_(3)C_(2)as an electron bridge was constructed.The photocatalytic performance of the prepared catalysts was evaluated by degrading the Rhodamine B(RhB)wastewater.Compared with the single g-C_(3)N_(4),the g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)composite photocatalyst exhibited efficient and stable photocatalytic degradation ability,with a degradation efficiency as high as 99.2%for RhB under optimal conditions(2%Ti_(3)C_(2),pH=3).The high degradation performance of g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)for RhB was attributed to the combination of Ti_(3)C_(2),TiO_(2),and g-C_(3)N_(4)components,forming a direct-Z-scheme heterojunction with a high-speed electron transport channel structure.The role of Z-scheme heterojunctions in electron transport is verified by photoelectrochemical characterization,along with photoluminescence(PL).Our research provides a simple method to design photocatalysts by constructing direct-Z-scheme electron transport channels for highly efficient treatment of dye wastewater.展开更多
Plasma-catalysis is considered as one of the most promising technologies for antibiotic degradation in water.In the plasma-catalytic system,one of the factors affecting the degradation effect is the performance of the...Plasma-catalysis is considered as one of the most promising technologies for antibiotic degradation in water.In the plasma-catalytic system,one of the factors affecting the degradation effect is the performance of the photocatalyst,which is usually restricted by the rapid recombination of electrons and holes as well as narrow light absorption range.In this research,a photocatalyst g-C_(3)N_(4)/TiO_(2) was prepared and coupled with gas-liquid discharge(GLD)to degrade tetracycline(TC).The performance was examined,and the degradation pathways and mechanisms were studied.Results show that a 90%degradation rate is achieved in the GLD with g-C_(3)N_(4)/TiO_(2) over a 10 min treatment.Increasing the pulse voltage is conducive to increasing the degradation rate,whereas the addition of excessive g-C_(3)N_(4)/TiO_(2) tends to precipitate agglomerates,resulting in a poor degradation efficiency.The redox properties of the g-C_(3)N_(4)/TiO_(2) surface promote the generation of oxidizing active species(H2O2,O3)in solution.Radical quenching experiments showed that·OH,hole(h^(+)),play important roles in the TC degradation by the discharge with g-C_(3)N_(4)/TiO_(2).Two potential degradation pathways were proposed based on the intermediates.The toxicity of tetracycline was reduced by treatment in the system.Furthermore,the g-C_(3)N_(4)/TiO_(2) composites exhibited excellent recoverability and stability.展开更多
The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(...The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.展开更多
High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface...High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.展开更多
基金financially supported by the National Natural Science Foundation of China (Nos.U2002212,52102058,52204414,52204413,and 52204412)the National Key R&D Program of China (Nos.2021YFC1910504,2019YFC1907101,2019YFC1907103,and 2017YFB0702304)+7 种基金the Key R&D Program of Ningxia Hui Autonomous Region,China (Nos.2021BEG01003 and2020BCE01001)the Xijiang Innovation and Entrepreneurship Team,China (No.2017A0109004)the Macao Young Scholars Program (No.AM2022024),Chinathe Beijing Natural Science Foundation (Nos.L212020 and 2214073),Chinathe Guangdong Basic and Applied Basic Research Foundation,China (Nos.2021A1515110998 and 2020A1515110408)the China Postdoctoral Science Foundation (No.2022M710349)the Fundamental Research Funds for the Central Universities,China (Nos.FRF-BD-20-24A,FRF-TP-20-031A1,FRF-IC-19-017Z,and 06500141)the Integration of Green Key Process Systems MIIT and Scientific and Technological Innovation Foundation of Foshan,China(Nos.BK22BE001 and BK21BE002)。
文摘Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.
基金supported by the National Natural Science Foundation of China(22078138)the Natural Science Foundation of Jiangxi Province(20202ACBL203009).
