BACKGROUND Colorectal cancer is currently the third most common malignant tumor and the second leading cause of cancer-related death worldwide.Neoadjuvant chemoradiotherapy(nCRT)is standard for locally advanced rectal...BACKGROUND Colorectal cancer is currently the third most common malignant tumor and the second leading cause of cancer-related death worldwide.Neoadjuvant chemoradiotherapy(nCRT)is standard for locally advanced rectal cancer(LARC).Except for pathological examination after resection,it is not known exactly whether LARC patients have achieved pathological complete response(pCR)before surgery.To date,there are no clear clinical indicators that can predict the efficacy of nCRT and patient outcomes.AIM To investigate the indicators that can predict pCR and long-term outcomes following nCRT in patients with LARC.METHODS Clinical data of 128 LARC patients admitted to our hospital between September 2013 and November 2022 were retrospectively analyzed.Patients were categorized into pCR and non-pCR groups.Univariate analysis(using the χ^(2) test or Fisher’s exact test)and logistic multivariate regression analysis were used to study clinical predictors affecting pCR.The 5-year disease-free survival(DFS)and overall survival(OS)rates were calculated using Kaplan-Meier analysis,and differences in survival curves were assessed with the log-rank test.RESULTS Univariate analysis showed that pretreatment carcinoembryonic antigen(CEA)level,lymphocyte-monocyte ratio(LMR),time interval between neoadjuvant therapy completion and total mesorectal excision,and tumor size were correlated with pCR.Multivariate results showed that CEA≤5 ng/mL(P=0.039),LMR>2.73(P=0.023),and time interval>10 wk(P=0.039)were independent predictors for pCR.Survival analysis demonstrated that patients in the pCR group had significantly higher 5-year DFS rates(94.7%vs 59.7%,P=0.002)and 5-year OS rates(95.8%vs 80.1%,P=0.019)compared to the non-pCR group.Tumor deposits(TDs)were significantly correlated with shorter DFS(P=0.002)and OS(P<0.001).CONCLUSION Pretreatment CEA,LMR,and time interval contribute to predicting nCRT efficacy in LARC patients.Achieving pCR demonstrates longer DFS and OS.TDs correlate with poor prognosis.展开更多
Two-dimensional (2-D) BiVO4 nanosheets-graphene (GR) composites with different weight addition ratios of GR have been prepared via a facile wet chemistry process. X-ray diffraction (XRD), Raman spectra, X-ray ph...Two-dimensional (2-D) BiVO4 nanosheets-graphene (GR) composites with different weight addition ratios of GR have been prepared via a facile wet chemistry process. X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectra (XPS), UV-vis diffuse reflectance spectra (DRS), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), nitrogen adsorption-desorption, transient photocurrent response and photoluminescence (PL) spectra were employed to determine the properties of the samples. It is found that BiVO4 nanosheets could pave well on the surface of graphene sheets. BiVO4 nanosheets-GR composites with a proper addition amount of GR exhibited higher photocatalytic activity than bare BiVO4 nanosheets toward liquid-phase degradation of rhodamine B (RhB) and methyl orange (MO) under visible light irradiation. The enhancement of photocatalytic activities of BiVO4 nanosheets-GR composites can be attributed to the effective separation of photoexcited electron-hole pairs. This work not only provides a simple strategy for fabricating specific 2-D semiconductor-2-D GR composites, but also opens a new window of such 2-D semiconductor-2-D GR composites as visible light photocatalysts toward an improved visible light photoactivity in purifying polluted water resources.展开更多
As a new member of carbon material family, carbon quantum dots (CQDs) have attracted tremendous attentions for their potentials in the heterogeneous photocatalysis applications. Due to the unique microstructure and op...As a new member of carbon material family, carbon quantum dots (CQDs) have attracted tremendous attentions for their potentials in the heterogeneous photocatalysis applications. Due to the unique microstructure and optical properties, the roles of CQDs played in the CQDs-based photocatalytic systems have been found to be diverse with the continuous researches in this regard. Herein, we provide a concise minireview to elaborate the multifarious roles of CQDs in photocatalysis, including photoelectron mediator and acceptor, photosensitizer, photocatalyst, reducing agent for metal salt, enhancing adsorption capacity and spectral converter. In addition, the perspectives on future research trends and challenges are proposed, which are anticipated to stimulate further research into this promising field on designing a variety of efficient CQDs-based photocatalysts for solar energy conversion. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B. V. and Science Press. All rights reserved.展开更多
