Our previous study has revealed that procyanidin A_(1)(A_(1))and its simulated digestive product(D-A,)can alleviate acrylamide(ACR)-induced intestine cell damage.However,the underlying mechanism remains unknown.In thi...Our previous study has revealed that procyanidin A_(1)(A_(1))and its simulated digestive product(D-A,)can alleviate acrylamide(ACR)-induced intestine cell damage.However,the underlying mechanism remains unknown.In this study,we elucidated the molecular mechanism for and D-A_(1) to alleviate ACR-stimulated IPEC-J2 cell damage.ACR slightly activated nuclear factor erythroid 2-related factor 2(Nrf2)signaling and its target genes,but this activation could not reduce intestine cell damage.A_(1) and D-A_(1) could alleviate ACR-induced cell damage,but the effect was abrogated in cells transiently transfected with Nrf2 small interfering RNA(siRNA).Further investigation confirmed that A_(1) and D-A_(1) interacted with Ketch-like ECH-associated protein 1(Keapl),which boosted the stabilization of Nrf2,subsequently promoted the translocation of Nrf2 into the nucleus,and further increased the expression of antioxidant proteins,thereby inhibiting glutathione(GSH)consumption,maintaining redox balance and eventually alleviating ACR-induced cell damage.Importantly,there was no difference between A_(1) and D-A_(1) treated groups,indicating that A_(1) can tolerate gastrointestinal digestion and may be a potential compound to limit the toxicity of ACR.展开更多
In this paper,we present a distal-scanning common path probe for optical coherence tomography(OCT)equipped with a hollow ultrasonic motor and a simple and specially designed beam-splitter.This novel probe proves to be...In this paper,we present a distal-scanning common path probe for optical coherence tomography(OCT)equipped with a hollow ultrasonic motor and a simple and specially designed beam-splitter.This novel probe proves to be able to effectively circumvent polarization and dispersion mismatch caused by fiber motion and is more robust to a variety of interfering factors during the imaging process,experimentally compared to a conventional noncommon path probe.Furthermore,our design counteracts the attenuation of backscattering with depth and the fall-off of the signal,resulting in a more balanced signal range and greater imaging depth.Spectral-domain OCT imaging of phantom and biological tissue is also demonstrated with a sensitivity of∼100dB and a lateral resolution of∼3μm.This low-cost probe offers simplified system configuration and excellent robustness,and is therefore particularly suitable for clinical diagnosis as one-off medical apparatus.展开更多
A simple procedure is described for the HPLC and UV determination of tea saponin in tea seed oil. Determinate was accomplished with UV wavelength detection 550 nm for saponification sample, and HPLC was done under con...A simple procedure is described for the HPLC and UV determination of tea saponin in tea seed oil. Determinate was accomplished with UV wavelength detection 550 nm for saponification sample, and HPLC was done under conditions: C18 analytical column of TC-C18, 4. 6 × 250 mm, column temperature at room temperature, injected sample volume was 10 μL, mobile phase’s methanol, flow-rate 0.8 ml/min and detection wavelength 280 nm.展开更多
Optical coherence tomography(OCT)enables in vivo imaging of port wine stains(PWS)lesions.The knowledge of vascular struct ure and epidermal thickness(ET)of PWS may aid the objectivediagnosis and optimal treatment.To o...Optical coherence tomography(OCT)enables in vivo imaging of port wine stains(PWS)lesions.The knowledge of vascular struct ure and epidermal thickness(ET)of PWS may aid the objectivediagnosis and optimal treatment.To obtain the structural parameters more rapidly and avoiduser intervention,an automated algorithm of energy map is introduced based on intensity andedge information to extract the skin surface using dynamic programming method.Subsequently,an averaged A-scan analysis is performed to obtain the mean ET and the relative intensity ofdermis indicating the corresponding vascular density.This approach is currently successfullyapplied in clinical diagnosis and shows promising guidance and assessment of PDT treatment.展开更多
In most coherent imaging modality,speckle noise is a major cause that blurs the boundary of tissues and degrades the image contrast.By utilizing the unique properties of supercontinuum(SC)generated by noise-like pulse...In most coherent imaging modality,speckle noise is a major cause that blurs the boundary of tissues and degrades the image contrast.By utilizing the unique properties of supercontinuum(SC)generated by noise-like pulses(NLPs)and a simple multi-frame averaging technique,we achieved significant speckle reduction in spectral domain optical coherence tomography(SD-OCT).We quantitatively compared the speckle of our proposed method with those of conventional swept source OCT(SS-OCT)and SD-OCT based on commercial light sources.The experimental results show that SC pumped by NLPs combined with noncoherent averaging method achieves better denoising performance in terms of contrast to noise ratio(CNR).展开更多
