Electrochemical CO_(2) reduction reaction(CO_(2)RR),driven by renewable energy,offers a promising solution to mitigate increasing CO_(2) emissions and establish a carbon-neutral cycle.Copper is a highly selective and ...Electrochemical CO_(2) reduction reaction(CO_(2)RR),driven by renewable energy,offers a promising solution to mitigate increasing CO_(2) emissions and establish a carbon-neutral cycle.Copper is a highly selective and active catalyst for CO_(2)RR but suffers from structural reconstruction challenges.Hybrid organic/inorganic materials address these issues by offering customizable compositions and interfaces.Recently,Buonsanti’s team developed hybrid Cu@AlOx nanocrystals with tunable alumina shells via a colloidal atomic layer deposition approach,achieving stable and selective methane production during CO_(2)RR.Mechanistic studies reveal that the alumina shell stabilizes oxidized copper species through Cu^(2+)-O-Al motifs coordinated with AlO_(4) Lewis acid sites,reducing copper dissolution and structural reconstruction.This study provides key insights into the mechanism underlying stabilization,highlighting the critical role of Lewis acidity in preserving the structural integrity of the catalyst.This highlight review aims to inspire the development of other high-performance and stable catalysts through colloidal atomic layer deposition strategies.展开更多
The 2-methylpyrazine was synthesized by catalytic reaction of ethylene diamine and propylene glycol at 380 ℃. The alumina supported copper catalysts with promoter were prepared by impregnation method, characterized b...The 2-methylpyrazine was synthesized by catalytic reaction of ethylene diamine and propylene glycol at 380 ℃. The alumina supported copper catalysts with promoter were prepared by impregnation method, characterized by ICP-AES, BET and TPR. The results demonstrated that the dehydrogenation was improved by addition of chromium promoter. The selectivity of 2-methylpyrazine reached 84.75%, while the conversions of reactants were also enhanced.展开更多
Copper(Cu)is considered to be the most effective catalyst for electrochemical conversion of carbon dioxide(CO_(2))into value-added hydrocarbons,but its stability still faces considerable challenge.Here,we report the p...Copper(Cu)is considered to be the most effective catalyst for electrochemical conversion of carbon dioxide(CO_(2))into value-added hydrocarbons,but its stability still faces considerable challenge.Here,we report the poisoning effect of carbon deposition during CO_(2)reduction on the active sites of Cu electrodea critical deactivation factor that is often overlooked.We find that,*C,an intermediate toward methane formation,could desorb on the electrode surface to form carbon species.We reveal a strong correlation between the formation of methane and the carbon deposition,and the reaction conditions favoring methane production result in more carbon deposition.The deposited carbon blocks the active sites and consequently causes rapid deterioration of the catalytic performance.We further demonstrate that the carbon deposition can be mitigated by increasing the roughness of the electrode and increasing the pH of the electrolyte.This work offers a new guidance for designing more stable catalysts for CO_(2)reduction.展开更多
N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and co...N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and considerablemethods rely on excessive use of strong base,which suffers severe environmental issues.Herein,benzonitrile derivatives are synthesized from oxidized ligninβ-O-4 model compounds in the presence of solid nitrogen source(NH_(4))_(2)CO_(3)under mild,base-free conditions over commercially available copper catalyst.Mechanism studies suggest the transformation undergoes a one-pot,highly coupled cascade reaction path involving oxidative C-C bond cleavage and in-situ formation of C≡N bond.Of which,Cu(OAc)2 catalyzes the transfer of hydrogen from C_(β)(C_(β)-H)to C_(α),leading to the cleavage of C_(α)-C_(β)bonds to offer benzaldehyde derivative,this intermediate then reacts in-situ with(NH_(4))_(2)CO_(3)to afford the targeted aromatic nitrile product.Tetrabutylammonium iodide(TBAI),acting as a promoter,plays a key role in breaking the C_(α)-C_(β)bonds to form the intermediate benzaldehyde derivative.With this protocol,the feasibility of the production of value-added syringonitrile from birchwood lignin has been demonstrated.This transformation provides a sustainable approach to benzonitrile chemicals from renewable source of lignin.展开更多