The conversion of biomass into valuable chemicals has promise for application in biorefineries.Light-driven photoredox catalysis,with the typical features of green route and operation under mild conditions,is consider...The conversion of biomass into valuable chemicals has promise for application in biorefineries.Light-driven photoredox catalysis,with the typical features of green route and operation under mild conditions,is considered a promising strategy for renewable biomass or biomass-derived intermediates conversion into high-value-added chemical feedstocks.In this review,we strongly emphasize the recent advances in photocatalytic valorization of lignin model compounds and biomassderived alcohols.We briefl y summarize the advances in photocatalytic cleavage of theβ-O-4 bond or C–C bond into usable chemicals in the lignin model.On the other hand,we clarify not only the hybrid system for cooperative biomass-relevant alcohols oxidation and hydrogen(H2)evolution but also the tunable accessibility to variation of the target products from the same alcohol reactant by catalyst design and optimization of reaction conditions.It is hoped that this review will inspire the rational design of photoredox catalysis-based systems toward efficient biomass-derived platform molecules valorization to obtain target-oriented valuable products.展开更多
Graphene (GR)-CdS nanocomposites with different weight addition ratios of GR have been assembled by a facile solvothermal treatment. The GR-CdS nanocomposite photocatalyst with an appropriate ratio of GR exhibits en...Graphene (GR)-CdS nanocomposites with different weight addition ratios of GR have been assembled by a facile solvothermal treatment. The GR-CdS nanocomposite photocatalyst with an appropriate ratio of GR exhibits enhanced photoactivity for selective reduction of aromatic nitro compounds to the corresponding aromatic amines in water under visible light irradiation as compared with blank-CdS. The characterization of GR-CdS nanocomposite photocatalysts by a collection of techniques discloses that: i) GR can tune the microscopic morphology of CdS nanoparticles and improve light absorption intensity in the visible light region; ii) GR scaffolds act as an electron reservoir to trap and shuttle the electrons photogenerated from CdS semiconductor under the visible light illumination; iii) the introduction of GR enhances the adsorption capacity of GR-CdS nanocomposites toward the substrates, aromatic nitro compounds. The synergistic effect of these factors should account for the photoactivity advancement of GR-CdS nanocomposites toward the probe reactions. Furthermore, because the photogenerated holes in the system are trapped by the quenching agent ammonium oxalate, the as-obtained GR-CdS photocataiyst is stable during the photocatalytic reduction reactions. A reasonable model has also been proposed to illustrate the reaction mechanism.展开更多
CdS nanowires-nitrogen doped graphene (CdS NWs-NGR) nanocomposites have been fabricated by an electrostatic self-assembly strategy followed by a hydrothermal reduction. The CdS NWs-NGR exhibits higher photoactivity ...CdS nanowires-nitrogen doped graphene (CdS NWs-NGR) nanocomposites have been fabricated by an electrostatic self-assembly strategy followed by a hydrothermal reduction. The CdS NWs-NGR exhibits higher photoactivity for selective reduction of aromatic nitro organics in water under visible light irradiation than blank CdS nanowires (CdS NWs) and CdS nanowires-reduced graphene oxide (CdS NWs-RGO) nanocomposites. The enhanced photoactivity of CdS NWs-NGR can be attributed to the improved electronic conductivity due to the introduc- tion of nitrogen atoms, which thus enhances the separation and transfer of charge carriers photogenerated from CdS NWs. Our work could provide a facile method to synthesize NGR based one-dimensional (1D) semiconductor composites for selective organic transformations, and broaden the potential applications for NGR as a cocatalyst.展开更多
