Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by ...Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by scanning electron microscopy,X-ray diffraction,N2 adsorption,X-ray photoelectron spectroscopy,UV-visible spectroscopy,and electrochemical impedance spectroscopy. Their photocatalytic activity was evaluated using the photocatalytic reduction of CO2. The N-doped TiO 2 sample exhibited a much higher visible light photocatalytic activity for CO2 reduction than its precursor TiN and commercial TiO 2（P25）. This was due to the synergistic effect of the formation of surface heterojunctions on the TiO 2 microsheet surface,enhanced visible light absorption by nitrogen-doping,and surface fluorination.展开更多
α‐,β‐,δ‐,andγ‐MnO2nanocrystals are successfully prepared.We then evaluated the NH3selective catalytic reduction(SCR)performance of the MnO2catalysts with different phases.The NOx conversion efficiency decrease...α‐,β‐,δ‐,andγ‐MnO2nanocrystals are successfully prepared.We then evaluated the NH3selective catalytic reduction(SCR)performance of the MnO2catalysts with different phases.The NOx conversion efficiency decreased in the order:γ‐MnO2>α‐MnO2>δ‐MnO2>β‐MnO2.The NOx conversion with the use ofγ‐MnO2andα‐MnO2catalysts reached90%in the temperature range of140–200°C,while that based onβ‐MnO2reached only40%at200°C.Theγ‐MnO2andα‐MnO2nanowire crystal morphologies enabled good dispersion of the catalysts and resulted in a relatively high specific surface area.We found thatγ‐MnO2andα‐MnO2possessed stronger reducing abilities and more and stronger acidic sites than the other catalysts.In addition,more chemisorbed oxygen existed on the surface of theγ‐MnO2andα‐MnO2catalysts.Theγ‐MnO2andα‐MnO2catalysts showed excellent performance in the low‐temperature SCR of NO to N2with NH3.展开更多
Obtaining a detailed understanding of the surface modification of supports is crucial;however,it is a challenging task for the development and large-scale fabrication of supported electrocatalysts that can be used as ...Obtaining a detailed understanding of the surface modification of supports is crucial;however,it is a challenging task for the development and large-scale fabrication of supported electrocatalysts that can be used as alternatives to Pt-based catalysts for the oxygen reduction reaction(ORR).In this study,commercial silicon carbide(SiC)was modified through surface oxidization(O-SiC)to support the use of Pd nanoparticles(Pd NPs)as electrocatalysts for ORR.The obtained Pd/O-SiC catalysts exhibited better ORR activity,stronger durability,and higher resistance to methanol poisoning than that exhibited by commercial Pt/C.The role of the support in enhancing the ORR performance,especially the oxidization of SiC surfaces,was discussed in detail based on the experimental characterizations and density functional theory calculations.The underlying mechanism of the superior ORR performance of Pd/O-SiC catalysts was attributed to the charge transfer from SiC_(x)O_(y)to Pd NPs on the surfaces of SiC and the strong metal–support interactions(SMSIs)between Pd and SiC_(x)O_(y).The charge transfer enhanced the ORR activity by inducing electron-rich Pd,increased the adsorption of the key intermediate OOH,and decreased the Gibbs free energy of the critical ORR step.Furthermore,SMSIs enhanced the ORR stability of the Pd/O-SiC catalyst.This study provided a facile route for designing and developing highly active Pd-based ORR electrocatalysts.展开更多
A series of Co–Cr–O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane.The reaction behaviors are closely related to the structural features of the mixed oxi...A series of Co–Cr–O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane.The reaction behaviors are closely related to the structural features of the mixed oxides.The catalyst with a Co/Cr molar ratio of 1:2(1 Co2 Cr)and a spinel structure has the best activity(with a reaction rate of 1.38μmol g^–1 s^–1 at 250℃),which is attributed to the synergistic roles of its high surface acidity and good low-temperature reducibility,as evidenced by the temperature-programmed desorption of ammonia,reduction of hydrogen,and surface reaction of propane.Kinetic study shows that the reaction orders of propane and oxygen on the 1 Co2 Cr catalyst(0.58±0.03 and 0.34±0.05,respectively)are lower than those on the 2 Co1 Cr catalyst(0.77±0.02 and 0.98±0.16,respectively)and 1 Co5 Cr(0.66±0.05 and 1.30±0.11,respectively),indicating that the coverages of propane and oxygen on 1 Co2 Cr are higher than those on the other catalysts due to its higher surface acidity and higher reducibility.In addition,in-situ diffuse reflectance infrared spectroscopic investigation reveals that the main surface species on 1 Co2 Cr during the reaction are polydentate carbonate species,which accumulate on the surface at low temperatures(<250℃)but decompose at relatively high temperatures.展开更多
Atomic layer deposition(ALD)attracts great attention nowadays due to its ability for designing and modifying catalytic systems at the molecular level.There are several reported review papers published recently discuss...Atomic layer deposition(ALD)attracts great attention nowadays due to its ability for designing and modifying catalytic systems at the molecular level.There are several reported review papers published recently discussing this technique in catalysis.However,the mechanism on how the deposited materials improve the catalyst stability and tune the reaction selectivity is still unclear.Herein,catalytic systems created via ALD on stepwise preparation and/or modification under self-limiting reaction conditions are summarized.The effects of deposited materials in terms of electronic/geometry modification over the catalytic nanoparticles(NPs)are discussed.These effects explain the mechanism of the catalytic stability improvement and the selectivity modification.The unique properties of ALD for designing new catalytic systems are further investigated for building up photocatalytic reaction nanobowls,tandem catalyst and bi-active-component metallic catalytic systems.展开更多