In this work,tungsten oxide with different concentrations(0,0.4 at%,2.0 at%and 3.2 at%)was introduced to the ceria nanorods via a deposition-precipitation(DP)approach,and copper species of ca.10 at%were sequentially a...In this work,tungsten oxide with different concentrations(0,0.4 at%,2.0 at%and 3.2 at%)was introduced to the ceria nanorods via a deposition-precipitation(DP)approach,and copper species of ca.10 at%were sequentially anchored onto the modified ceria support by a similar DP route.The aim of the study was to investigate the effect of the amount of tungsten oxide(0,0.4 at%,2.0 at%,and 3.2 at%)modifier on the copper-ceria catalysts for CO oxidation reaction and shed light on the structure-activity relationship.By the aids of multiple characterization techniques including N2 adsorption,high-resolution transmission electron microscopy(HRTEM),powder X-ray diffraction(XRD),X-ray absorption fine structure(XAFS),and temperature-programmed reduction by hydrogen(H2-TPR)in combination with the catalytic performance for CO oxidation reaction,it is found that the copper-ceria samples maintain the crystal structure of the fluorite fcc CeO2 phase with the same nanorod-like morphology with the introduction of tungsten oxide,while the textural properties(the surface area,pore volume and pore size)of ceria support and copper-ceria catalysts are changed,and the oxidation states of copper and tungsten are kept the same as Cu2+and W6+before and after the reaction,but the introduction of tungsten oxide(WO3)significantly changes the metal-support interaction(transfer the CuOx clusters to Cu-[Ox]-Ce species),which delivers to impair the catalytic activity of copper-ceria catalysts for CO oxidation reaction.展开更多
Copolymerization of ethylene with carbon monoxide was pertormed with Cu catalyst systems. Novel catalystsystems based on Cu (Cu(CH_3COO)_2/ligand/acid) were firstly reported for the copolymerization of ethylene with c...Copolymerization of ethylene with carbon monoxide was pertormed with Cu catalyst systems. Novel catalystsystems based on Cu (Cu(CH_3COO)_2/ligand/acid) were firstly reported for the copolymerization of ethylene with carbonmonoxide, in which the ligand was a bidentate phosphorus chelating ligand. The experimental results showed that this kindof Cu catalyst system exhibited high activity. When DPPP (1, 3-bis(diphenylphosphine)propane) and CH_3COOH were usedas ligand and acid, the corresponding catalyst system had the best activity of 108.1 g copolymer/(gCu·h). The novel Cu catalyst system had the advantages of high stability and low cost.展开更多
Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research,however it remains elusive whether molecular-like metal clusters with excitonic behavior can...Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research,however it remains elusive whether molecular-like metal clusters with excitonic behavior can be used as light-harvesting materials in solar energy utilization such as photocatalytic methanol steam reforming.In this work,we report an atomically precise Cu_(13)cluster protected by dual ligands of thiolate and phosphine that can be viewed as the assembly of one top Cu atom and three Cu_(4)tetrahedra.The Cu_(13)H_(10)(SR)_(3)(PR’_(3))_(7)(SR=2,4-dichlorobenzenethiol,PR’_(3)=P(4-FC_(6)H_(4))_(3))cluster can give rise to highly efficient light-driven activity for methanol steam reforming toward H_(2)production.展开更多
To improve the electrocatalytic transformation of carbon dioxide (CO_(2)) to multi-carbon (C_(2+)) products is of great importance.Here we developed a nitrogen-doped Cu catalyst,by which the maximum C_(2+) Faradaic ef...To improve the electrocatalytic transformation of carbon dioxide (CO_(2)) to multi-carbon (C_(2+)) products is of great importance.Here we developed a nitrogen-doped Cu catalyst,by which the maximum C_(2+) Faradaic efficiency can reach 72.7%in flow-cell system,with the partial current density reaching 0.62 A cm^(-2).The in situ Raman spectra demonstrate that the *CO adsorption can be strengthened on such a N-doped Cu catalyst,thus promoting the *CO utilization in the subsequent C–C coupling step.Simultaneously,the water activation can be well enhanced by N doping on Cu catalyst.Owing to the synergistic effects,the selectivity and activity for C_(2+) products over the N-deoped Cu catalyst are much improved.展开更多
