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
光催化灭活是公认的控制病原微生物最具前景手段之一。本文以尿素和硫代巴比妥酸为起始原料,通过热聚合反应制备S掺杂g-C_(3)N_(4)(SCN),随后采用光还原法将Ag纳米粒负载于SCN表面获得新颖的可见光响应型Ag/SCN抗菌材料。对所制备纳米...光催化灭活是公认的控制病原微生物最具前景手段之一。本文以尿素和硫代巴比妥酸为起始原料,通过热聚合反应制备S掺杂g-C_(3)N_(4)(SCN),随后采用光还原法将Ag纳米粒负载于SCN表面获得新颖的可见光响应型Ag/SCN抗菌材料。对所制备纳米材料进行XRD、SEM、TEM、XPS及UV-Vis DRS表征,并深入探讨其在可见光下灭活大肠杆菌(E.coli)的性能和机制。结果表明,Ag纳米粒均匀且牢固地负载在SCN表面,纳米材料表现出显著增强的可见光响应能力。当负载量为6%时,Ag/SCN-6呈现出最佳的光催化灭菌活性,60 min内能够将6.2 lg CFU·mL^(-1)的E.coli全部灭活。自由基捕获实验结果表明,超氧自由基(·O-2)是灭活过程中最主要活性物种,它协同光生空穴(h+)和羟基自由基(·OH)主导了光催化抗菌的进程。展开更多
Carbon nitrides with two-dimensional layered structures and high theoretical capacities are attractive as anode materials for sodium-ion batteries while their low crystallinity and insufficient structural stability st...Carbon nitrides with two-dimensional layered structures and high theoretical capacities are attractive as anode materials for sodium-ion batteries while their low crystallinity and insufficient structural stability strongly restrict their practical applications.Coupling carbon nitrides with conductive carbon may relieve these issues.However,little is known about the influence of nitrogen(N)configurations on the interactions between carbon and C_(3)N_(4),which is fundamentally critical for guiding the precise design of advanced C_(3)N_(4)-related electrodes.Herein,highly crystalline C_(3)N_(4)(poly(triazine imide),PTI)based all-carbon composites were developed by molten salt strategy.More importantly,the vital role of pyrrolic-N for enhancing charge transfer and boosting Na+storage of C_(3)N_(4)-based composites,which was confirmed by both theoretical and experimental evidence,was spot-highlighted for the first time.By elaborately controlling the salt composition,the composite with high pyrrolic-N and minimized graphitic-N content was obtained.Profiting from the formation of highly crystalline PTI and electrochemically favorable pyrrolic-N configurations,the composite delivered an unusual reverse growth and record-level cycling stability even after 5000 cycles along with high reversible capacity and outstanding full-cell capacity retention.This work broadens the energy storage applications of C_(3)N_(4) and provides new prospects for the design of advanced all-carbon electrodes.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.
文摘光催化灭活是公认的控制病原微生物最具前景手段之一。本文以尿素和硫代巴比妥酸为起始原料,通过热聚合反应制备S掺杂g-C_(3)N_(4)(SCN),随后采用光还原法将Ag纳米粒负载于SCN表面获得新颖的可见光响应型Ag/SCN抗菌材料。对所制备纳米材料进行XRD、SEM、TEM、XPS及UV-Vis DRS表征,并深入探讨其在可见光下灭活大肠杆菌(E.coli)的性能和机制。结果表明,Ag纳米粒均匀且牢固地负载在SCN表面,纳米材料表现出显著增强的可见光响应能力。当负载量为6%时,Ag/SCN-6呈现出最佳的光催化灭菌活性,60 min内能够将6.2 lg CFU·mL^(-1)的E.coli全部灭活。自由基捕获实验结果表明,超氧自由基(·O-2)是灭活过程中最主要活性物种,它协同光生空穴(h+)和羟基自由基(·OH)主导了光催化抗菌的进程。
基金supported by the National Natural Science Foundation of China(51904059)Applied Basic Research Program of Liaoning(2022JH2/101300200)+1 种基金Guangdong Basic and Applied Basic Research Foundation(2022A1515140188)Fundamental Research Funds for the Central Universities(N_(2)002005,N_(2)125004,N_(2)225044)。
文摘Carbon nitrides with two-dimensional layered structures and high theoretical capacities are attractive as anode materials for sodium-ion batteries while their low crystallinity and insufficient structural stability strongly restrict their practical applications.Coupling carbon nitrides with conductive carbon may relieve these issues.However,little is known about the influence of nitrogen(N)configurations on the interactions between carbon and C_(3)N_(4),which is fundamentally critical for guiding the precise design of advanced C_(3)N_(4)-related electrodes.Herein,highly crystalline C_(3)N_(4)(poly(triazine imide),PTI)based all-carbon composites were developed by molten salt strategy.More importantly,the vital role of pyrrolic-N for enhancing charge transfer and boosting Na+storage of C_(3)N_(4)-based composites,which was confirmed by both theoretical and experimental evidence,was spot-highlighted for the first time.By elaborately controlling the salt composition,the composite with high pyrrolic-N and minimized graphitic-N content was obtained.Profiting from the formation of highly crystalline PTI and electrochemically favorable pyrrolic-N configurations,the composite delivered an unusual reverse growth and record-level cycling stability even after 5000 cycles along with high reversible capacity and outstanding full-cell capacity retention.This work broadens the energy storage applications of C_(3)N_(4) and provides new prospects for the design of advanced all-carbon electrodes.