The development of active and durable non-Pt electrocatalysts with well-defined microstructure is of great importance to both fuel cell applications and fundamental understanding.Herein,we report a surface-doping proc...The development of active and durable non-Pt electrocatalysts with well-defined microstructure is of great importance to both fuel cell applications and fundamental understanding.Herein,we report a surface-doping process to prepare well-defined W-doped Pd nanocubes with a tunable atomic percent of W from 0 to 1.5%by using the Pd nanocubes as seeds.The obtained 1.2%W-doped Pd nanocubes/C exhibited greatly enhanced electrocatalytic performance toward oxygen reduction reaction in alkaline media,presenting an enhancement factor of 4.7 in specific activity and 2.5 in mass activity compared to the activity of a commercial Pt/C catalyst.The downshift of the d-band center due to a negative charge transfer from W to Pd intrinsically accounts for such improvement in activity by weakening the adsorption of reaction intermediates.Also,the 1.2%W-doped Pd nanocubes/C showed superior catalytic properties for the ethanol oxidation reaction,showing great potential for serving as a bifunctional electrocatalyst in fuel cells.展开更多
In this paper, the surface of the carbon graphite working electrode has been modified using pyrimethamine/2-sulfanilamido-3-methoxypyrazine （metakelfin） and lumefantrine/artemeter （coartem）-potent antimalarials. T...In this paper, the surface of the carbon graphite working electrode has been modified using pyrimethamine/2-sulfanilamido-3-methoxypyrazine （metakelfin） and lumefantrine/artemeter （coartem）-potent antimalarials. The electrochemical profiles of the surface modified electrodes have been studied using cyclic voltammetry. The results indicate that the metakelfin and lumefantrine/artemeter （coartem） have redox active moieties with the oxidation and reduction peaks for pyrimethamine/2-sulfanilamido-3-methoxypyrazine （metakelfin） modified electrode occurring at 0.510 V and 0.315 V, and that for lumefantrine/artemeter （coartem） occurring at 0.510 V and 0.300 V. Bentonite, a clay montmorrilonite with octahedral and tetrahedral sites which can undergo isomorphous substitution and other interactions was also used modify the electrode surface. The bentonite modified electrode was then used to study metakelfin and lumefantrine/artemeter （coartem）. It was observed that the redox properties of metakelfin and lumefantrine/artemeter （coartem） did not change significantly on the bentonite host matrix. It was observed that the redox activity of artemeter was totally inhibited on the bentonite matrix. Interaction of pyrimethamine/2-sulfanilamido-3-methoxypyrazine （metakelfin） and lumefantrine/artemeter （coartem） modified electrodes with selected biomolecules （methionine, arginine, leucine, tyrosine）, isonicotinic acid and acetyl salicyclic acid is also reported.展开更多
Electrocatalytic CO_(2) reduction has attracted growing attention as a promising route to realize artificial carbon recycling.Proton transfer plays an essential role in CO_(2) reduction and dramatically impacts produc...Electrocatalytic CO_(2) reduction has attracted growing attention as a promising route to realize artificial carbon recycling.Proton transfer plays an essential role in CO_(2) reduction and dramatically impacts product distribution.However,the precise control of proton transfer during CO_(2) reduction remains challenging.In this study,we present a well-controlled proton transfer through the modification of several purines with similar molecular structures,and reveal a direct correlation between surface proton transfer capability and CO_(2) reduction selectivity over Cu electrode.With a moderate proton transfer capability,the guanine modification can remarkably boost CH_(4) production and suppress C2 products formation.In-situ ATR-SEIRAS suggests a weakened^(*)CO intermediate adsorption and a relatively low local pH environment after the guanine modification,which facilitates the^(*)CO protonation and detachment for CH_(4) generation.展开更多
Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which...Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which include thermal and chemical reduction with ethylene glycol, KOH and Fe powder. The changes in microstructure and surface chemistry of RGOs were extensively characterized by SEM, TEM, AFM, XRD, XPS and Raman spectrum. The results show that significant exfoliation occurs during oxidation and is retained in reduction processes, along with the formation of curled wavy morphology. Compared with large d spacing(0.852 nm) of graphene oxide(GO), the(002) plane distance decreases to 0.358-0.384 nm of RGOs, indicating efficient tuning of surface functionalities through mild reduction methods. The ID/IG ratio of RGOs is about 1.0-1.15, indicating that reconstructed sp^2 domains have smaller sizes and larger quantity. The content of sp^2 bonded C in GO(36.93%, molar fraction) increases to 45.48%-72.92%(molar fraction) in RGOs, along with a drastic decrease in hydroxyl and epoxy and minor changes in carbonyl and carboxyl. Thermal reduction or chemical reduction produces RGOs with residual functionalities, which may render different chemical activity and is desirable in various applications.展开更多
