Though there are numerous intrinsic merits of metal-organic frameworks(MOFs),low charge separation efficiency has imposed heavy restrictions on their photocatalytic application.Herein,in situ porphyrin ligand substitu...Though there are numerous intrinsic merits of metal-organic frameworks(MOFs),low charge separation efficiency has imposed heavy restrictions on their photocatalytic application.Herein,in situ porphyrin ligand substitution,as a strategy for improving the charge separation efficiency and increasing the amounts of active sites,has been designed and realized in a Hf-biphenyl dicarboxylic acid(BPDC)MOF.Specifically,a size and geometry matched meso-tetra(4-carboxyphenyl)porphyrin(TCPP)ligand was selected and doped into Hf-BPDC MOF by forming coordinating bonds with Hf centers,forming dualligand Hf-BPDC-TCPP MOF.The resultant Hf-BPDC-TCPP MOF showed significantly improved activity and chemical stability in the photocatalytic H_(2)generation(261μmol·g^(-1)·h^(-1))and tetracycline(TC)degradation reactions(95.8%),which was 48 and 1.47 folds higher than that of the Hf-BPDC MOF.Photophysical and electrochemical studies revealed that the introduction of porphyrin ligand could generate a stronger internal electric field for boosting the charge separation and transfer,increase the specific surface area for providing more active sites,and narrow the band gap to enhance the visible light absorption.This in situ ligand substitution method provides a promising approach to build a tunable platform for constructing high-performance MOF photocatalysts.展开更多
Artificial photosynthesis is deemed as an efficient protocol for transforming abundant solar energy into valuable fuel. In this paper, the well-defined one-dimensional(1D) core–shell MnO_(2)@CdS hybrids were construc...Artificial photosynthesis is deemed as an efficient protocol for transforming abundant solar energy into valuable fuel. In this paper, the well-defined one-dimensional(1D) core–shell MnO_(2)@CdS hybrids were constructed by employing MnO_(2) nanotubes and CdS nanoparticles as nano-building blocks via a chemical coprecipitation route. The rationally designed core–shell structure provided an intimate heterojunction interface between the CdS shell and MnO_(2) core. All the MnO_(2)@CdS core–shell nanocomposites possess higher H_(2) evolution rate through visible light irradiation contrary to pristine CdS, and the optimal MnO_(2)@CdS hybrid exhibits the utmost H_(2) evolution rate of 3.94 mmol·g^(-1)·h^(-1), which is2.8-fold higher compared with that of CdS. Appertaining to XPS and Mott-Schottky(M-S) analysis, such enhanced photocatalytic H_(2) generation of MnO_(2)@CdS heterojunction was ascribed to an S-scheme mechanism, which suppressed the charge recombination along with a fast detachment of electron–hole pairs(e^(-)–h^(+)) and significantly improved the severance of carriers, thus improved H_(2) evolution performance. These findings envision a new insight into the development of S-scheme heterostructure for photocatalytic H_(2) generation.展开更多
Background:There is no consensus on whether triplet regimen is better than doublet regimen in the first-line treatment of advanced gastric cancer(AGC).We aimed to compare the efficacy and safety of oxaliplatin plus ca...Background:There is no consensus on whether triplet regimen is better than doublet regimen in the first-line treatment of advanced gastric cancer(AGC).We aimed to compare the efficacy and safety of oxaliplatin plus capecitabine(XELOX)and epirubicin,oxaliplatin,plus capecitabine(EOX)regimens in treating AGC.Methods:This phase III trial enrolled previously untreated patients with AGC whowere randomly assigned to receive the XELOXor EOXregimen.The primary endpoint was non-inferiority in progression-free survival(PFS)for XELOX as compared with EOX on an intention-to-treat basis.Results:Between April 10,2015 andAugust 20,2020,448AGCpatientswere randomized to receive XELOX(n=222)or EOX(n=226).The median PFS(mPFS)was 5.0 months(95%confidence interval[CI]=4.5-6.0 months)in the XELOX arm and 5.5 months(95%CI=5.0-6.0 months)in the EOX arm(hazard ratio[HR]=0.989,95%CI=0.812-1.203;P_(non-inferiority)=0.003).There was no significant difference inmedian overall survival(mOS)(12.0 vs.12.0months,P=0.384)or objective response rate(37.4%vs.45.1%,P=0.291)between the two groups.In patients with poorly differentiated adenocarcinoma and liver metastasis,the EOX arm had a significantly longer mOS(P=0.021)and a trend of longer mPFS(P=0.073)than the XELOX arm.The rate of grade 3/4 adverse events(AEs)was 42.2%(90/213)in the XELOX arm and 72.5%(156/215)in the EOX arm(P=0.001).The global health-related quality of life(QoL)score was significantly higher in the XELOX arm than in the EOX arm during chemotherapy.Conclusions:This non-inferiority trial demonstrated that the doublet regimen was as effective as the triplet regimen and had a better safety profile and QoL as a first-line treatment for AGC patients.However,the triplet regimen might have a survival advantage in patients with poorly differentiated adenocarcinoma and liver metastasis.展开更多