The dynamic evolution of active site coordination structure during a high-temperature reaction is critically significant but often difficult for the research of efficient single-atom catalysts(SACs).Herein,we for the ...The dynamic evolution of active site coordination structure during a high-temperature reaction is critically significant but often difficult for the research of efficient single-atom catalysts(SACs).Herein,we for the first time report the in situ activation behaviors of the local coordination structure of Pt single atoms(Pt_(1))during the high-temperature oxidation of light alkanes.The distinctly enhanced activity of the catalyst is attributed to the in situ evolved Pt_(1)−oxygen vacancy(Pt_(1)−OV)combination ensemble as an efficient and stable active site.Theoretical calculations reveal that the lattice oxygen adjacent to Pt_(1)and the H dissociated from CH4 constitute the lattice hydroxyl,which is the initial step in the formation of the Pt_(1)−OV combination.Pt_(1)and nearby unsaturated Mn can donate the charge back to O−O to promote the dissociation of O_(2).This work provides molecular-level insight into the in situ reaction-induced evolution of a single-atom coordination environment for designing efficient SACs under harsh conditions.展开更多
Ternary composites of reduced graphene oxide(GR)-CdS-Pd have been successfully synthesized via solvothermal and photodeposition methods for photocatalytic selective conversion of benzyl alcohol(BA)coupled with hydroge...Ternary composites of reduced graphene oxide(GR)-CdS-Pd have been successfully synthesized via solvothermal and photodeposition methods for photocatalytic selective conversion of benzyl alcohol(BA)coupled with hydrogen(H_(2))production, which exhibit significantly improved photoactivity and selectivity than bare CdS. Mechanistic studies unveil that the cooperative effect of the close interface contact and matched energy level alignment between electrical conducting GR nanosheets(NSs) and CdS nanoparticles(NPs) in GR-CdS-Pd composite not only benefits the separation and transfer of photogenerated carriers but also improves the photocorrosion resistance of CdS. The photodeposited Pd NPs further promote the photogenerated charge separation and accelerate the formation of intermediate products(α-hydroxybenzyl radicals), thereby contributing to enhanced conversion of BA. This work would facilitate the rational design of GR as cocatalyst to construct an efficient and stable CdS-based composite photocatalyst for cooperative coupling of fine chemical synthesis and H_(2) evolution.展开更多
Semiconductor quantum dots have been emerging as one of the most ideal materials for artificial photosynthesis.Here,we report the assembled ZnS-CdS hybrid heterostructure for efficient coupling cooperative redox catal...Semiconductor quantum dots have been emerging as one of the most ideal materials for artificial photosynthesis.Here,we report the assembled ZnS-CdS hybrid heterostructure for efficient coupling cooperative redox catalysis toward the oxidation of 1-phenylethanol to acetophenone/2,3-diphenyl-2,3-butanediol(pinacol)integrated with the reduction of protons to H2.The strong interaction and typical type-I band-position alignment between CdS quantum dots and ZnS quantum dots result in efficient separation and transfer of electron-hole pairs,thus distinctly enhancing the coupled photocatalyzed-redox activity and stability.The optimal ZnS-CdS hybrid also delivers a superior performance for various aromatic alcohol coupling photoredox reaction,and the ratio of electrons and holes consumed in such redox reaction is close to 1.0,indicating a high atom economy of cooperative coupling catalysis.In addition,by recycling the scattered light in the near field of a SiO_(2)sphere,the SiO_(2)-supported ZnS-CdS(denoted as ZnS-CdS/SiO_(2))catalyst can further achieve a 3.5-fold higher yield than ZnS-CdS hybrid.Mechanistic research clarifies that the oxidation of 1-phenylethanol proceeds through the pivotal radical intermediates of•C(CH_(3))(OH)Ph.This work is expected to promote the rational design of semiconductor quantum dots-based heterostructured catalysts for coupling photoredox catalysis in organic synthesis and clean fuels production.展开更多