The application of naive Koutecky-Levich analysis to micro- and nano-particle modified rotating disk electrodes of partially covered and non-planar geometry is critically analysed. Assuming strong overlap of the diffu...The application of naive Koutecky-Levich analysis to micro- and nano-particle modified rotating disk electrodes of partially covered and non-planar geometry is critically analysed. Assuming strong overlap of the diffusion fields of the particles such that transport to the entire surface is time-independent and one-dimensional, the observed voltammetric response reflects an apparent electrochemical rate o constant koapp, equal to the true rate constant ko describing the redox reaction of interest on the surface of the nanoparticles and the ratio,ψ, of the total electroactive surface area to the geometric area of the rotating disk surface. It is demonstrated that Koutecky-Levich analysis is applicable and yields the expected plots of I-1 versus ω-1 where I is the current and ω is the rotation speed but that the values of the electrochemical rate constants inferred are thereof koapp, not ko. Thus, for ψ 〉 1 apparent electrocatalysis might be naively but wrongly inferred whereas for ψ 〈 1 the deduced electrochemical rate constant will be less than ko. Moreover, the effect of ψ on the observed rotating disk electrode voltammograms is significant, signalling the need for care in the overly simplistic application of Koutecky-Levich analysis to modified rotating electrodes, as is commonly applied for example in the analysis of possible oxygen reduction catalysts.展开更多
An efficient photocatalytic CO_(2) reduction has been reported in ZIF-67-derived-Co nanoparticles(NPs)encapsulated in nitrogen-doped carbon layers(N-C/Co).This work demonstrates that the pyrolysis temperature is cruci...An efficient photocatalytic CO_(2) reduction has been reported in ZIF-67-derived-Co nanoparticles(NPs)encapsulated in nitrogen-doped carbon layers(N-C/Co).This work demonstrates that the pyrolysis temperature is crucial in tuning the grain size and components of metallic Co^(0) of N-C/Co composite catalysts,which optimizes their photocatalytic activities.Syntheses were conducted at 600,700,and 800℃ giving the N-C/Co-600,N-C/Co-700,and N-C/Co-800 samples,respectively.N-C layers can well wrap the Co NPs obtained at a low pyrolysis temperature(600℃)owing to their smaller grains than those of other samples.A high metallic Co^(0) content in the N-C/Co-600 sample can be attributed to the effective inhibition of surface oxidation.By contrast,the surface CoOx oxides in the N-C/Co-700 and N-C/Co-800 samples cover inside Co cores,inhibiting charge separation and transfer.As a result,the N-C/Co-600 sample yields the best photocatalytic activity.The carbon monoxide and hydrogen generation rates are as high as 1.62×10^(4) and 2.01×10^(4)μmol g^(−1)h^(−1),respectively.Additionally,the Co NPs make composite catalysts magnetic,enabling rapid and facile recovery of catalysts with the assistance of an external magnetic field.This work is expected to provide an instructive guideline for designing metal-organic framework-derived carbon/metal composite catalysts.展开更多
Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on...Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on-Pt and Ni Ox-on-Pt catalysts and their activity to CO oxidation reactions using both model catalysts and supported nanocatalysts.Although the active Fe O1x structure is stabilized on the Pt surface in a reductive reaction atmosphere,it is prone to change to an Fe O2x structure in oxidative reaction gases and becomes deactivated.In contrast,a Ni O1x surface structure supported on Pt is stable in both reductive and oxidative CO oxidation atmospheres.Consequently,CO oxidation over the Ni O1x-on-Pt catalyst is further enhanced in the CO oxidation atmosphere with an excess of O2.The present results demonstrate that the stability of the active oxide surface phases depends on the stabilization effect of the substrate surface and is also related to whether the oxide exhibits a variable oxidation state.展开更多
By reference of the δ18O and δ13C isotopic compositions of G.sacculifer and accelerator mass spectrometry (AMS)14C dates, the U K 37 , ∑C – 21 /∑C +- 22 and Pr/Pn in core DGKS9603 have been used to characterize t...By reference of the δ18O and δ13C isotopic compositions of G.sacculifer and accelerator mass spectrometry (AMS)14C dates, the U K 37 , ∑C – 21 /∑C +- 22 and Pr/Pn in core DGKS9603 have been used to characterize the changes of paleooceanographic environment occurring in the East China Sea (ECS) during the last 35000 years. The stratigraphic records of these proxies have shown that during the last 35 ka the Okinawa Trough has gone through 7 stronger cold-climate events (C1–C7) and 9 terrigenous matter-decreasing events (e2–e9), of which, the C1 corresponds to the cold episode occurring in the middle late Holocene, C2–C4 and C7 correspond to the H1–H4 events, respectively. e1 and e3–e8 correspond to the decrease of sea surface temperature (SST), respectively. The terrigenous inputs increased when Heinrich events occurred. Climate colding resulted in the decrease of terrigenous matter transported by rivers, and the increase of that transported by winter monsoon. Heinrich events are closely related to East Asia monsoon. During the Last Glacial Maximum (LGM, 15.5–25.8 Cal ka BP), reduction environment fluctuated strongly, bringing forth three stronger reduction events (R1–R3) and one weaker reduction event (O), of which, R1–R3 correspond to the decrease of SST and increase of terrigenous nutrient and O corresponds to the decrease of terrigenous nutrient. The fluctuation of reduction condition must be related to the change of sea surface productivity.展开更多