Carbon dioxide capture and reduction(CCR)process emerges as an efficient catalytic strategy for CO_(2)capture and conversion to valuable chemicals.K-promoted Cu/Al_(2)O_(3)catalysts exhibited promising CO_(2)capture e...Carbon dioxide capture and reduction(CCR)process emerges as an efficient catalytic strategy for CO_(2)capture and conversion to valuable chemicals.K-promoted Cu/Al_(2)O_(3)catalysts exhibited promising CO_(2)capture efficiency and highly selective conversion to syngas(CO+H_(2)).The dynamic nature of the Cu-K system at reaction conditions complicates the identification of the catalytically active phase and surface sites.The present work aims at more precise understanding of the roles of the potassium and copper and the contribution of the metal oxide support.Whileγ-Al_(2)O_(3)guarantees high dispersion and destabilisation of the potassium phase,potassium and copper act synergistically to remove CO_(2)from diluted streams and promote fast regeneration of the active phase for CO_(2)capture releasing CO while passing H_(2).A temperature of 350℃is found necessary to activate H_(2)dissociation and generate the active sites for CO_(2)capture.The effects of synthesis parameters on the CCR activity are also described by combination of ex-situ characterisation of the materials and catalytic testing.展开更多
Strain engineering on metal-based catalysts has been utilized as an efficacious strategy to regulate the mechanism and pathways in various electrocatalytic reactions.However,controlling strain and establishing the str...Strain engineering on metal-based catalysts has been utilized as an efficacious strategy to regulate the mechanism and pathways in various electrocatalytic reactions.However,controlling strain and establishing the strain-activity relationship still remain significant challenges.Herein,three different and continuous tensile strains(CuPd-1.90%,CuAu-3.37%,and CuAg-4.33%)are successfully induced by introducing heteroatoms with different atomic radius.The catalytic performances of CuPd-1.90%,CuAu-3.37%,and CuAg-4.33%display a positive correlation against tensile strains in electrochemical CO_(2) reduction reaction(CO_(2)RR).Specifically,CuAg-4.33%exhibits superior catalytic performance with a 77.9%Faradaic efficiency of multi-carbon products at−300mA cm^(-2) current density,significantly higher than those of pristine Cu(Cu-0%).Theoretical calculations and in situ spectroscopies verify that tensile strain can affect the d-band center of Cu,thereby altering the binding energy of*CO intermediates and Gibbs free energies of the C-C coupling procedure.This work might highlight a new method for precisely regulating the lattice strain of metallic catalysts in different electrocatalytic reactions.展开更多
The copper based catalysts, CuO/T-Al2O3, CuO/y-Al2O3-cordierite （Cord） and CuO/Cord, were prepared by impregnation method. The catalytic activity of the catalysts was tested in absence and presence of water vapor,an...The copper based catalysts, CuO/T-Al2O3, CuO/y-Al2O3-cordierite （Cord） and CuO/Cord, were prepared by impregnation method. The catalytic activity of the catalysts was tested in absence and presence of water vapor,and the catalysts were characterized. Temperature program desorption （TPD） experiments or toluene and water on the catalysts were carried out. The influence of water vapor on the activity of the catalysts was discussed. Results showed that addition of the water vapor has a significant negative effect on the catalytic activity of the catalysts.The higher the concentration of the Water vapor in feed steam was, the lower the catalytic activity of the copper based catalysts became, which could be mainly ascribed to the competition of water molecules with toluene molecules for adsorption on the catalyst surfaces. TPD experiments showed that the strength of the interaction between water molecules and three catalysts followed the order： CuO/γ-Al2O3〉CuO/γ-Al2O3-Cord〉CuO/Cord. As a consequence of that, the degree of degradation in the catalytic activity of these three catalysts by the water vapor followed the order： CuO/γ-Al2O3〉CuO/y-Al2O3-Cord〉CuO/Cord. However, the negative effect of the water vapor was reversible.展开更多
