Despite surgical improvements and pharmacological advances,management of late-stage gastric cancer patients,especially those with hepatic metastasis remains challenging[1–3].Although nationwide registry data from SEE...Despite surgical improvements and pharmacological advances,management of late-stage gastric cancer patients,especially those with hepatic metastasis remains challenging[1–3].Although nationwide registry data from SEER(Surveillance,Epidemiology,and End Results)[4]and the Nordic database[5]in Western countries have provided epidemiological information for patients with gastric cancer liver metastasis(GCLM),little is known about the detailed clinical characteristics.展开更多
Pretreatment of the carrier for supported catalysts can effectively improve the strong metal-support interaction(SMSI)and increase the dispersion of precious metals,which are critical to many important catalytic react...Pretreatment of the carrier for supported catalysts can effectively improve the strong metal-support interaction(SMSI)and increase the dispersion of precious metals,which are critical to many important catalytic reactions.In this work,we tuned SMSI on Pd/TiO_(2)catalysts through inducing surface defects of TiO_(2)by pretreated with different atmospheres(H_(2)/N_(2),N_(2),O_(2)/N_(2))at the high temperature(800℃).Multiple characterization results illustrated that surface defects anchored Pd species and thus enhanced their dispersion.During reduction,Ti^(3+)species formed and transferred onto the metallic Pd species and then induced SMSI,which effectively stabilize Pd species in the metallic state.The stronger MSI,the more stability of Pd species.As a case,Pd/TiO_(2)–800H_(2),with strongest MSI,displayed the best HCHO oxidation performance at low temperature(10℃).展开更多
Rh single atom catalysts(SACs)have been insensitively investigated recently due to the maximum utilization efficiency of Rh,one of the most expensive precious metals.Although great efforts have been made in the develo...Rh single atom catalysts(SACs)have been insensitively investigated recently due to the maximum utilization efficiency of Rh,one of the most expensive precious metals.Although great efforts have been made in the development and application of Rh SACs,there are few reports on the precise control of the local coordination environment of Rh single sites on CeO_(2) and their catalytic performance for N_(2)O decomposition.Herein,Rh/CeO_(2) catalysts with different Rh-O coordination numbers(CNs)were successfully prepared using different CeO_(2) supports and a simple incipient wetness impregnation(IWI)method.It is observed that the Rh/CeO_(2) catalyst with slightly higher CN of Rh-O(Rh/CeO_(2)-H)prepared from CeO_(2) shows much higher N_(2)O decomposition activity than the catalyst with lower CN of Rh-O(Rh/CeO_(2)-L)obtained from Ce(OH)_(x).The Rh species within Rh/CeO_(2)-H are found to be more reactive than those within Rh/CeO_(2)-L,which can better facilitate the O_(2)desorption once formed during N_(2)O deco mposition.In additio n,more surface oxygen vacancies are present on Rh/CeO_(2)-H than on Rh/CeO_(2)-L,well explaining the superior N_(2)O adsorption and activation capability on the former catalyst.It is concluded that more abundant oxygen vacancies and reactive Rh single atom sites with slightly higher CN of Rh-O and significantly higher reducibility altogether contribute to the superior N_(2)O decomposition activity on the Rh/CeO_(2)-H catalyst.展开更多
Three-dimensionally ordered mesoporous Fe2O3（meso-Fe2O3） and its supported Au, Pd,and Au-Pd alloy（xA uP dy/meso-Fe2O3; x = 0.08–0.72 wt.%; Pd/Au molar ratio（y） = 1.48–1.85）photocatalysts have been prepared via...Three-dimensionally ordered mesoporous Fe2O3（meso-Fe2O3） and its supported Au, Pd,and Au-Pd alloy（xA uP dy/meso-Fe2O3; x = 0.08–0.72 wt.%; Pd/Au molar ratio（y） = 1.48–1.85）photocatalysts have been prepared via the KIT-6-templating and polyvinyl alcohol-protected reduction routes, respectively. Physical properties of the samples were characterized, and their photocatalytic activities were evaluated for the photocatalytic oxidation of acetone in the presence of a small amount of H2O2 under visible-light illumination. It was found that the meso-Fe2O3 was rhombohedral in crystal structure. The as-obtained samples displayed a high surface area of 111.0–140.8 m^2/g and a bandgap energy of 1.98–2.12 eV. The Au, Pd and/or Au–Pd alloy nanoparticles（NPs） with a size of 3–4 nm were uniformly dispersed on the surface of the meso-Fe2O3 support. The 0.72 wt.% AuP d1.48/meso-Fe2O3 sample performed the best in the presence of 0.06 mol/L H2O2 aqueous solution, showing a 100% acetone conversion within4 hr of visible-light illumination. It was concluded that the good performance of 0.72 wt.%AuPd（1.48）/meso-Fe2O3 for photocatalytic acetone oxidation was associated with its ordered mesoporous structure, high adsorbed oxygen species concentration, plasmonic resonance effect between AuPd（1.48） NPs and meso-Fe2O3, and effective separation of the photogenerated charge carriers. In addition, the introduction of H2O2 and the involvement of the photo-Fenton process also played important roles in enhancing the photocatalytic activity of 0.72 wt.%AuPd（1.48）/meso-Fe2O3.展开更多