Two-dimensional Sn2Ta2O7 nanosheets with a thickness of^10 nm were successfully prepared through a novel tantalic acid-based solid-state reaction method at reduced temperature.The as-obtained samples were characterize...Two-dimensional Sn2Ta2O7 nanosheets with a thickness of^10 nm were successfully prepared through a novel tantalic acid-based solid-state reaction method at reduced temperature.The as-obtained samples were characterized by powder X-ray diffraction(XRD),ultraviolet–visible(UV–Vis)diffuse reflectance spectra,scanning electron microscopy(SEM),transmission electron microscopy(TEM)and Brunauer–Emmett–Teller(BET)analysis.The photocatalytic performance of Sn2 Ta2 O7 nanosheets was evaluated by photocatalytic water splitting for hydrogen evolution under visible light irradiation(k C 400 nm).The Sn2Ta2O7 nanosheets with a large surface area of 25.9 m^2·g^-1 showed higher H2 production activity,which was about 4.4 times higher than that of bulk Sn2 Ta2O7 in lactic acid aqueous solutions using Pt as a cocatalyst.The improved photocatalytic performance mainly benefited from the nanosheet structure,which provided abundant surface active sites and facilitated the photogenerated charge carrier separation efficiently.This workmay open up new opportunity to develop novel nanostructured tantalum-based semiconductors with improved catalytic performance for solar energy conversion.展开更多
With the continuous progress and development of current industrial civilization,energy crisis and envi-ronmental pollution are serious problems that threaten human beings need to be solved.Photocatalytic technolo-gies...With the continuous progress and development of current industrial civilization,energy crisis and envi-ronmental pollution are serious problems that threaten human beings need to be solved.Photocatalytic technolo-gies that can use clean solar light energy to manufacture clean H2 fuel and high value chemicals provide a feasibility to solve the above problem.However,traditional photo-catalytic water splitting mainly focused on the utilization of photogenerated electrons to produce H_(2) which leads to the waste of the holes.It is vital to develop photocatalysts capable of synchronously utilizing photogenerated elec-trons and holes for the future practical application.In this paper,the latest progress of photocatalytic system with collaborative photooxidation-reduction application has been summarized,and water splitting for H_(2) production combining different organic synchronous reaction process has been clarified.Finally,the prospect of photocatalysts capable of synchronously utilizing photogenerated elec-trons and holes are proposed.展开更多
The reasonable employment of cocatalyst in photocatalysis can effectively promote the photocatalytic H_(2)production activity.In this study,carbon hollow spheres(C),as a good conductive nonmetallic material,have been ...The reasonable employment of cocatalyst in photocatalysis can effectively promote the photocatalytic H_(2)production activity.In this study,carbon hollow spheres(C),as a good conductive nonmetallic material,have been utilized as a novel cocatalyst and a matrix for loading the Cu-doped-TiO_(2)nanoparticles by a successive hydrother-mal method and metal molten salt method.The Cu-doped-TiO_(2)nanoparticles were tightly anchored on the surface of carbon hollow sphere to form a zero-dimensional/three dimensional(0D/3D)Cu-doped-TiO2/C heterojunction.The optimal Cu-doped-TiO_(2)/C heterojunction demon-strated greatly enhanced photocatalytic H_(2) generation activity(14.4 mmol·g^(-1)·h^(-1))compared with TiO_(2)(0.33 mmol·g^(-1)·h^(-1))and TiO_(2)/C(0.7 mmol·g^(-1)·h^(-1)).The performance improvement was mainly due to the syner-gistic effect of carbon hollow sphere cocatalyst and Cu-doping,the Cu-doping in TiO_(2)nanoparticles can minimize charge recombination and enhance the available photoex-cited electrons,while the 3D carbon hollow spheres can act as electron traps to accelerate the charge separation and offer abundant active sites for solar water splitting reaction.展开更多
基金financially supported by the National Nature Science Foundation of China(Nos.22102064 and 21972058)supported by the Open Project Program of Fujian Provincial Key Laboratory of Ecology-Toxicological Effects and Control for Emerging Contaminants,Putian University。
文摘Though there are numerous intrinsic merits of metal-organic frameworks(MOFs),low charge separation efficiency has imposed heavy restrictions on their photocatalytic application.Herein,in situ porphyrin ligand substitution,as a strategy for improving the charge separation efficiency and increasing the amounts of active sites,has been designed and realized in a Hf-biphenyl dicarboxylic acid(BPDC)MOF.Specifically,a size and geometry matched meso-tetra(4-carboxyphenyl)porphyrin(TCPP)ligand was selected and doped into Hf-BPDC MOF by forming coordinating bonds with Hf centers,forming dualligand Hf-BPDC-TCPP MOF.The resultant Hf-BPDC-TCPP MOF showed significantly improved activity and chemical stability in the photocatalytic H_(2)generation(261μmol·g^(-1)·h^(-1))and tetracycline(TC)degradation reactions(95.8%),which was 48 and 1.47 folds higher than that of the Hf-BPDC MOF.Photophysical and electrochemical studies revealed that the introduction of porphyrin ligand could generate a stronger internal electric field for boosting the charge separation and transfer,increase the specific surface area for providing more active sites,and narrow the band gap to enhance the visible light absorption.This in situ ligand substitution method provides a promising approach to build a tunable platform for constructing high-performance MOF photocatalysts.