In the process of Higher Vocational classified examination enrollment reform,Jilin Province has adopted a diversified examination enrollment model and“cultural quality test+vocational skill test”evaluation method,an...In the process of Higher Vocational classified examination enrollment reform,Jilin Province has adopted a diversified examination enrollment model and“cultural quality test+vocational skill test”evaluation method,and established the“vocational education college entrance examination”system.This paper analyzes the important role and practical difficulties of“vocational skill test”in Higher Vocational classified examination,studies the existing problems,and puts forward to reasonably divide the proportion of“cultural quality test”and“vocational skill test”,sets diversified admission standards,scientifically sets up the assessment methods and contents of“vocational skill test”,further improves the“cultural quality test+vocational skill test”evaluation method and builds a classified examination and enrollment system more in line with the characteristics of vocational education.展开更多
A highly efficient,transition-metal-and light-free approach to polyheterocycles via regioselective cascade radical cyclization is developed.The redox-neutral protocol has a broad substrate scope with good functional g...A highly efficient,transition-metal-and light-free approach to polyheterocycles via regioselective cascade radical cyclization is developed.The redox-neutral protocol has a broad substrate scope with good functional group tolerance and probably undergoes a SET process,which is initiated by catalytic amounts of quinone in combination with 2.0 equiv.of Cs_(2)CO_(3).展开更多
Formic acid oxidation is an important electrocatalytic reaction in proton- exchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have deve...Formic acid oxidation is an important electrocatalytic reaction in proton- exchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCO0* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/ activation towards improved electrocatalytic performance.展开更多
Atomically dispersed metal has gained much attention because of the new opportunities they offer in catalysis. However, it is still crucial to understand the mechanism of single-atom catalysis at molecular level for e...Atomically dispersed metal has gained much attention because of the new opportunities they offer in catalysis. However, it is still crucial to understand the mechanism of single-atom catalysis at molecular level for expanding them to other more difficult catalytic reactions, such as ammonia synthesis from nitrogen. In fact, developing ammonia synthesis under ambient conditions to overcome the high energy consumption in well-established Haber-Bosch process has fascinated scientists for many years.Herein, we demonstrate that single Cu atom yields facile valence-electron isolation from the conjugated π electron cloud of p-CN. Electron spin resonance measurements reveal that these isolated valence electrons can be easily excited to generate free electrons under photo-illumination, thus inducing high efficient photo-induced ammonia synthesis under ambient conditions.The NH_3 producing rate of copper modified carbon nitride(Cu-CN) reached 186 μmol g^(-1) h^(-1) under visible light irradiation with the quantum efficiency achieved 1.01% at 420 nm monochromatic light. This finding surely offers a model to open up a new vista for the ammonia synthesis at gentle conditions. The introduction of single atom to isolate the valence electron also represents a new paradigm for many other photocatalytic reactions, since the most photoinduced processes have been successfully exploited sharing the same origin.展开更多
To fully realize the commercial viability of Pt in fuel cells, the usage of scarce Pt must be reduced while the activity and durability in 02 reduction reaction (ORR) must be enhanced. Here we report a metallic stac...To fully realize the commercial viability of Pt in fuel cells, the usage of scarce Pt must be reduced while the activity and durability in 02 reduction reaction (ORR) must be enhanced. Here we report a metallic stack design achieving these goals for ORR, based on atomically precise materials synthesis. Au@Pd@Pt nanostructures with atomically thin Pt shells and high-index surfaces form an excellent platform for integrating the effects of electronic structures, surface facets, and substrate stabilization to boost ORR performance. Au@Pd@Pt trisoctahedrons (TOH) achieve mass activity 6.1 times higher than that of commercial Pt/C and dramatically enhanced durability beyond 1.0 V vs. a reversible hydrogen electrode in oxidation potential. Meanwhile, Pt comprises only 3.2% of the nanostructures. To further improve the ORR activity and demonstrate the versatility of our strategy, we implement the same design in PtNi alloy electrocatalysts. The Au@Pd@PtNi TOHs exhibit mass activity 14.3 times higher than that of commercial Pt/C as well as excellent durability. This work demonstrates an alternative strategy for fabricating high-performance and low-cost catalysts, and highlights the importance of simultaneous surface and interfacial engineering with atomic precision in designing catalysts.展开更多