Developing non-precious metal catalysts to selectively reduce functionalized nitroarenes with high efficiency is urgently desirable for the production of value-added amines.Herein,we report a novel,efficient,anti-pois...Developing non-precious metal catalysts to selectively reduce functionalized nitroarenes with high efficiency is urgently desirable for the production of value-added amines.Herein,we report a novel,efficient,anti-poisoning single-atom cobalt catalyst(Co-NAC)for the highly selective hydrogenation of the nitro to amino group for nitroarenes baring various functional groups,including vinyl,cyano,and halogen.Using a combination of structure characterization techniques,we have confirmed that the cobalt species are predominantly present in the form of four-coordinated Co single sites anchored on nitrogen-assembly carbon(NAC)as the ordered mesoporous support.Co-NAC catalysts enable the full conversion and>99%selectivity with molecular H2 as a green reductant under mild conditions(80℃,2 MPa H2).As for the selective hydrogenation of 3-nitrostyrene,Co-NAC catalyst affords high catalytic productivity(19.7 h-1),which is superior to the cobalt nanoparticles(NPs)catalysts and most of the recently reported Co-based catalysts.This is attributed to the highly accessible atomically-dispersed Co active sites,the high surface area with ordered-mesoporous morphology and the prominent high content of nitrogen dopants.Notably,Co-NAC catalyst displays resistance towards sulfur-containing poisons(20 equivalents)and strong non-oxidizing acid(8 M),showing great potential for continuous application in the chemical industry.展开更多
FeTiOx has been recognized as an environmental-friendly and cost-effective catalyst for selective catalytic reduction(SCR)of NOx with NH3.Aimed at further improving the low-temperature DeNOx efficiency of FeTiOx catal...FeTiOx has been recognized as an environmental-friendly and cost-effective catalyst for selective catalytic reduction(SCR)of NOx with NH3.Aimed at further improving the low-temperature DeNOx efficiency of FeTiOx catalyst,a simple strategy of CeO_(2) doping was proposed.The low-temperature(<250°C)NH3-SCR activity of FeTiOx catalyst could be dramatically enhanced by CeO2 doping,and the optimal composition of the catalyst was confirmed as FeCe_(0.2)TiOx,which performed a NOx conversion of 90%at ca.200°C.According to X-ray diffraction(XRD),Raman spectra and X-ray absorption fine structure spectroscopy(XAFS)analysis,FeCe_(0.2)TiOx showed low crystallinity,with Fe and Ce species well mixed with each other.Based on the fitting results of extended X-ray absorption fine structure(EXAFS),a unique Ce-O-Fe structure was formed in FeCe_(0.2)TiOx catalyst.The well improved specific surface area and the newly formed Ce-O-Fe structure dramatically contributed to the improvement of the redox property of FeCe_(0.2)TiOx catalyst,which was well confirmed by H2-temperature-programmed reduction(H2-TPR)and in situ XAFS experiments.Such enhanced redox capability could benefit the activation of NO and NH_(3) at low temperatures for NOx removal.The detailed reaction mechanism study further suggested that the facile oxidative dehydrogenation of NH_(3) to highly reactive-NH_(2) played a key role in enhancing the low-temperature NH_(3)-SCR performance of FeCe_(0.2)TiOx catalyst.展开更多
基金supported by the Ph.D.Program Foundation of Ministry of Education of China(20131103110002)the NNSF of China(21377008)+2 种基金National High Technology Research and Development Program(863 Program,2015AA034603)Foundation on the Creative Research Team Con-struction Promotion Project of Beijing Municipal InstitutionsScientific Research Base Construction-Science and Technology Creation Plat-form-National Materials Research Base Construction~~
基金This work was supported by the National Natural Science Foundation of China(81972790)the Beijing Nova Program(Z181100006218011).