Au nanoclusters （AuNCs） hold tremendous potential to be employed in a wide variety of biological applications. Despite the rapid development in the field of NCs synthesis, a comprehensive understanding of how cells ...Au nanoclusters （AuNCs） hold tremendous potential to be employed in a wide variety of biological applications. Despite the rapid development in the field of NCs synthesis, a comprehensive understanding of how cells interact with this class of ultra-small nanoparticles （〈2 nm） having defined sizes and surface chemistry, remains poorly understood. In this study, we show that the choice of the surface ligand used to protect AuNCs can significantly perturb cellular uptake and intracellular redox signaling. A panel of monodisperse, atomically precise AuNCs with different core Au atom number （i.e., Auls, Au18 and Au25） protected with either mercaptopropionic acid （MPA） or glutathione （GSH） capping agent were synthesized and their effects on the generation of intracellular reactive oxygen species （ROS）, cytotoxicity and genotoxicity of the NCs were assessed. Both mitochondrial superoxide anion （O2^-） and cytoplasmic ROS were found to be higher in cells exposed to MPA but not GSH capped AuNCs. The unregulated state of intracellular ROS is correlated to the amount of internalized AuNCs. Interestingly, MPA-AuNCs induction of ROS level did not lead to any detrimental cellular effects such as cell death or DNA damage. Instead, it was observed that the increase in redox status corresponded to higher cellular metabolism and proliferative capacity. Our study illustrates that surface chemistry of AuNCs plays a pivotal role in affecting the biological outcomes and the new insights gained will be useful to form the basis of defining specific design rules to enable rational engineering of ultra-small complex nanostructures for biological applications.展开更多
Based on the analysis of tin penetration mechanism in the float glass process, the oxidation model of stannous ion is constructed considering the oxygen activity and the redox reaction in the glass surface layer. The ...Based on the analysis of tin penetration mechanism in the float glass process, the oxidation model of stannous ion is constructed considering the oxygen activity and the redox reaction in the glass surface layer. The calculation of stannous ion's oxidation rate makes it possible to predict both stannous and stannic ion's concentrations independently. And it is also the necessary precondition for the numerical verification of tin penetration mechanism. Coupled diffusion simulation method is established to simulate the penetration process of both stannous and stannic ions simultaneously. The result shows that when the green glass is formed in the reducing atmosphere in tin bath, the stannic ion is accumulated at the position where oxygen activity changes sharply. Satellite peak (internal local concentration maximum) occurs in the tin concentration profile of green glass, which is quite different from that in low iron glass. Compared with gradually cooling temperature regulation, the tin penetrated shifts to greater depth and the depth and magnitude of the satellite peak also increase when reheating temperature regulation is applied. In order to reduce the amount of penetrated tin, the residual time in the high temperature region should be shortened.展开更多
基金supported by the National Natural Science Foundation of China (21073088)the Specialized Research Fund for the Doctoral Program of Higher Education (200802841038)+1 种基金the National Basic Research Program of China (2005CB221400)the Fundamental Research Funds for the Central Universities~~
基金supported by the National Basic Research Program of China(973 Program2013CB632402)+7 种基金the National Natural Science Foundation of China(513201050015137219051402025and 21433007)the Natural Science Foundation of Hubei Province(2015CFA001)the Fundamental Research Funds for the Central Universities(WUT:2014-VII-010)the Self-Determined and Innovative Research Funds of State Key Laboratory of Advanced Technology for Material Synthesis and ProcessingWuhan University of Technology(2013-ZD-1)~~
文摘Nitrogen-doped anatase TiO 2 microsheets with 65%（001） and 35%（101） exposed faces were fabricated by the hydrothermal method using TiN as precursor in the presence of HF and HCl. The samples were characterized by scanning electron microscopy,X-ray diffraction,N2 adsorption,X-ray photoelectron spectroscopy,UV-visible spectroscopy,and electrochemical impedance spectroscopy. Their photocatalytic activity was evaluated using the photocatalytic reduction of CO2. The N-doped TiO 2 sample exhibited a much higher visible light photocatalytic activity for CO2 reduction than its precursor TiN and commercial TiO 2（P25）. This was due to the synergistic effect of the formation of surface heterojunctions on the TiO 2 microsheet surface,enhanced visible light absorption by nitrogen-doping,and surface fluorination.