Cathodic oxygen reduction reaction (ORR) is a highly important electrochemical reaction in renewable-energy technologies. In general, the surface area, exposed facets and electrical conductivity of catalysts all pla...Cathodic oxygen reduction reaction (ORR) is a highly important electrochemical reaction in renewable-energy technologies. In general, the surface area, exposed facets and electrical conductivity of catalysts all play important roles in determining their electrocatalytic activities, while their performance durability can be improved by integration with supporting materials. In this work we have developed a method to synthesize hybrid structures between PtPd bimetallic nanocages and graphene by employing selective epitaxial growth of single-crystal Pt shells on Pd nanocubes supported on reduced graphene oxide (rGO), followed by Pd etching. The hollow nature, {100} surface facets and bimetallic composition of PtPd nanocages, together with the good conductivity and stability of graphene, enable high electrocatalytic performance in ORR. The obtained PtPd nanocage-rGO structures exhibit mass activity (0.534 A.m-1) and which are 4.4 times and 3.9 times greater than the specific activity (0.482 mA-cm-2) corresponding values for Pt/C.展开更多
Supports are commonly implemented in the industrial application of heterogeneous catalysts to improve the stability and recyclability of catalysts.The supported catalysts often show the enhanced activity and selectivi...Supports are commonly implemented in the industrial application of heterogeneous catalysts to improve the stability and recyclability of catalysts.The supported catalysts often show the enhanced activity and selectivity in various catalytic reactions.However,the specific contributions of electronic and steric effects to a catalytic system often remain elusive due to the lack of well-defined model systems.In this work,two types of uniform Pd nanocrystals covered by{111}facets in tetrahedral and octahedral shapes,respectively,are synthesized with identical chemical environment and loaded on Ti O_2supports to form hybrid structures(Pd{111}-Ti O_2)towards the application of formic acid decomposition.Our observation suggests that the polarization effect at the interface of Pd-Ti O_2enhances its activity in formic acid decomposition.Moreover,the Pd tetrahedrons-Ti O_2hybrid structure whose Pd{111}-Ti O_2interface possesses a larger angle shows higher catalytic activity,owing to the reduced steric effect as compared to Pd octahedrons-Ti O_2.This study reveals the nature of interface effects in formic acid decomposition,and provides a guidance for the related catalyst design.展开更多
Anodic oxygen evolution reaction(OER)is the key bottleneck for water electrolysis technique owing to its sluggish reaction kinetics.Interfacial engineering on the rationally designed heterostructure can regulate the e...Anodic oxygen evolution reaction(OER)is the key bottleneck for water electrolysis technique owing to its sluggish reaction kinetics.Interfacial engineering on the rationally designed heterostructure can regulate the electronic states efficiently for intrinsic activity improvement.Here,we report a co-phosphorization approach to construct a VPO_(4)-Ni_(2)P heterostructure on nickel foam with strongly chemical binding,wherein phosphate acts as electronic modifier for Ni_(2)P electrocatalyst.Profiting from the interfacial interaction,it is uncovered that electron shifts from Ni_(2)P to VPO_(4)to render valence increment in Ni species.Such an electronic manipulation rationalizes the chemical affinities of various oxygen intermediates in OER pathway,giving a substantially reduced energy barrier.As a result,the advanced VPO_(4)-Ni_(2)P heterostructure only requires an overpotential of 289 mV to deliver a high current density of 350 mA/cm^(2)for OER in alkaline electrolyte,together with a Tafel slope as low as 28 mV/dec.This work brings fresh insights into interfacial engineering for advanced electrocatalyst design.展开更多
Efficient catalytic system with low energy consumption exhibits increasing importance due to the upcoming energy crisis.Given this situation,it should be an admirable strategy for reducing energy input by effectively ...Efficient catalytic system with low energy consumption exhibits increasing importance due to the upcoming energy crisis.Given this situation,it should be an admirable strategy for reducing energy input by effectively utilizing incident solar energy as a heat source during catalytic reactions.Herein,aza-fused7 r-conjugated microporous polymer(aza-CMP)with broad light absorption and high photothermal conversion efficiency was synthesized and utilized as a support for bimetallic AuPd nanocatalysts in light-driven benzyl alcohol oxidation.The AuPd nanoparticles anchored on aza-CMP(aza-CM P/Au_xPdy)exhibited excellent catalytic performance for benzyl alcohol oxidation under 50 mW/cm^2 light irradiation.The improved catalytic performance by the aza-CMP/Au_xPdy is attributed to the unique photothermal effect induced by aza-CMP,which can promote the catalytic benzyl alcohol oxidation occurring at Au Pd.This work presents a novel approach to effectively utilize solar energy for conventional catalytic reactions through photothermal effect.展开更多