基金financially supported by the National Natural Science Foundation of China(Nos.51672113,21975110 and 21972058)。
文摘Artificial photosynthesis is deemed as an efficient protocol for transforming abundant solar energy into valuable fuel. In this paper, the well-defined one-dimensional(1D) core–shell MnO_(2)@CdS hybrids were constructed by employing MnO_(2) nanotubes and CdS nanoparticles as nano-building blocks via a chemical coprecipitation route. The rationally designed core–shell structure provided an intimate heterojunction interface between the CdS shell and MnO_(2) core. All the MnO_(2)@CdS core–shell nanocomposites possess higher H_(2) evolution rate through visible light irradiation contrary to pristine CdS, and the optimal MnO_(2)@CdS hybrid exhibits the utmost H_(2) evolution rate of 3.94 mmol·g^(-1)·h^(-1), which is2.8-fold higher compared with that of CdS. Appertaining to XPS and Mott-Schottky(M-S) analysis, such enhanced photocatalytic H_(2) generation of MnO_(2)@CdS heterojunction was ascribed to an S-scheme mechanism, which suppressed the charge recombination along with a fast detachment of electron–hole pairs(e^(-)–h^(+)) and significantly improved the severance of carriers, thus improved H_(2) evolution performance. These findings envision a new insight into the development of S-scheme heterostructure for photocatalytic H_(2) generation.
基金National Key Research and Development Program of China,Grant/Award Number:2017YFC1308900The clinical research and cultivation project of shanghai Shenkang hospital development center,Grant/Award Number:SHDC12017×01Sun Yat-sen University Xie Tong Chuang Xin Program,Grant/Award Number:ZLYXXTCX201504。
文摘Background:There is no consensus on whether triplet regimen is better than doublet regimen in the first-line treatment of advanced gastric cancer(AGC).We aimed to compare the efficacy and safety of oxaliplatin plus capecitabine(XELOX)and epirubicin,oxaliplatin,plus capecitabine(EOX)regimens in treating AGC.Methods:This phase III trial enrolled previously untreated patients with AGC whowere randomly assigned to receive the XELOXor EOXregimen.The primary endpoint was non-inferiority in progression-free survival(PFS)for XELOX as compared with EOX on an intention-to-treat basis.Results:Between April 10,2015 andAugust 20,2020,448AGCpatientswere randomized to receive XELOX(n=222)or EOX(n=226).The median PFS(mPFS)was 5.0 months(95%confidence interval[CI]=4.5-6.0 months)in the XELOX arm and 5.5 months(95%CI=5.0-6.0 months)in the EOX arm(hazard ratio[HR]=0.989,95%CI=0.812-1.203;P_(non-inferiority)=0.003).There was no significant difference inmedian overall survival(mOS)(12.0 vs.12.0months,P=0.384)or objective response rate(37.4%vs.45.1%,P=0.291)between the two groups.In patients with poorly differentiated adenocarcinoma and liver metastasis,the EOX arm had a significantly longer mOS(P=0.021)and a trend of longer mPFS(P=0.073)than the XELOX arm.The rate of grade 3/4 adverse events(AEs)was 42.2%(90/213)in the XELOX arm and 72.5%(156/215)in the EOX arm(P=0.001).The global health-related quality of life(QoL)score was significantly higher in the XELOX arm than in the EOX arm during chemotherapy.Conclusions:This non-inferiority trial demonstrated that the doublet regimen was as effective as the triplet regimen and had a better safety profile and QoL as a first-line treatment for AGC patients.However,the triplet regimen might have a survival advantage in patients with poorly differentiated adenocarcinoma and liver metastasis.