基金supported by the National Natural Science Foundation of China(51502221)~~
文摘α‐,β‐,δ‐,andγ‐MnO2nanocrystals are successfully prepared.We then evaluated the NH3selective catalytic reduction(SCR)performance of the MnO2catalysts with different phases.The NOx conversion efficiency decreased in the order:γ‐MnO2>α‐MnO2>δ‐MnO2>β‐MnO2.The NOx conversion with the use ofγ‐MnO2andα‐MnO2catalysts reached90%in the temperature range of140–200°C,while that based onβ‐MnO2reached only40%at200°C.Theγ‐MnO2andα‐MnO2nanowire crystal morphologies enabled good dispersion of the catalysts and resulted in a relatively high specific surface area.We found thatγ‐MnO2andα‐MnO2possessed stronger reducing abilities and more and stronger acidic sites than the other catalysts.In addition,more chemisorbed oxygen existed on the surface of theγ‐MnO2andα‐MnO2catalysts.Theγ‐MnO2andα‐MnO2catalysts showed excellent performance in the low‐temperature SCR of NO to N2with NH3.
文摘Obtaining a detailed understanding of the surface modification of supports is crucial;however,it is a challenging task for the development and large-scale fabrication of supported electrocatalysts that can be used as alternatives to Pt-based catalysts for the oxygen reduction reaction(ORR).In this study,commercial silicon carbide(SiC)was modified through surface oxidization(O-SiC)to support the use of Pd nanoparticles(Pd NPs)as electrocatalysts for ORR.The obtained Pd/O-SiC catalysts exhibited better ORR activity,stronger durability,and higher resistance to methanol poisoning than that exhibited by commercial Pt/C.The role of the support in enhancing the ORR performance,especially the oxidization of SiC surfaces,was discussed in detail based on the experimental characterizations and density functional theory calculations.The underlying mechanism of the superior ORR performance of Pd/O-SiC catalysts was attributed to the charge transfer from SiC_(x)O_(y)to Pd NPs on the surfaces of SiC and the strong metal–support interactions(SMSIs)between Pd and SiC_(x)O_(y).The charge transfer enhanced the ORR activity by inducing electron-rich Pd,increased the adsorption of the key intermediate OOH,and decreased the Gibbs free energy of the critical ORR step.Furthermore,SMSIs enhanced the ORR stability of the Pd/O-SiC catalyst.This study provided a facile route for designing and developing highly active Pd-based ORR electrocatalysts.
基金financially supported by the National Natural Science Foundation of China(21773212,21872124)~~
文摘A series of Co–Cr–O mixed oxides with different Co/Cr molar ratios are synthesized and tested for the total oxidation of propane.The reaction behaviors are closely related to the structural features of the mixed oxides.The catalyst with a Co/Cr molar ratio of 1:2(1 Co2 Cr)and a spinel structure has the best activity(with a reaction rate of 1.38μmol g^–1 s^–1 at 250℃),which is attributed to the synergistic roles of its high surface acidity and good low-temperature reducibility,as evidenced by the temperature-programmed desorption of ammonia,reduction of hydrogen,and surface reaction of propane.Kinetic study shows that the reaction orders of propane and oxygen on the 1 Co2 Cr catalyst(0.58±0.03 and 0.34±0.05,respectively)are lower than those on the 2 Co1 Cr catalyst(0.77±0.02 and 0.98±0.16,respectively)and 1 Co5 Cr(0.66±0.05 and 1.30±0.11,respectively),indicating that the coverages of propane and oxygen on 1 Co2 Cr are higher than those on the other catalysts due to its higher surface acidity and higher reducibility.In addition,in-situ diffuse reflectance infrared spectroscopic investigation reveals that the main surface species on 1 Co2 Cr during the reaction are polydentate carbonate species,which accumulate on the surface at low temperatures(<250℃)but decompose at relatively high temperatures.