The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support,...The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support, one （ZrO2-1） was obtained from the commercial ZrO2 and the other （ZrO2-2） was issued from the thermal decomposition of zirconium nitrate. It was found that the CuO/ZrO2-2 catalyst was more active than CuO/ZrO2-1. N2 adsorption, H2-TPR and XRD measurements showed that larger surface area, better reduction property, presence of tetragonal ZrO2 and higher dispersion of active component for CuO/ZrO2-2 than that of CuO/ZrO2-1. These factors could be the dominating reasons for its higher activity for methane combustion.展开更多
Rare earth-doped copper-manganese mixed oxide catalysts were prepared by coprecipitation and mechanical mixing using copper sulfate, manganese sulfate, and rare-earth oxides REO （REO indicates La2O3, CeO2, Y2O3, or P...Rare earth-doped copper-manganese mixed oxide catalysts were prepared by coprecipitation and mechanical mixing using copper sulfate, manganese sulfate, and rare-earth oxides REO （REO indicates La2O3, CeO2, Y2O3, or Pr6O11） as raw materials. The samples were characterized by X-ray diffraction （XRD）, temperature-programmed reduction （TPR）, temperature-programmed reduc-tion of oxidized surfaces （s-TPR）, and temperature-programmed desorption （TPD）. Catalytic activities were tested for a water-gas shift reaction. Doping rare earth oxides did not alter the crystal structure of the original copper-manganese mixed oxides but changed the interplanar spacing, adsorption performance and reaction performance. Doping with La2O3 enhanced the activity and stability of Cu-Mn mixed oxides because of high copper distribution and fine reduction. Doping with CeO2 and Y2O3 also decreased the reduc-tion temperatures of the samples to different degrees while improving the dispersion of Cu on the surface, thus, catalytic activity was better than that of undoped Cu-Mn sample. The Pr6O11-doped sample was difficult to reduce, the dispersion of surface coppers was lowered, resulting in poor activity.展开更多
Copper-ceria sheets catalysts with different loadings of copper（2 wt.%, 5 wt.% and 10 wt.%） supported on ceria nanosheets were synthesized via a depositioneprecipitation（DP） method. The prepared catalysts were sys...Copper-ceria sheets catalysts with different loadings of copper（2 wt.%, 5 wt.% and 10 wt.%） supported on ceria nanosheets were synthesized via a depositioneprecipitation（DP） method. The prepared catalysts were systematically characterized with various structural and textural detections including X-ray diffraction（XRD）, Raman spectra, transmission electron microscopy（TEM）, X-ray absorption fine structure（XAFS）, and temperature-programmed reduction by hydrogen（H2-TPR）, and tested for the CO oxidation reaction. Notably, the sample containing 5 wt.% of Cu exhibited the best catalytic performance as a result of the highest number of active CuO species on the catalyst surface. Further increase of copper content strongly affects the dispersion of copper and thus leads to the formation of less active bulk CuO phase, which was verified by XRD and H2-TPR analysis. Moreover, on the basis of in-situ diffuse reflectance infrared Fourier transform spectroscopy（in-situ DRIFTS） results, the surface Cu~＋ species, which are derived from the reduction of Cu^（2＋）, are likely to play a crucial role in the catalyzing CO oxidation.Consequently, the superior catalytic performance of the copper-ceria sheets is mainly attributed to the highly dispersed CuOx cluster rather than Cu-[Ox]-Ce structure, while the bulk CuO phase is adverse to the catalytic activity of CO oxidation.展开更多
Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation ...Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation methods of aluminum emulsions on physicochemical and catalytic properties of catalysts were studied by XRD, SEM, XPS,N2 adsorption-desorption techniques and methanol synthesis from syngas. The preparation methods of aluminum emulsions were found to influence the catalytic activity, CuO crystallite size, surface area and Cu0 surface area and reduction process. The results show that the catalyst CN using the aluminum source prepared by addition the ammonia into the aluminum nitrate （NP） exhibited the best catalytic performance for methanol synthesis from syngas.展开更多