Imposing phase engineering to porous materials is promising to realize outperforming electrocatalytic performances by taking advantages of the merits of porous nanoarchitecture and heterophase structure.In this work,a...Imposing phase engineering to porous materials is promising to realize outperforming electrocatalytic performances by taking advantages of the merits of porous nanoarchitecture and heterophase structure.In this work,amorphous/crystalline ruthenium oxide(RuO_(2))porous particles with rationally regulated heterophases are successfully prepared by integrating the phase engineering into the porous material synthesis.The resultant defect-rich amorphous/crystalline RuO_(2)porous particles exhibit excellent electrocatalytic performance toward the oxygen evolution reaction,achieving a low overpotential of 165 mV at a current density of 10 mA·cm^(−2)and a high mass activity up to 133.8 mA·cm^(-2)at a low overpotential of 200 mV.This work indicates that the synergistic effect of amorphous/crystalline heterophase and porous structural characteristics enables RuO_(2)to trigger a superior electrocatalytic activity.展开更多
A low-cost manganese-catalyzed oxidant-free selective C–H acylation of indole with ketene is reported.This protocol features mild reaction conditions and good functional group tolerance.The yield is from middle to ex...A low-cost manganese-catalyzed oxidant-free selective C–H acylation of indole with ketene is reported.This protocol features mild reaction conditions and good functional group tolerance.The yield is from middle to excellent.The acylation products can be further converted to diverse useful compounds.Mechanism study reveals the acylation transformation possibly undergoes a cyclomanganated complex species as reactive intermediate.展开更多
Photooxidation provides a promising strategy for removing the dominant indoor pollutant of HCHO,while the underlying photooxidation mechanism is still unclear,especially the exact role of H2O molecules.Herein,we utili...Photooxidation provides a promising strategy for removing the dominant indoor pollutant of HCHO,while the underlying photooxidation mechanism is still unclear,especially the exact role of H2O molecules.Herein,we utilize in-situ spectral techniques to unveil the H2O-mediated HCHO photooxidation mechanism.As an example,the synthetic defective Bi2WO6 ultrathin sheets realize high-rate HCHO photooxidation with the assistance of H2O at room temperature.In-situ electron paramagnetic resonance spectroscopy demonstrates the existence of•OH radicals,possibly stemmed from H2O oxidation by the photoexcited holes.Synchrotron-radiation vacuum ultraviolet photoionization mass spectroscopy and H218O isotope-labeling experiment directly evidence the formed•OH radicals as the source of oxygen atoms,trigger HCHO photooxidation to produce CO2,while in-situ Fourier transform infrared spectroscopy discloses the HCOO*radical is the main photooxidation intermediate.Density-functional-theory calculations further reveal the•OH formation process is the rate-limiting step,strongly verifying the critical role of H2O in promoting HCHO photooxidation.This work first clearly uncovers the H2O-mediated HCHO photooxidation mechanism,holding promise for high-efficiency indoor HCHO removal at ambient conditions.展开更多
基金supported by the project from National Natural Science Foundation of China (31671962)Fundamental Research Funds for the Central Universities (2662019PY034)。
文摘Our previous study has revealed that procyanidin A_(1)(A_(1))and its simulated digestive product(D-A,)can alleviate acrylamide(ACR)-induced intestine cell damage.However,the underlying mechanism remains unknown.In this study,we elucidated the molecular mechanism for and D-A_(1) to alleviate ACR-stimulated IPEC-J2 cell damage.ACR slightly activated nuclear factor erythroid 2-related factor 2(Nrf2)signaling and its target genes,but this activation could not reduce intestine cell damage.A_(1) and D-A_(1) could alleviate ACR-induced cell damage,but the effect was abrogated in cells transiently transfected with Nrf2 small interfering RNA(siRNA).Further investigation confirmed that A_(1) and D-A_(1) interacted with Ketch-like ECH-associated protein 1(Keapl),which boosted the stabilization of Nrf2,subsequently promoted the translocation of Nrf2 into the nucleus,and further increased the expression of antioxidant proteins,thereby inhibiting glutathione(GSH)consumption,maintaining redox balance and eventually alleviating ACR-induced cell damage.Importantly,there was no difference between A_(1) and D-A_(1) treated groups,indicating that A_(1) can tolerate gastrointestinal digestion and may be a potential compound to limit the toxicity of ACR.