基金supported by the U.S. Department of Energy, Office of Science, and Office of the Basic Energy Sciences, under Contract DE-AC-02-06CH11357~~
文摘Atomic layer deposition(ALD)attracts great attention nowadays due to its ability for designing and modifying catalytic systems at the molecular level.There are several reported review papers published recently discussing this technique in catalysis.However,the mechanism on how the deposited materials improve the catalyst stability and tune the reaction selectivity is still unclear.Herein,catalytic systems created via ALD on stepwise preparation and/or modification under self-limiting reaction conditions are summarized.The effects of deposited materials in terms of electronic/geometry modification over the catalytic nanoparticles(NPs)are discussed.These effects explain the mechanism of the catalytic stability improvement and the selectivity modification.The unique properties of ALD for designing new catalytic systems are further investigated for building up photocatalytic reaction nanobowls,tandem catalyst and bi-active-component metallic catalytic systems.
基金supported by Collaborative Innovation Center of Suzhou Nano ScienceTechnology, MOST of China (2014CB932700)+5 种基金the National Natural Science Foundation of China (21603208, 21573206)Key Research Program of Frontier Sciences of the CAS (QYZDBSSW-SLH017)Anhui Provincial Key Scientific and Technological Project (1704a0902013)Major Program of Development Foundation of Hefei Center for Physical Science and Technology (2017FXZY002)Fundamental Research Funds for the Central UniversitiesCAS-TWAS president’s fellowship~~
文摘The development of active and durable non-Pt electrocatalysts with well-defined microstructure is of great importance to both fuel cell applications and fundamental understanding.Herein,we report a surface-doping process to prepare well-defined W-doped Pd nanocubes with a tunable atomic percent of W from 0 to 1.5%by using the Pd nanocubes as seeds.The obtained 1.2%W-doped Pd nanocubes/C exhibited greatly enhanced electrocatalytic performance toward oxygen reduction reaction in alkaline media,presenting an enhancement factor of 4.7 in specific activity and 2.5 in mass activity compared to the activity of a commercial Pt/C catalyst.The downshift of the d-band center due to a negative charge transfer from W to Pd intrinsically accounts for such improvement in activity by weakening the adsorption of reaction intermediates.Also,the 1.2%W-doped Pd nanocubes/C showed superior catalytic properties for the ethanol oxidation reaction,showing great potential for serving as a bifunctional electrocatalyst in fuel cells.
文摘In this paper, the surface of the carbon graphite working electrode has been modified using pyrimethamine/2-sulfanilamido-3-methoxypyrazine （metakelfin） and lumefantrine/artemeter （coartem）-potent antimalarials. The electrochemical profiles of the surface modified electrodes have been studied using cyclic voltammetry. The results indicate that the metakelfin and lumefantrine/artemeter （coartem） have redox active moieties with the oxidation and reduction peaks for pyrimethamine/2-sulfanilamido-3-methoxypyrazine （metakelfin） modified electrode occurring at 0.510 V and 0.315 V, and that for lumefantrine/artemeter （coartem） occurring at 0.510 V and 0.300 V. Bentonite, a clay montmorrilonite with octahedral and tetrahedral sites which can undergo isomorphous substitution and other interactions was also used modify the electrode surface. The bentonite modified electrode was then used to study metakelfin and lumefantrine/artemeter （coartem）. It was observed that the redox properties of metakelfin and lumefantrine/artemeter （coartem） did not change significantly on the bentonite host matrix. It was observed that the redox activity of artemeter was totally inhibited on the bentonite matrix. Interaction of pyrimethamine/2-sulfanilamido-3-methoxypyrazine （metakelfin） and lumefantrine/artemeter （coartem） modified electrodes with selected biomolecules （methionine, arginine, leucine, tyrosine）, isonicotinic acid and acetyl salicyclic acid is also reported.
文摘Electrocatalytic CO_(2) reduction has attracted growing attention as a promising route to realize artificial carbon recycling.Proton transfer plays an essential role in CO_(2) reduction and dramatically impacts product distribution.However,the precise control of proton transfer during CO_(2) reduction remains challenging.In this study,we present a well-controlled proton transfer through the modification of several purines with similar molecular structures,and reveal a direct correlation between surface proton transfer capability and CO_(2) reduction selectivity over Cu electrode.With a moderate proton transfer capability,the guanine modification can remarkably boost CH_(4) production and suppress C2 products formation.In-situ ATR-SEIRAS suggests a weakened^(*)CO intermediate adsorption and a relatively low local pH environment after the guanine modification,which facilitates the^(*)CO protonation and detachment for CH_(4) generation.