基金financially supported by the National Key R&D Program of China (Nos. 2017YFA0206904, 2017YFA0206900 and 2016YFB0600901)the National Natural Science Foundation of China (Nos. 51825205, U1662118, 51772305, 51572270, 21871279 and 21802154)+4 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences (No. XDB17000000)the Beijing Natural Science Foundation (No. 2182078), the Beijing Municipal Science and Technology Project (No. Z181100005118007)the Royal Society-Newton Advanced Fellowship (No. NA170422)the International Partnership Program of Chinese Academy of Sciences (No. GJHZ1819)the K. C. Wong Education Foundation
文摘Two-dimensional Sn2Ta2O7 nanosheets with a thickness of^10 nm were successfully prepared through a novel tantalic acid-based solid-state reaction method at reduced temperature.The as-obtained samples were characterized by powder X-ray diffraction(XRD),ultraviolet–visible(UV–Vis)diffuse reflectance spectra,scanning electron microscopy(SEM),transmission electron microscopy(TEM)and Brunauer–Emmett–Teller(BET)analysis.The photocatalytic performance of Sn2 Ta2 O7 nanosheets was evaluated by photocatalytic water splitting for hydrogen evolution under visible light irradiation(k C 400 nm).The Sn2Ta2O7 nanosheets with a large surface area of 25.9 m^2·g^-1 showed higher H2 production activity,which was about 4.4 times higher than that of bulk Sn2 Ta2O7 in lactic acid aqueous solutions using Pt as a cocatalyst.The improved photocatalytic performance mainly benefited from the nanosheet structure,which provided abundant surface active sites and facilitated the photogenerated charge carrier separation efficiently.This workmay open up new opportunity to develop novel nanostructured tantalum-based semiconductors with improved catalytic performance for solar energy conversion.
基金financially supported by the National Natural Science Foundation of China (Nos. 21975110 and 21972058)Taishan Youth Scholar Program of Shandong Province
文摘With the continuous progress and development of current industrial civilization,energy crisis and envi-ronmental pollution are serious problems that threaten human beings need to be solved.Photocatalytic technolo-gies that can use clean solar light energy to manufacture clean H2 fuel and high value chemicals provide a feasibility to solve the above problem.However,traditional photo-catalytic water splitting mainly focused on the utilization of photogenerated electrons to produce H_(2) which leads to the waste of the holes.It is vital to develop photocatalysts capable of synchronously utilizing photogenerated elec-trons and holes for the future practical application.In this paper,the latest progress of photocatalytic system with collaborative photooxidation-reduction application has been summarized,and water splitting for H_(2) production combining different organic synchronous reaction process has been clarified.Finally,the prospect of photocatalysts capable of synchronously utilizing photogenerated elec-trons and holes are proposed.
基金financially supported by the National Natural Science Foundation of China (Nos.21975110 and 21972058)Taishan Youth Scholar Program of Shandong Province
文摘The reasonable employment of cocatalyst in photocatalysis can effectively promote the photocatalytic H_(2)production activity.In this study,carbon hollow spheres(C),as a good conductive nonmetallic material,have been utilized as a novel cocatalyst and a matrix for loading the Cu-doped-TiO_(2)nanoparticles by a successive hydrother-mal method and metal molten salt method.The Cu-doped-TiO_(2)nanoparticles were tightly anchored on the surface of carbon hollow sphere to form a zero-dimensional/three dimensional(0D/3D)Cu-doped-TiO2/C heterojunction.The optimal Cu-doped-TiO_(2)/C heterojunction demon-strated greatly enhanced photocatalytic H_(2) generation activity(14.4 mmol·g^(-1)·h^(-1))compared with TiO_(2)(0.33 mmol·g^(-1)·h^(-1))and TiO_(2)/C(0.7 mmol·g^(-1)·h^(-1)).The performance improvement was mainly due to the syner-gistic effect of carbon hollow sphere cocatalyst and Cu-doping,the Cu-doping in TiO_(2)nanoparticles can minimize charge recombination and enhance the available photoex-cited electrons,while the 3D carbon hollow spheres can act as electron traps to accelerate the charge separation and offer abundant active sites for solar water splitting reaction.