基金supported in part by the National Natural Science Foundation of China under Grants 61975091,61905015,61575108,and 61505034by the Tsinghua Precision Medicine Foundation and“Bio-Brain+X”Advanced Imaging Instrument Development Seed Grant.
文摘In this paper,we present a distal-scanning common path probe for optical coherence tomography(OCT)equipped with a hollow ultrasonic motor and a simple and specially designed beam-splitter.This novel probe proves to be able to effectively circumvent polarization and dispersion mismatch caused by fiber motion and is more robust to a variety of interfering factors during the imaging process,experimentally compared to a conventional noncommon path probe.Furthermore,our design counteracts the attenuation of backscattering with depth and the fall-off of the signal,resulting in a more balanced signal range and greater imaging depth.Spectral-domain OCT imaging of phantom and biological tissue is also demonstrated with a sensitivity of∼100dB and a lateral resolution of∼3μm.This low-cost probe offers simplified system configuration and excellent robustness,and is therefore particularly suitable for clinical diagnosis as one-off medical apparatus.
文摘A simple procedure is described for the HPLC and UV determination of tea saponin in tea seed oil. Determinate was accomplished with UV wavelength detection 550 nm for saponification sample, and HPLC was done under conditions: C18 analytical column of TC-C18, 4. 6 × 250 mm, column temperature at room temperature, injected sample volume was 10 μL, mobile phase’s methanol, flow-rate 0.8 ml/min and detection wavelength 280 nm.
基金supported in part by the National Natural Science Foundation of China under Grant 61227807by the Ministry of Science and Technology of China under contracts 2006AA02Z472,001CB510307 and 2009CB929400+1 种基金by the Ministryof Education of China Grant 20130002110079 for Doctoral Programby the Tsinghua Initiative Scientific Research Program Grant 2013THZ02-3.
文摘Optical coherence tomography(OCT)enables in vivo imaging of port wine stains(PWS)lesions.The knowledge of vascular struct ure and epidermal thickness(ET)of PWS may aid the objectivediagnosis and optimal treatment.To obtain the structural parameters more rapidly and avoiduser intervention,an automated algorithm of energy map is introduced based on intensity andedge information to extract the skin surface using dynamic programming method.Subsequently,an averaged A-scan analysis is performed to obtain the mean ET and the relative intensity ofdermis indicating the corresponding vascular density.This approach is currently successfullyapplied in clinical diagnosis and shows promising guidance and assessment of PDT treatment.
基金This research was supported by the National Natural Science Foundation of China(61227807,61575108 and 61505034)Tsinghua Initiative Scientific Research Program(2013THZ02-3)C.L.Pan and Y.J.You were supported in part by the Ministry of Science and Technology,Taiwan,under Grant 103-2622-E-007-006-CC2 and by the National Tsing Hua University Research Program Grant 104N2711E1.C.L.Pan is also supported by the Air Force Office of Scientific Research FA2386-13-1-4086.The first three authors contribute equally to this paper。
文摘In most coherent imaging modality,speckle noise is a major cause that blurs the boundary of tissues and degrades the image contrast.By utilizing the unique properties of supercontinuum(SC)generated by noise-like pulses(NLPs)and a simple multi-frame averaging technique,we achieved significant speckle reduction in spectral domain optical coherence tomography(SD-OCT).We quantitatively compared the speckle of our proposed method with those of conventional swept source OCT(SS-OCT)and SD-OCT based on commercial light sources.The experimental results show that SC pumped by NLPs combined with noncoherent averaging method achieves better denoising performance in terms of contrast to noise ratio(CNR).
基金This work was supported by the Social Science Project of the 13th Five-Year Plan of Jilin Provincial Department of Education under Grant no.JJKH20200635SKthe 2019 Vocational Education and Adult Education Teaching Reform Research Project of Jilin Provincial Department of Education under Grant nos.2019ZCZ067,2019ZCY413 and 2019ZCY414.