In order to improve the mechanical properties of deposited metal of ilmenite type welding electrode, CeO2/La rare earth elements were added into electrodes based on E4301 electrode, then electrodes were produced, test...In order to improve the mechanical properties of deposited metal of ilmenite type welding electrode, CeO2/La rare earth elements were added into electrodes based on E4301 electrode, then electrodes were produced, test plates were welded, and mechanical properties were tested based on National Standards of China. For the sake of solving the problems of large amount of mechanical properties tests, long test cycle and high test cost during the conventional production process of electrode, a prediction model of the mechanical properties of deposited metal based on Takagi-Sugeno (T-S) fuzzy neural network was established. Mn, Si and C contents of medium manganese in electrode, CeO2, and La contents of electrode and welding speed were selected as input variables of the prediction model, and the tensile strength, lower yield strength, elongation, impact energy and hardness of de- posited metal were selected as output variables. Finally, predicting experiment was done under test samples, and results show that average relative prediction error of the tensile strength, lower yield strength, elongation and hardness are 0.91%, 2.57 %, 4.94 % and 1.94 %, respec- tively, which reach the need of actual production. The re- sults of prediction show that the mechanical properties of deposited metal of electrode containing rare earth can be forecasted accurately through material composition of electrode and welding parameters based on T-S fuzzy neural network model.展开更多
The ilmenite welding electrode has advantages of low cost and excellent welding technological properties.However, the welding quality is affected adversely by its poor crack resistance.To solve this problem, 12 kinds ...The ilmenite welding electrode has advantages of low cost and excellent welding technological properties.However, the welding quality is affected adversely by its poor crack resistance.To solve this problem, 12 kinds of rare earths coating formulas were optimized by means of orthogonal test design and curve fitting.Then the powders containing La/Ce O2 were extruded into ilmenite welding electrode through screw-type pressing–scribbling machine.After that, a series of mechanical properties tests were conducted according to national standards.Next, the mechanical properties data were analyzed comprehensively by analyzing variance, boxplot as well as Minitab 3D surface chart.The results show that compared with the formula without rare earth, the deposited metal’s impact toughness,the lower yield strength, the tensile strength, and the hardness are increased by 54.44 %, 9.25 %, 6.37 %, and4.27 %, respectively.In other words, Electrode 6 with the La/Ce O2 amount of 0.5 %/0.1 % in coating has better mechanical properties.展开更多
Photocatalyzed organic transformations have spurred immense interest in synthetic chemistry for the efficient conversion of solar energy into chemical energy.However,the crucial roles of support,which fixes catalytic ...Photocatalyzed organic transformations have spurred immense interest in synthetic chemistry for the efficient conversion of solar energy into chemical energy.However,the crucial roles of support,which fixes catalytic sites and improves the light-harvesting ability,are often ignored in photoredox transformations.Herein,we report the utilization of spherical SiO2 support to engineer AuPd alloy particles(denoted as AuPd/SiO2),conceptually different from traditional methods for tuning optical absorption of plasmonic Au or AuPd particles,to manipulate light-harvesting ability of AuPd particles for highly selective and efficient photocatalytic Suzuki cross-coupling reactions.In this deliberately designed system,typically without the size and shape alternation of AuPd particles,the supported AuPd particles recycle the scattering light from spherical SiO2 support and achieve the significant broad light-harvesting ability instead of the surface plasmon resonance peak.The engineered AuPd/SiO2 composites by the use of near-field scattering-promoted optical absorption showcase the remarkably enhanced activity for visible-light-induced photocatalytic Suzuki cross-coupling reactions in comparison with that using commercial SiO2 support,highlighting the spherical-support-effect induced efficient utilization of scattered light.This work highlights the feasibility of manipulating the light-harvesting capability of bimetallic particles by the near-field scattering-promoted optical absorption model toward efficient photo-driven Suzuki cross-coupling reaction and other C-C coupling organic synthesis to produce high value-added chemicals.展开更多
基金Supported by the National Natural Science Foundation of China,No.82073476the National Key R&D Program of China,No.2022YFC2503700 and No.2022YFC2503703+1 种基金Jiangsu Provincial Medical Key Discipline,No.ZDXK202235Innovation Research Project of Medical and Industrial Cooperation in Suzhou,No.SLJ2021005.