基金Project(51274248)supported by the National Natural Science Foundation of ChinaProjects(2015DFR50580,2013DFA31440)supported by the International Scientific and Technological Cooperation Program of China
文摘Reduced graphene oxide(RGO) sheets with varied contents and types of oxygenated groups were synthesized by Hummers treatment of natural graphite powders followed by different nontoxic and mild reduction methods, which include thermal and chemical reduction with ethylene glycol, KOH and Fe powder. The changes in microstructure and surface chemistry of RGOs were extensively characterized by SEM, TEM, AFM, XRD, XPS and Raman spectrum. The results show that significant exfoliation occurs during oxidation and is retained in reduction processes, along with the formation of curled wavy morphology. Compared with large d spacing(0.852 nm) of graphene oxide(GO), the(002) plane distance decreases to 0.358-0.384 nm of RGOs, indicating efficient tuning of surface functionalities through mild reduction methods. The ID/IG ratio of RGOs is about 1.0-1.15, indicating that reconstructed sp^2 domains have smaller sizes and larger quantity. The content of sp^2 bonded C in GO(36.93%, molar fraction) increases to 45.48%-72.92%(molar fraction) in RGOs, along with a drastic decrease in hydroxyl and epoxy and minor changes in carbonyl and carboxyl. Thermal reduction or chemical reduction produces RGOs with residual functionalities, which may render different chemical activity and is desirable in various applications.
文摘The application of naive Koutecky-Levich analysis to micro- and nano-particle modified rotating disk electrodes of partially covered and non-planar geometry is critically analysed. Assuming strong overlap of the diffusion fields of the particles such that transport to the entire surface is time-independent and one-dimensional, the observed voltammetric response reflects an apparent electrochemical rate o constant koapp, equal to the true rate constant ko describing the redox reaction of interest on the surface of the nanoparticles and the ratio,ψ, of the total electroactive surface area to the geometric area of the rotating disk surface. It is demonstrated that Koutecky-Levich analysis is applicable and yields the expected plots of I-1 versus ω-1 where I is the current and ω is the rotation speed but that the values of the electrochemical rate constants inferred are thereof koapp, not ko. Thus, for ψ 〉 1 apparent electrocatalysis might be naively but wrongly inferred whereas for ψ 〈 1 the deduced electrochemical rate constant will be less than ko. Moreover, the effect of ψ on the observed rotating disk electrode voltammograms is significant, signalling the need for care in the overly simplistic application of Koutecky-Levich analysis to modified rotating electrodes, as is commonly applied for example in the analysis of possible oxygen reduction catalysts.
基金financially supported by the National Key Research and Development Program of China(2020YFA0710303)the National Natural Science Foundation of China(51972061,U1905215 and 52072076)。
文摘An efficient photocatalytic CO_(2) reduction has been reported in ZIF-67-derived-Co nanoparticles(NPs)encapsulated in nitrogen-doped carbon layers(N-C/Co).This work demonstrates that the pyrolysis temperature is crucial in tuning the grain size and components of metallic Co^(0) of N-C/Co composite catalysts,which optimizes their photocatalytic activities.Syntheses were conducted at 600,700,and 800℃ giving the N-C/Co-600,N-C/Co-700,and N-C/Co-800 samples,respectively.N-C layers can well wrap the Co NPs obtained at a low pyrolysis temperature(600℃)owing to their smaller grains than those of other samples.A high metallic Co^(0) content in the N-C/Co-600 sample can be attributed to the effective inhibition of surface oxidation.By contrast,the surface CoOx oxides in the N-C/Co-700 and N-C/Co-800 samples cover inside Co cores,inhibiting charge separation and transfer.As a result,the N-C/Co-600 sample yields the best photocatalytic activity.The carbon monoxide and hydrogen generation rates are as high as 1.62×10^(4) and 2.01×10^(4)μmol g^(−1)h^(−1),respectively.Additionally,the Co NPs make composite catalysts magnetic,enabling rapid and facile recovery of catalysts with the assistance of an external magnetic field.This work is expected to provide an instructive guideline for designing metal-organic framework-derived carbon/metal composite catalysts.
基金financially supported by the National Natural Science Foundation of China(21222305,11079005,20923001)the National Basic Research Program of China(2011CBA00503,2013CB933100)
文摘Oxide nanostructures grown on noble metal surfaces are often highly active in many reactions,in which the oxide/metal interfaces play an important role.In the present work,we studied the surface structures of Fe Ox-on-Pt and Ni Ox-on-Pt catalysts and their activity to CO oxidation reactions using both model catalysts and supported nanocatalysts.Although the active Fe O1x structure is stabilized on the Pt surface in a reductive reaction atmosphere,it is prone to change to an Fe O2x structure in oxidative reaction gases and becomes deactivated.In contrast,a Ni O1x surface structure supported on Pt is stable in both reductive and oxidative CO oxidation atmospheres.Consequently,CO oxidation over the Ni O1x-on-Pt catalyst is further enhanced in the CO oxidation atmosphere with an excess of O2.The present results demonstrate that the stability of the active oxide surface phases depends on the stabilization effect of the substrate surface and is also related to whether the oxide exhibits a variable oxidation state.