文摘In the process of Higher Vocational classified examination enrollment reform,Jilin Province has adopted a diversified examination enrollment model and“cultural quality test+vocational skill test”evaluation method,and established the“vocational education college entrance examination”system.This paper analyzes the important role and practical difficulties of“vocational skill test”in Higher Vocational classified examination,studies the existing problems,and puts forward to reasonably divide the proportion of“cultural quality test”and“vocational skill test”,sets diversified admission standards,scientifically sets up the assessment methods and contents of“vocational skill test”,further improves the“cultural quality test+vocational skill test”evaluation method and builds a classified examination and enrollment system more in line with the characteristics of vocational education.
基金the financial support from the National Natural Science Foundation of China(No.21472159)the Natural Science Foundation of Guangdong Province(No.2018A0303130021)+2 种基金the Guangdong Basic and Applied Basic Research Funds(No.2021A1515012023)Fundamental Research Funds for the Central Universities(Nos.21620318 and 2019QNGG22)the Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications(No.2020B121201005).
文摘A highly efficient,transition-metal-and light-free approach to polyheterocycles via regioselective cascade radical cyclization is developed.The redox-neutral protocol has a broad substrate scope with good functional group tolerance and probably undergoes a SET process,which is initiated by catalytic amounts of quinone in combination with 2.0 equiv.of Cs_(2)CO_(3).
文摘Formic acid oxidation is an important electrocatalytic reaction in proton- exchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCO0* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/ activation towards improved electrocatalytic performance.
基金supported by the National Key R&D Program of China (2017YFA0207301)the National Natural Science Foundation of China (21622107, 11621063, U1532265)+2 种基金the Key Research Program of Frontier Sciences (QYZDY-SSW-SLH011), the Youth Innovation Promotion Association CAS (2016392)the Fundamental Research Funds of Central University (WK2340000075)the Major Program of Development Foundation of Hefei Center for Physical Science and Technology (2017FXZY003)
文摘Atomically dispersed metal has gained much attention because of the new opportunities they offer in catalysis. However, it is still crucial to understand the mechanism of single-atom catalysis at molecular level for expanding them to other more difficult catalytic reactions, such as ammonia synthesis from nitrogen. In fact, developing ammonia synthesis under ambient conditions to overcome the high energy consumption in well-established Haber-Bosch process has fascinated scientists for many years.Herein, we demonstrate that single Cu atom yields facile valence-electron isolation from the conjugated π electron cloud of p-CN. Electron spin resonance measurements reveal that these isolated valence electrons can be easily excited to generate free electrons under photo-illumination, thus inducing high efficient photo-induced ammonia synthesis under ambient conditions.The NH_3 producing rate of copper modified carbon nitride(Cu-CN) reached 186 μmol g^(-1) h^(-1) under visible light irradiation with the quantum efficiency achieved 1.01% at 420 nm monochromatic light. This finding surely offers a model to open up a new vista for the ammonia synthesis at gentle conditions. The introduction of single atom to isolate the valence electron also represents a new paradigm for many other photocatalytic reactions, since the most photoinduced processes have been successfully exploited sharing the same origin.
文摘To fully realize the commercial viability of Pt in fuel cells, the usage of scarce Pt must be reduced while the activity and durability in 02 reduction reaction (ORR) must be enhanced. Here we report a metallic stack design achieving these goals for ORR, based on atomically precise materials synthesis. Au@Pd@Pt nanostructures with atomically thin Pt shells and high-index surfaces form an excellent platform for integrating the effects of electronic structures, surface facets, and substrate stabilization to boost ORR performance. Au@Pd@Pt trisoctahedrons (TOH) achieve mass activity 6.1 times higher than that of commercial Pt/C and dramatically enhanced durability beyond 1.0 V vs. a reversible hydrogen electrode in oxidation potential. Meanwhile, Pt comprises only 3.2% of the nanostructures. To further improve the ORR activity and demonstrate the versatility of our strategy, we implement the same design in PtNi alloy electrocatalysts. The Au@Pd@PtNi TOHs exhibit mass activity 14.3 times higher than that of commercial Pt/C as well as excellent durability. This work demonstrates an alternative strategy for fabricating high-performance and low-cost catalysts, and highlights the importance of simultaneous surface and interfacial engineering with atomic precision in designing catalysts.