文摘BACKGROUND Colorectal cancer is currently the third most common malignant tumor and the second leading cause of cancer-related death worldwide.Neoadjuvant chemoradiotherapy(nCRT)is standard for locally advanced rectal cancer(LARC).Except for pathological examination after resection,it is not known exactly whether LARC patients have achieved pathological complete response(pCR)before surgery.To date,there are no clear clinical indicators that can predict the efficacy of nCRT and patient outcomes.AIM To investigate the indicators that can predict pCR and long-term outcomes following nCRT in patients with LARC.METHODS Clinical data of 128 LARC patients admitted to our hospital between September 2013 and November 2022 were retrospectively analyzed.Patients were categorized into pCR and non-pCR groups.Univariate analysis(using the χ^(2) test or Fisher’s exact test)and logistic multivariate regression analysis were used to study clinical predictors affecting pCR.The 5-year disease-free survival(DFS)and overall survival(OS)rates were calculated using Kaplan-Meier analysis,and differences in survival curves were assessed with the log-rank test.RESULTS Univariate analysis showed that pretreatment carcinoembryonic antigen(CEA)level,lymphocyte-monocyte ratio(LMR),time interval between neoadjuvant therapy completion and total mesorectal excision,and tumor size were correlated with pCR.Multivariate results showed that CEA≤5 ng/mL(P=0.039),LMR>2.73(P=0.023),and time interval>10 wk(P=0.039)were independent predictors for pCR.Survival analysis demonstrated that patients in the pCR group had significantly higher 5-year DFS rates(94.7%vs 59.7%,P=0.002)and 5-year OS rates(95.8%vs 80.1%,P=0.019)compared to the non-pCR group.Tumor deposits(TDs)were significantly correlated with shorter DFS(P=0.002)and OS(P<0.001).CONCLUSION Pretreatment CEA,LMR,and time interval contribute to predicting nCRT efficacy in LARC patients.Achieving pCR demonstrates longer DFS and OS.TDs correlate with poor prognosis.
基金supported by the National Natural Science Foundation of China(NSFC)(20903022,20903023,21173045)the Award Program for Minjiang Scholar Professorship+1 种基金the Science and Technology Development of Foundation of Fuzhou University(2009-XQ-10)the Open Fund of Photocatalysis of Fuzhou University(0380038004)
文摘Two-dimensional (2-D) BiVO4 nanosheets-graphene (GR) composites with different weight addition ratios of GR have been prepared via a facile wet chemistry process. X-ray diffraction (XRD), Raman spectra, X-ray photoelectron spectra (XPS), UV-vis diffuse reflectance spectra (DRS), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), nitrogen adsorption-desorption, transient photocurrent response and photoluminescence (PL) spectra were employed to determine the properties of the samples. It is found that BiVO4 nanosheets could pave well on the surface of graphene sheets. BiVO4 nanosheets-GR composites with a proper addition amount of GR exhibited higher photocatalytic activity than bare BiVO4 nanosheets toward liquid-phase degradation of rhodamine B (RhB) and methyl orange (MO) under visible light irradiation. The enhancement of photocatalytic activities of BiVO4 nanosheets-GR composites can be attributed to the effective separation of photoexcited electron-hole pairs. This work not only provides a simple strategy for fabricating specific 2-D semiconductor-2-D GR composites, but also opens a new window of such 2-D semiconductor-2-D GR composites as visible light photocatalysts toward an improved visible light photoactivity in purifying polluted water resources.
基金financial support from the key project of the National Natural Science Foundation of China (U1463204)the project of National Natural Science Foundation of China (NSFC) (20903023,21173045)+4 种基金the Award Program for Minjiang Scholar Professorshipthe Natural Science Foundation (NSF) of Fujian Province for Distinguished Young Investigator Grant (2012J06003)the Independent Research Project of State Key Laboratory of Photocatalysis on Energy and Environment (No.2014A05)the 1st Program of Fujian Province for Top Creative Young Talentsthe Program for Returned High-Level Overseas Chinese Scholars of Fujian Province
文摘As a new member of carbon material family, carbon quantum dots (CQDs) have attracted tremendous attentions for their potentials in the heterogeneous photocatalysis applications. Due to the unique microstructure and optical properties, the roles of CQDs played in the CQDs-based photocatalytic systems have been found to be diverse with the continuous researches in this regard. Herein, we provide a concise minireview to elaborate the multifarious roles of CQDs in photocatalysis, including photoelectron mediator and acceptor, photosensitizer, photocatalyst, reducing agent for metal salt, enhancing adsorption capacity and spectral converter. In addition, the perspectives on future research trends and challenges are proposed, which are anticipated to stimulate further research into this promising field on designing a variety of efficient CQDs-based photocatalysts for solar energy conversion. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B. V. and Science Press. All rights reserved.