基金This work was supported by the National Natural Science Foundation of China and National Bureau of Oceanography Foundation for Youth (Grant Nos. 49706068, 49736210 and 99506).
文摘By reference of the δ18O and δ13C isotopic compositions of G.sacculifer and accelerator mass spectrometry (AMS)14C dates, the U K 37 , ∑C – 21 /∑C +- 22 and Pr/Pn in core DGKS9603 have been used to characterize the changes of paleooceanographic environment occurring in the East China Sea (ECS) during the last 35000 years. The stratigraphic records of these proxies have shown that during the last 35 ka the Okinawa Trough has gone through 7 stronger cold-climate events (C1–C7) and 9 terrigenous matter-decreasing events (e2–e9), of which, the C1 corresponds to the cold episode occurring in the middle late Holocene, C2–C4 and C7 correspond to the H1–H4 events, respectively. e1 and e3–e8 correspond to the decrease of sea surface temperature (SST), respectively. The terrigenous inputs increased when Heinrich events occurred. Climate colding resulted in the decrease of terrigenous matter transported by rivers, and the increase of that transported by winter monsoon. Heinrich events are closely related to East Asia monsoon. During the Last Glacial Maximum (LGM, 15.5–25.8 Cal ka BP), reduction environment fluctuated strongly, bringing forth three stronger reduction events (R1–R3) and one weaker reduction event (O), of which, R1–R3 correspond to the decrease of SST and increase of terrigenous nutrient and O corresponds to the decrease of terrigenous nutrient. The fluctuation of reduction condition must be related to the change of sea surface productivity.
文摘Au nanoclusters （AuNCs） hold tremendous potential to be employed in a wide variety of biological applications. Despite the rapid development in the field of NCs synthesis, a comprehensive understanding of how cells interact with this class of ultra-small nanoparticles （〈2 nm） having defined sizes and surface chemistry, remains poorly understood. In this study, we show that the choice of the surface ligand used to protect AuNCs can significantly perturb cellular uptake and intracellular redox signaling. A panel of monodisperse, atomically precise AuNCs with different core Au atom number （i.e., Auls, Au18 and Au25） protected with either mercaptopropionic acid （MPA） or glutathione （GSH） capping agent were synthesized and their effects on the generation of intracellular reactive oxygen species （ROS）, cytotoxicity and genotoxicity of the NCs were assessed. Both mitochondrial superoxide anion （O2^-） and cytoplasmic ROS were found to be higher in cells exposed to MPA but not GSH capped AuNCs. The unregulated state of intracellular ROS is correlated to the amount of internalized AuNCs. Interestingly, MPA-AuNCs induction of ROS level did not lead to any detrimental cellular effects such as cell death or DNA damage. Instead, it was observed that the increase in redox status corresponded to higher cellular metabolism and proliferative capacity. Our study illustrates that surface chemistry of AuNCs plays a pivotal role in affecting the biological outcomes and the new insights gained will be useful to form the basis of defining specific design rules to enable rational engineering of ultra-small complex nanostructures for biological applications.
基金supported by the National Basic Research Program of China ("973" Project) (Grant No. 2007CB206901)the Key Projects in the National Science & Technology Pillar Program during the Eleventh Five-Year Plan Period (Grant No. 2006BAF02A27)
文摘Based on the analysis of tin penetration mechanism in the float glass process, the oxidation model of stannous ion is constructed considering the oxygen activity and the redox reaction in the glass surface layer. The calculation of stannous ion's oxidation rate makes it possible to predict both stannous and stannic ion's concentrations independently. And it is also the necessary precondition for the numerical verification of tin penetration mechanism. Coupled diffusion simulation method is established to simulate the penetration process of both stannous and stannic ions simultaneously. The result shows that when the green glass is formed in the reducing atmosphere in tin bath, the stannic ion is accumulated at the position where oxygen activity changes sharply. Satellite peak (internal local concentration maximum) occurs in the tin concentration profile of green glass, which is quite different from that in low iron glass. Compared with gradually cooling temperature regulation, the tin penetrated shifts to greater depth and the depth and magnitude of the satellite peak also increase when reheating temperature regulation is applied. In order to reduce the amount of penetrated tin, the residual time in the high temperature region should be shortened.