文摘Cathodic oxygen reduction reaction (ORR) is a highly important electrochemical reaction in renewable-energy technologies. In general, the surface area, exposed facets and electrical conductivity of catalysts all play important roles in determining their electrocatalytic activities, while their performance durability can be improved by integration with supporting materials. In this work we have developed a method to synthesize hybrid structures between PtPd bimetallic nanocages and graphene by employing selective epitaxial growth of single-crystal Pt shells on Pd nanocubes supported on reduced graphene oxide (rGO), followed by Pd etching. The hollow nature, {100} surface facets and bimetallic composition of PtPd nanocages, together with the good conductivity and stability of graphene, enable high electrocatalytic performance in ORR. The obtained PtPd nanocage-rGO structures exhibit mass activity (0.534 A.m-1) and which are 4.4 times and 3.9 times greater than the specific activity (0.482 mA-cm-2) corresponding values for Pt/C.
基金supported in part by National Key R&D Program of China (2017YFA0207301)the National Natural Science Foundation of China (21725102, 21471141, U1532135, 21601173)+3 种基金CAS Key Research Program of Frontier Sciences (QYZDB-SSW-SLH018)CAS Interdisciplinary Innovation Team, Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology (2016FXCX003)Anhui Provincial Natural Science Foundation (1608085QB24)Chinese Universities Scientific Fund(WK2310000067)
文摘Supports are commonly implemented in the industrial application of heterogeneous catalysts to improve the stability and recyclability of catalysts.The supported catalysts often show the enhanced activity and selectivity in various catalytic reactions.However,the specific contributions of electronic and steric effects to a catalytic system often remain elusive due to the lack of well-defined model systems.In this work,two types of uniform Pd nanocrystals covered by{111}facets in tetrahedral and octahedral shapes,respectively,are synthesized with identical chemical environment and loaded on Ti O_2supports to form hybrid structures(Pd{111}-Ti O_2)towards the application of formic acid decomposition.Our observation suggests that the polarization effect at the interface of Pd-Ti O_2enhances its activity in formic acid decomposition.Moreover,the Pd tetrahedrons-Ti O_2hybrid structure whose Pd{111}-Ti O_2interface possesses a larger angle shows higher catalytic activity,owing to the reduced steric effect as compared to Pd octahedrons-Ti O_2.This study reveals the nature of interface effects in formic acid decomposition,and provides a guidance for the related catalyst design.
基金financially supported in part by National Key R&D Program of China(Nos.2020YFA0406103,2017YFA0207301)National Natural Science Foundation of China(Nos.21725102,91961106,U1832156,22075267,21803002)+4 种基金Science and Technological Fund of Anhui Province for Outstanding Youth(No.2008085J05)Youth Innovation Promotion Association of CAS(No.2019444)Young Elite Scientist Sponsorship Program by CAST,MOST(No.2018YFA0208603)Users with Excellence Program of Hefei Science Center CAS(No.2020HSC-UE003)Postdoc Matching Fund Scheme of the Hong Kong Polytechnic University(No.1-W144)。
文摘Anodic oxygen evolution reaction(OER)is the key bottleneck for water electrolysis technique owing to its sluggish reaction kinetics.Interfacial engineering on the rationally designed heterostructure can regulate the electronic states efficiently for intrinsic activity improvement.Here,we report a co-phosphorization approach to construct a VPO_(4)-Ni_(2)P heterostructure on nickel foam with strongly chemical binding,wherein phosphate acts as electronic modifier for Ni_(2)P electrocatalyst.Profiting from the interfacial interaction,it is uncovered that electron shifts from Ni_(2)P to VPO_(4)to render valence increment in Ni species.Such an electronic manipulation rationalizes the chemical affinities of various oxygen intermediates in OER pathway,giving a substantially reduced energy barrier.As a result,the advanced VPO_(4)-Ni_(2)P heterostructure only requires an overpotential of 289 mV to deliver a high current density of 350 mA/cm^(2)for OER in alkaline electrolyte,together with a Tafel slope as low as 28 mV/dec.This work brings fresh insights into interfacial engineering for advanced electrocatalyst design.