基金This work was supported by the National Natural Science Foundation of China(Nos.21872029,20903023,U1463204 and 21173045)the Program for Leading Talents of Fujian Universities,the Natural Science Foundation of Fujian Province for the Distinguished Young Investigator Rolling Grant(No.2017J07002)+1 种基金the 1st Program of Fujian Province for Top Creative Young Talents,the Natural Science Foundation of Fujian Province(No.2019J0106)the Award Program for Minjiang Scholar Professorship is gratefully acknowledged.
文摘The conversion of biomass into valuable chemicals has promise for application in biorefineries.Light-driven photoredox catalysis,with the typical features of green route and operation under mild conditions,is considered a promising strategy for renewable biomass or biomass-derived intermediates conversion into high-value-added chemical feedstocks.In this review,we strongly emphasize the recent advances in photocatalytic valorization of lignin model compounds and biomassderived alcohols.We briefl y summarize the advances in photocatalytic cleavage of theβ-O-4 bond or C–C bond into usable chemicals in the lignin model.On the other hand,we clarify not only the hybrid system for cooperative biomass-relevant alcohols oxidation and hydrogen(H2)evolution but also the tunable accessibility to variation of the target products from the same alcohol reactant by catalyst design and optimization of reaction conditions.It is hoped that this review will inspire the rational design of photoredox catalysis-based systems toward efficient biomass-derived platform molecules valorization to obtain target-oriented valuable products.
基金supported by the National Natural Science Foundation of China(NSFC)(21173045,20903023)the Award Program for Minjiang Scholar Professorship+3 种基金the Natural Science Foundation(NSF)of Fujian Province for Distinguished Young Investigator(Grant No.2012J06003)the Program for Changjiang Scholars and Innovative Research Team in Universities(PCSIRT0818)the Program for Returned High-Level Overseas Chinese Scholars of Fujian provincethe Project Sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry
文摘Graphene (GR)-CdS nanocomposites with different weight addition ratios of GR have been assembled by a facile solvothermal treatment. The GR-CdS nanocomposite photocatalyst with an appropriate ratio of GR exhibits enhanced photoactivity for selective reduction of aromatic nitro compounds to the corresponding aromatic amines in water under visible light irradiation as compared with blank-CdS. The characterization of GR-CdS nanocomposite photocatalysts by a collection of techniques discloses that: i) GR can tune the microscopic morphology of CdS nanoparticles and improve light absorption intensity in the visible light region; ii) GR scaffolds act as an electron reservoir to trap and shuttle the electrons photogenerated from CdS semiconductor under the visible light illumination; iii) the introduction of GR enhances the adsorption capacity of GR-CdS nanocomposites toward the substrates, aromatic nitro compounds. The synergistic effect of these factors should account for the photoactivity advancement of GR-CdS nanocomposites toward the probe reactions. Furthermore, because the photogenerated holes in the system are trapped by the quenching agent ammonium oxalate, the as-obtained GR-CdS photocataiyst is stable during the photocatalytic reduction reactions. A reasonable model has also been proposed to illustrate the reaction mechanism.
基金supported by the National Natural Science Foundation of China(NSFC)(20903022,20903023,21173045)the Award Program for Minjiang Scholar Professorship+2 种基金the Science and Technology Development of Foundation of Fuzhou University(2009-XQ-10)the Open Fund of Photocatalysis of Fuzhou University(0380038004)the Program for Returned High-Level Overseas Chinese Scholars of Fujian Province
文摘CdS nanowires-nitrogen doped graphene (CdS NWs-NGR) nanocomposites have been fabricated by an electrostatic self-assembly strategy followed by a hydrothermal reduction. The CdS NWs-NGR exhibits higher photoactivity for selective reduction of aromatic nitro organics in water under visible light irradiation than blank CdS nanowires (CdS NWs) and CdS nanowires-reduced graphene oxide (CdS NWs-RGO) nanocomposites. The enhanced photoactivity of CdS NWs-NGR can be attributed to the improved electronic conductivity due to the introduc- tion of nitrogen atoms, which thus enhances the separation and transfer of charge carriers photogenerated from CdS NWs. Our work could provide a facile method to synthesize NGR based one-dimensional (1D) semiconductor composites for selective organic transformations, and broaden the potential applications for NGR as a cocatalyst.
基金the National Nature Science Foundation of China[No.21976172,22172030]the Strategic Priority Research Program of the Chinese Academy of Sciences[No.XDPB1902].