文摘Despite surgical improvements and pharmacological advances,management of late-stage gastric cancer patients,especially those with hepatic metastasis remains challenging[1–3].Although nationwide registry data from SEER(Surveillance,Epidemiology,and End Results)[4]and the Nordic database[5]in Western countries have provided epidemiological information for patients with gastric cancer liver metastasis(GCLM),little is known about the detailed clinical characteristics.
基金supported by the Youth Innovation Promotion Association,CAS(No.2020310)the Science and Technology Planning Project of Xiamen City(No.3502Z20191021)the Science and Technology Innovation“2025”major program in Ningbo(No.2022Z028)。
文摘Pretreatment of the carrier for supported catalysts can effectively improve the strong metal-support interaction(SMSI)and increase the dispersion of precious metals,which are critical to many important catalytic reactions.In this work,we tuned SMSI on Pd/TiO_(2)catalysts through inducing surface defects of TiO_(2)by pretreated with different atmospheres(H_(2)/N_(2),N_(2),O_(2)/N_(2))at the high temperature(800℃).Multiple characterization results illustrated that surface defects anchored Pd species and thus enhanced their dispersion.During reduction,Ti^(3+)species formed and transferred onto the metallic Pd species and then induced SMSI,which effectively stabilize Pd species in the metallic state.The stronger MSI,the more stability of Pd species.As a case,Pd/TiO_(2)–800H_(2),with strongest MSI,displayed the best HCHO oxidation performance at low temperature(10℃).
基金Project supported by the Startup Fund(F.L.)from the University of Central Florida(UCF)National Science Foundation grants(CHE-1955343,DMR-1920050).
文摘Rh single atom catalysts(SACs)have been insensitively investigated recently due to the maximum utilization efficiency of Rh,one of the most expensive precious metals.Although great efforts have been made in the development and application of Rh SACs,there are few reports on the precise control of the local coordination environment of Rh single sites on CeO_(2) and their catalytic performance for N_(2)O decomposition.Herein,Rh/CeO_(2) catalysts with different Rh-O coordination numbers(CNs)were successfully prepared using different CeO_(2) supports and a simple incipient wetness impregnation(IWI)method.It is observed that the Rh/CeO_(2) catalyst with slightly higher CN of Rh-O(Rh/CeO_(2)-H)prepared from CeO_(2) shows much higher N_(2)O decomposition activity than the catalyst with lower CN of Rh-O(Rh/CeO_(2)-L)obtained from Ce(OH)_(x).The Rh species within Rh/CeO_(2)-H are found to be more reactive than those within Rh/CeO_(2)-L,which can better facilitate the O_(2)desorption once formed during N_(2)O deco mposition.In additio n,more surface oxygen vacancies are present on Rh/CeO_(2)-H than on Rh/CeO_(2)-L,well explaining the superior N_(2)O adsorption and activation capability on the former catalyst.It is concluded that more abundant oxygen vacancies and reactive Rh single atom sites with slightly higher CN of Rh-O and significantly higher reducibility altogether contribute to the superior N_(2)O decomposition activity on the Rh/CeO_(2)-H catalyst.
基金supported by the National Natural Science Foundation of China (No. 21377008)the National High Technology Research and Development Program of China ("863"Program)(No. 2015AA034603)the Foundation of the Creative Research Team Construction Promotion Project of Beijing Municipal Institutions
文摘Three-dimensionally ordered mesoporous Fe2O3（meso-Fe2O3） and its supported Au, Pd,and Au-Pd alloy（xA uP dy/meso-Fe2O3; x = 0.08–0.72 wt.%; Pd/Au molar ratio（y） = 1.48–1.85）photocatalysts have been prepared via the KIT-6-templating and polyvinyl alcohol-protected reduction routes, respectively. Physical properties of the samples were characterized, and their photocatalytic activities were evaluated for the photocatalytic oxidation of acetone in the presence of a small amount of H2O2 under visible-light illumination. It was found that the meso-Fe2O3 was rhombohedral in crystal structure. The as-obtained samples displayed a high surface area of 111.0–140.8 m^2/g and a bandgap energy of 1.98–2.12 eV. The Au, Pd and/or Au–Pd alloy nanoparticles（NPs） with a size of 3–4 nm were uniformly dispersed on the surface of the meso-Fe2O3 support. The 0.72 wt.% AuP d1.48/meso-Fe2O3 sample performed the best in the presence of 0.06 mol/L H2O2 aqueous solution, showing a 100% acetone conversion within4 hr of visible-light illumination. It was concluded that the good performance of 0.72 wt.%AuPd（1.48）/meso-Fe2O3 for photocatalytic acetone oxidation was associated with its ordered mesoporous structure, high adsorbed oxygen species concentration, plasmonic resonance effect between AuPd（1.48） NPs and meso-Fe2O3, and effective separation of the photogenerated charge carriers. In addition, the introduction of H2O2 and the involvement of the photo-Fenton process also played important roles in enhancing the photocatalytic activity of 0.72 wt.%AuPd（1.48）/meso-Fe2O3.