基金supported by National Key R&D Program of China (Nos.2017YFA0207301,2017YFA0207302)the National Natural Science Foundation of China (NSFC,Nos.21725102,21601173, U1832156,21881240040,21573212)+3 种基金CAS Key Research Program of Frontier Sciences (No.QYZDB-SSW-SLH018)CAS Interdisciplinary Innovation Team,and Chinese Universities Scientific Fund (No. WK2310000067)funded by Chinese Academy of Sciences President’s International Fellowship Initiative (No. 2019PC0114)support from USTC Center for Microand Nanoscale Research and Fabrication
文摘Efficient catalytic system with low energy consumption exhibits increasing importance due to the upcoming energy crisis.Given this situation,it should be an admirable strategy for reducing energy input by effectively utilizing incident solar energy as a heat source during catalytic reactions.Herein,aza-fused7 r-conjugated microporous polymer(aza-CMP)with broad light absorption and high photothermal conversion efficiency was synthesized and utilized as a support for bimetallic AuPd nanocatalysts in light-driven benzyl alcohol oxidation.The AuPd nanoparticles anchored on aza-CMP(aza-CM P/Au_xPdy)exhibited excellent catalytic performance for benzyl alcohol oxidation under 50 mW/cm^2 light irradiation.The improved catalytic performance by the aza-CMP/Au_xPdy is attributed to the unique photothermal effect induced by aza-CMP,which can promote the catalytic benzyl alcohol oxidation occurring at Au Pd.This work presents a novel approach to effectively utilize solar energy for conventional catalytic reactions through photothermal effect.
文摘Imposing phase engineering to porous materials is promising to realize outperforming electrocatalytic performances by taking advantages of the merits of porous nanoarchitecture and heterophase structure.In this work,amorphous/crystalline ruthenium oxide(RuO_(2))porous particles with rationally regulated heterophases are successfully prepared by integrating the phase engineering into the porous material synthesis.The resultant defect-rich amorphous/crystalline RuO_(2)porous particles exhibit excellent electrocatalytic performance toward the oxygen evolution reaction,achieving a low overpotential of 165 mV at a current density of 10 mA·cm^(−2)and a high mass activity up to 133.8 mA·cm^(-2)at a low overpotential of 200 mV.This work indicates that the synergistic effect of amorphous/crystalline heterophase and porous structural characteristics enables RuO_(2)to trigger a superior electrocatalytic activity.
基金supported by the“Fundamental Research Funds for the Central Universities”(Nos.21620318,2019QNGG22)“the Open Fund of Guangdong Provincial Key Laboratory of Functional Supramolecular Coordination Materials and Applications”(No.2020B121201005).
文摘A low-cost manganese-catalyzed oxidant-free selective C–H acylation of indole with ketene is reported.This protocol features mild reaction conditions and good functional group tolerance.The yield is from middle to excellent.The acylation products can be further converted to diverse useful compounds.Mechanism study reveals the acylation transformation possibly undergoes a cyclomanganated complex species as reactive intermediate.
基金This work was financially supported by National Key R&D Program of China(Nos.2019YFA0210004 and 2017YFA0207301)the National Natural Science Foundation of China(Nos.21975242 and 21890754)+5 种基金the Strategic Priority Research Program of Chinese Academy of Sciences(No.XDB36000000)Youth Innovation Promotion Association of CAS(No.CX2340007003)Major Program of Development Foundation of Hefei Center for Physical Science and Technology(No.2020HSC-CIP003)Key Research Program of Frontier Sciences of CAS(No.QYZDYSSW-SLH011)the Fok Ying-Tong Education Foundation(No.161012)Supercomputing USTC and National Supercomputing Center in Shenzhen are acknowledged for computational support.
文摘Photooxidation provides a promising strategy for removing the dominant indoor pollutant of HCHO,while the underlying photooxidation mechanism is still unclear,especially the exact role of H2O molecules.Herein,we utilize in-situ spectral techniques to unveil the H2O-mediated HCHO photooxidation mechanism.As an example,the synthetic defective Bi2WO6 ultrathin sheets realize high-rate HCHO photooxidation with the assistance of H2O at room temperature.In-situ electron paramagnetic resonance spectroscopy demonstrates the existence of•OH radicals,possibly stemmed from H2O oxidation by the photoexcited holes.Synchrotron-radiation vacuum ultraviolet photoionization mass spectroscopy and H218O isotope-labeling experiment directly evidence the formed•OH radicals as the source of oxygen atoms,trigger HCHO photooxidation to produce CO2,while in-situ Fourier transform infrared spectroscopy discloses the HCOO*radical is the main photooxidation intermediate.Density-functional-theory calculations further reveal the•OH formation process is the rate-limiting step,strongly verifying the critical role of H2O in promoting HCHO photooxidation.This work first clearly uncovers the H2O-mediated HCHO photooxidation mechanism,holding promise for high-efficiency indoor HCHO removal at ambient conditions.