文摘The dynamic evolution of active site coordination structure during a high-temperature reaction is critically significant but often difficult for the research of efficient single-atom catalysts(SACs).Herein,we for the first time report the in situ activation behaviors of the local coordination structure of Pt single atoms(Pt_(1))during the high-temperature oxidation of light alkanes.The distinctly enhanced activity of the catalyst is attributed to the in situ evolved Pt_(1)−oxygen vacancy(Pt_(1)−OV)combination ensemble as an efficient and stable active site.Theoretical calculations reveal that the lattice oxygen adjacent to Pt_(1)and the H dissociated from CH4 constitute the lattice hydroxyl,which is the initial step in the formation of the Pt_(1)−OV combination.Pt_(1)and nearby unsaturated Mn can donate the charge back to O−O to promote the dissociation of O_(2).This work provides molecular-level insight into the in situ reaction-induced evolution of a single-atom coordination environment for designing efficient SACs under harsh conditions.
基金supported by the Natural Science Foundation of China (Nos. 22172030, 22072023, 21872029, U1463204 and 21173045)the Program for National Science and Technology Innovation Leading Talents (No. 00387072)+2 种基金the Program for Leading Talents of Fujian Universitiesthe 1st Program of Fujian Province for Top Creative Young Talentsthe Natural Science Foundation of Fujian Province (Nos. 2017J07002 and 2019J01631)。
文摘Ternary composites of reduced graphene oxide(GR)-CdS-Pd have been successfully synthesized via solvothermal and photodeposition methods for photocatalytic selective conversion of benzyl alcohol(BA)coupled with hydrogen(H_(2))production, which exhibit significantly improved photoactivity and selectivity than bare CdS. Mechanistic studies unveil that the cooperative effect of the close interface contact and matched energy level alignment between electrical conducting GR nanosheets(NSs) and CdS nanoparticles(NPs) in GR-CdS-Pd composite not only benefits the separation and transfer of photogenerated carriers but also improves the photocorrosion resistance of CdS. The photodeposited Pd NPs further promote the photogenerated charge separation and accelerate the formation of intermediate products(α-hydroxybenzyl radicals), thereby contributing to enhanced conversion of BA. This work would facilitate the rational design of GR as cocatalyst to construct an efficient and stable CdS-based composite photocatalyst for cooperative coupling of fine chemical synthesis and H_(2) evolution.
基金The support from the NSFC(22072023,22172030,21872029,U1463204,and 21173045)the Program for National Science and Technology Innovation Leading Talents(00387072)the Award Program for Minjiang Scholar Professorship,the Program for Leading Talents of Fujian Universities,the First Program of Fujian Province for Top Creative Young Talents,and the NSF of Fujian Province(2019J01631 and 2017J07002)is gratefully acknowledged.
文摘Semiconductor quantum dots have been emerging as one of the most ideal materials for artificial photosynthesis.Here,we report the assembled ZnS-CdS hybrid heterostructure for efficient coupling cooperative redox catalysis toward the oxidation of 1-phenylethanol to acetophenone/2,3-diphenyl-2,3-butanediol(pinacol)integrated with the reduction of protons to H2.The strong interaction and typical type-I band-position alignment between CdS quantum dots and ZnS quantum dots result in efficient separation and transfer of electron-hole pairs,thus distinctly enhancing the coupled photocatalyzed-redox activity and stability.The optimal ZnS-CdS hybrid also delivers a superior performance for various aromatic alcohol coupling photoredox reaction,and the ratio of electrons and holes consumed in such redox reaction is close to 1.0,indicating a high atom economy of cooperative coupling catalysis.In addition,by recycling the scattered light in the near field of a SiO_(2)sphere,the SiO_(2)-supported ZnS-CdS(denoted as ZnS-CdS/SiO_(2))catalyst can further achieve a 3.5-fold higher yield than ZnS-CdS hybrid.Mechanistic research clarifies that the oxidation of 1-phenylethanol proceeds through the pivotal radical intermediates of•C(CH_(3))(OH)Ph.This work is expected to promote the rational design of semiconductor quantum dots-based heterostructured catalysts for coupling photoredox catalysis in organic synthesis and clean fuels production.