基金supported by the National Key R&D Program of China(No.2016YFA0202900)the National Natural Science Foundation of China(Nos.21878266,22078288,and 22108243)+4 种基金L.Q.and Y.T.L.were supported by the U.S.Department of Energy(DOE),Office of Basic Energy Sciences,Division of Chemical Sciences,Geosciences,and BiosciencesThe Ames Laboratory is operated for the U.S.DOE by Iowa State University under Contract No.DE-AC02-07CH11358W.Y.H.,J.Q.Y.,and X.W.thank the support from Iowa State University.F.D.L.thanks the Startup Fund from the University of Central Florida(UCF)S.H.X.thanks the support from the Preeminent Postdoctoral Program(P3)at UCFThis research used beamline 7-BM(QAS)of the National Synchrotron Light Source II,a U.S.Department of Energy(DOE)Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No.DE-SC0012704.
文摘Developing non-precious metal catalysts to selectively reduce functionalized nitroarenes with high efficiency is urgently desirable for the production of value-added amines.Herein,we report a novel,efficient,anti-poisoning single-atom cobalt catalyst(Co-NAC)for the highly selective hydrogenation of the nitro to amino group for nitroarenes baring various functional groups,including vinyl,cyano,and halogen.Using a combination of structure characterization techniques,we have confirmed that the cobalt species are predominantly present in the form of four-coordinated Co single sites anchored on nitrogen-assembly carbon(NAC)as the ordered mesoporous support.Co-NAC catalysts enable the full conversion and>99%selectivity with molecular H2 as a green reductant under mild conditions(80℃,2 MPa H2).As for the selective hydrogenation of 3-nitrostyrene,Co-NAC catalyst affords high catalytic productivity(19.7 h-1),which is superior to the cobalt nanoparticles(NPs)catalysts and most of the recently reported Co-based catalysts.This is attributed to the highly accessible atomically-dispersed Co active sites,the high surface area with ordered-mesoporous morphology and the prominent high content of nitrogen dopants.Notably,Co-NAC catalyst displays resistance towards sulfur-containing poisons(20 equivalents)and strong non-oxidizing acid(8 M),showing great potential for continuous application in the chemical industry.
基金support from the Key Project of National Natural Science Foundation of China(No.21637005)Accelerator Research Organization(KEK)(Japan)for the generous help in XAS experiments conducted at Photon Factory,KEK,Japan(No.2012G537).
文摘FeTiOx has been recognized as an environmental-friendly and cost-effective catalyst for selective catalytic reduction(SCR)of NOx with NH3.Aimed at further improving the low-temperature DeNOx efficiency of FeTiOx catalyst,a simple strategy of CeO_(2) doping was proposed.The low-temperature(<250°C)NH3-SCR activity of FeTiOx catalyst could be dramatically enhanced by CeO2 doping,and the optimal composition of the catalyst was confirmed as FeCe_(0.2)TiOx,which performed a NOx conversion of 90%at ca.200°C.According to X-ray diffraction(XRD),Raman spectra and X-ray absorption fine structure spectroscopy(XAFS)analysis,FeCe_(0.2)TiOx showed low crystallinity,with Fe and Ce species well mixed with each other.Based on the fitting results of extended X-ray absorption fine structure(EXAFS),a unique Ce-O-Fe structure was formed in FeCe_(0.2)TiOx catalyst.The well improved specific surface area and the newly formed Ce-O-Fe structure dramatically contributed to the improvement of the redox property of FeCe_(0.2)TiOx catalyst,which was well confirmed by H2-temperature-programmed reduction(H2-TPR)and in situ XAFS experiments.Such enhanced redox capability could benefit the activation of NO and NH_(3) at low temperatures for NOx removal.The detailed reaction mechanism study further suggested that the facile oxidative dehydrogenation of NH_(3) to highly reactive-NH_(2) played a key role in enhancing the low-temperature NH_(3)-SCR performance of FeCe_(0.2)TiOx catalyst.