文摘Direct-Z-scheme g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)photocatalyst with giant internal electric field was prepared by onestep aqueous sonication self-assembly method using g-C_(3)N_(4)and MXene of Ti_(3)C_(2)as the source materials.The chemical composition and structure of the catalysts was characterized by FT-IR,XRD,SEM,TEM,and XPS.The XPS characterization indicated that Ti_(3)C_(2)was partially oxidized to TiO_(2)during the composite process.As a result,an efficient direct-Z-scheme heterojunction structure consisting of the g-C_(3)N_(4)and TiO_(2)with Ti_(3)C_(2)as an electron bridge was constructed.The photocatalytic performance of the prepared catalysts was evaluated by degrading the Rhodamine B(RhB)wastewater.Compared with the single g-C_(3)N_(4),the g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)composite photocatalyst exhibited efficient and stable photocatalytic degradation ability,with a degradation efficiency as high as 99.2%for RhB under optimal conditions(2%Ti_(3)C_(2),pH=3).The high degradation performance of g-C_(3)N_(4)/Ti_(3)C_(2)/TiO_(2)for RhB was attributed to the combination of Ti_(3)C_(2),TiO_(2),and g-C_(3)N_(4)components,forming a direct-Z-scheme heterojunction with a high-speed electron transport channel structure.The role of Z-scheme heterojunctions in electron transport is verified by photoelectrochemical characterization,along with photoluminescence(PL).Our research provides a simple method to design photocatalysts by constructing direct-Z-scheme electron transport channels for highly efficient treatment of dye wastewater.
基金supported by National Natural Science Foundation of China(Nos.52277151 and 51907088)Innovative Talents Team Project of‘Six Talent Peaks’of Jiangsu Province(No.TD-JNHB-006).
文摘Plasma-catalysis is considered as one of the most promising technologies for antibiotic degradation in water.In the plasma-catalytic system,one of the factors affecting the degradation effect is the performance of the photocatalyst,which is usually restricted by the rapid recombination of electrons and holes as well as narrow light absorption range.In this research,a photocatalyst g-C_(3)N_(4)/TiO_(2) was prepared and coupled with gas-liquid discharge(GLD)to degrade tetracycline(TC).The performance was examined,and the degradation pathways and mechanisms were studied.Results show that a 90%degradation rate is achieved in the GLD with g-C_(3)N_(4)/TiO_(2) over a 10 min treatment.Increasing the pulse voltage is conducive to increasing the degradation rate,whereas the addition of excessive g-C_(3)N_(4)/TiO_(2) tends to precipitate agglomerates,resulting in a poor degradation efficiency.The redox properties of the g-C_(3)N_(4)/TiO_(2) surface promote the generation of oxidizing active species(H2O2,O3)in solution.Radical quenching experiments showed that·OH,hole(h^(+)),play important roles in the TC degradation by the discharge with g-C_(3)N_(4)/TiO_(2).Two potential degradation pathways were proposed based on the intermediates.The toxicity of tetracycline was reduced by treatment in the system.Furthermore,the g-C_(3)N_(4)/TiO_(2) composites exhibited excellent recoverability and stability.
文摘The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.
基金supported by the National Key R&D Program of China(Grant No.2023YFB2503900)the National Natural Science Foundation of China(Grant No.52372203)+1 种基金the National Natural Science Foundation of China(Grant No.52202259)the Shandong Province Natural Science Foundation(ZR2022QE093).
文摘High-capacity nickel-rich layered oxides are promising cathode materials for high-energy-density lithium batteries.However,the poor structural stability and severe side reactions at the electrode/electrolyte interface result in unsatisfactory cycle performance.Herein,the thin layer of two-dimensional(2D)graphitic carbon-nitride(g-C_(3)N_(4))is uniformly coated on the LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(denoted as NCM811@CN)using a facile chemical vaporization-assisted synthesis method.As an ideal protective layer,the g-C_(3)N_(4)layer effectively avoids direct contact between the NCM811 cathode and the electrolyte,preventing harmful side reactions and inhibiting secondary crystal cracking.Moreover,the unique nanopore structure and abundant nitrogen vacancy edges in g-C_(3)N_(4)facilitate the adsorption and diffusion of lithium ions,which enhances the lithium deintercalation/intercalation kinetics of the NCM811 cathode.As a result,the NCM811@CN-3wt%cathode exhibits 161.3 mAh g^(−1)and capacity retention of 84.6%at 0.5 C and 55°C after 400 cycles and 95.7 mAh g^(−1)at 10 C,which is greatly superior to the uncoated NCM811(i.e.129.3 mAh g^(−1)and capacity retention of 67.4%at 0.5 C and 55°C after 220 cycles and 28.8 mAh g^(−1)at 10 C).The improved cycle performance of the NCM811@CN-3wt%cathode is also applicable to solid–liquid-hybrid cells composed of PVDF:LLZTO electrolyte membranes,which show 163.8 mAh g^(−1)and the capacity retention of 88.1%at 0.1 C and 30°C after 200 cycles and 95.3 mAh g^(−1)at 1 C.