基金financially supported by the National Natural Science Foundation of China (No.51305178)Xuzhou City Science and Technology Plan Project (No. XC12A013)the Research and Innovation Key Project of Graduate of Jiangsu Normal University (No. 2013YZD016)
文摘In order to improve the mechanical properties of deposited metal of ilmenite type welding electrode, CeO2/La rare earth elements were added into electrodes based on E4301 electrode, then electrodes were produced, test plates were welded, and mechanical properties were tested based on National Standards of China. For the sake of solving the problems of large amount of mechanical properties tests, long test cycle and high test cost during the conventional production process of electrode, a prediction model of the mechanical properties of deposited metal based on Takagi-Sugeno (T-S) fuzzy neural network was established. Mn, Si and C contents of medium manganese in electrode, CeO2, and La contents of electrode and welding speed were selected as input variables of the prediction model, and the tensile strength, lower yield strength, elongation, impact energy and hardness of de- posited metal were selected as output variables. Finally, predicting experiment was done under test samples, and results show that average relative prediction error of the tensile strength, lower yield strength, elongation and hardness are 0.91%, 2.57 %, 4.94 % and 1.94 %, respec- tively, which reach the need of actual production. The re- sults of prediction show that the mechanical properties of deposited metal of electrode containing rare earth can be forecasted accurately through material composition of electrode and welding parameters based on T-S fuzzy neural network model.
基金financially supported by the National Natural Science Foundation of China (No.51305178)Xuzhou City Science and Technology Plan Project (No.XC12A013)
文摘The ilmenite welding electrode has advantages of low cost and excellent welding technological properties.However, the welding quality is affected adversely by its poor crack resistance.To solve this problem, 12 kinds of rare earths coating formulas were optimized by means of orthogonal test design and curve fitting.Then the powders containing La/Ce O2 were extruded into ilmenite welding electrode through screw-type pressing–scribbling machine.After that, a series of mechanical properties tests were conducted according to national standards.Next, the mechanical properties data were analyzed comprehensively by analyzing variance, boxplot as well as Minitab 3D surface chart.The results show that compared with the formula without rare earth, the deposited metal’s impact toughness,the lower yield strength, the tensile strength, and the hardness are increased by 54.44 %, 9.25 %, 6.37 %, and4.27 %, respectively.In other words, Electrode 6 with the La/Ce O2 amount of 0.5 %/0.1 % in coating has better mechanical properties.
基金the National Natural Science Foundation of China(Nos.22172030,22072023,21872029,and U1463204)the Program for National Science and Technology Innovation Leading Talents(No.00387072)+1 种基金the 1st Program of Fujian Province for Top Creative Young Talents,the Award Program for Minjiang Scholar Professorship,the Natural Science Foundation(No.2019J0106)of Fujian Provincethe Natural Science Foundation of Fujian Province for Distinguished Young Investigator Rolling Grant(No.2017J07002)is gratefully acknowledged.
文摘Photocatalyzed organic transformations have spurred immense interest in synthetic chemistry for the efficient conversion of solar energy into chemical energy.However,the crucial roles of support,which fixes catalytic sites and improves the light-harvesting ability,are often ignored in photoredox transformations.Herein,we report the utilization of spherical SiO2 support to engineer AuPd alloy particles(denoted as AuPd/SiO2),conceptually different from traditional methods for tuning optical absorption of plasmonic Au or AuPd particles,to manipulate light-harvesting ability of AuPd particles for highly selective and efficient photocatalytic Suzuki cross-coupling reactions.In this deliberately designed system,typically without the size and shape alternation of AuPd particles,the supported AuPd particles recycle the scattering light from spherical SiO2 support and achieve the significant broad light-harvesting ability instead of the surface plasmon resonance peak.The engineered AuPd/SiO2 composites by the use of near-field scattering-promoted optical absorption showcase the remarkably enhanced activity for visible-light-induced photocatalytic Suzuki cross-coupling reactions in comparison with that using commercial SiO2 support,highlighting the spherical-support-effect induced efficient utilization of scattered light.This work highlights the feasibility of manipulating the light-harvesting capability of bimetallic particles by the near-field scattering-promoted optical absorption model toward efficient photo-driven Suzuki cross-coupling reaction and other C-C coupling organic synthesis to produce high value-added chemicals.