The performances of CO selective oxidation in hydrogen-rich gas over fourcatalytic systems of CuO/ZrO_2, CuO/MnO_2, CuO/CoO and CuO/CeO_2 were compared. The reducibility ofthese catalysts and the effect of CuO and CeO...The performances of CO selective oxidation in hydrogen-rich gas over fourcatalytic systems of CuO/ZrO_2, CuO/MnO_2, CuO/CoO and CuO/CeO_2 were compared. The reducibility ofthese catalysts and the effect of CuO and CeO_2 molar ratio of CuO/CeO_2 catalysts on the activityof selective CO oxidation are investigated by XRD and TPR methods. The results show that thecatalysts with the exception of CuO/ZrO_2 have the interactions between CuO and CoO, CeO_2 or MnO_2,which result in a decrease in the reduction temperature. Among the catalysts studied, CuO/ZrO_2catalyst shows the lowest catalytic activity while CuO/CeO_2 catalyst exhibits the best catalyticperformance. The CuO(10%)/CeO_2 catalyst attains the highest CO conversion and selectivity at 140and 160℃. The addition of 9% H_2O in the reactant feed decreases the activity of CuO/CeO_2 catalystbut increases its CO selectivity.展开更多
Alcohol-assisted low-temperature methanol synthesis was conducted over Cu/ZnO;catalysts while varying the copper content（X）. Unlike conventional methanol synthesis, ethanol acted as both solvent and reaction interme...Alcohol-assisted low-temperature methanol synthesis was conducted over Cu/ZnO;catalysts while varying the copper content（X）. Unlike conventional methanol synthesis, ethanol acted as both solvent and reaction intermediate in this reaction, creating a different reaction pathway. The formation of crystalline phases and characteristic morphology of the co-precipitated precursors during the co-precipitation step were important factors in obtaining an efficient Cu/ZnO catalyst with a high dispersion of metallic copper,which is one of the main active sites for methanol synthesis. The acidic properties of the Cu/ZnO catalyst were also revealed as important factors, since alcohol esterification is considered the rate-limiting step in alcohol-assisted low-temperature methanol synthesis. As a consequence, bifunctionality of the Cu/ZnO catalyst such as metallic copper and acidic properties was required for this reaction. In this respect, the copper content（X） strongly affected the catalytic activity of the Cu/ZnO;catalysts, and accordingly, the Cu/ZnO;.5 catalyst with a high copper dispersion and sufficient acid sites exhibited the best catalytic performance in this reaction.展开更多
High surface area CeO2 was prepared by the surfactant-assisted route and was employed as catalyst support. The 0-3 at.% Cu doped Cu-Ni/CeO2 catalysts with 10 wt.% and 15 wt.% of total metal loading were prepared by an...High surface area CeO2 was prepared by the surfactant-assisted route and was employed as catalyst support. The 0-3 at.% Cu doped Cu-Ni/CeO2 catalysts with 10 wt.% and 15 wt.% of total metal loading were prepared by an impregnation-coprecipitation method. The influence of Cu atomic content on the catalytic performance was investigated on the steam reforming of ethanol （SRE） for H2 production and the catalysts were characterized by N2 adsorption, inductively coupled plasma （ICP）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, temperature-programmed rerduction （TPR） and H2-pulse chemisorption techniques. The activity and products distribution behaviors of the catalysts were significantly affected by the doped Cu molar content based on the promotion effect on the dispersion of NiO particles and the interactions between Cu-Ni metal and CeO2 support. Significant increase in the ethanol conversion and hydrogen selectivity were obtained when moderate Cu metal was doped into the Ni/CeO2 catalyst. Over both of the 10Ni98.5Cu1.5/CeO2 and 15Ni98.5Cu1.5/CeO2 catalysts, more than 80% of ethanol conversion and 60% of H2 selectivity were obtained in the ethanol steam-reforming when the reaction temperature was above 450 ℃.展开更多
The solid structures and thermostabilities of Cu-Fe-O and Cu-Fe-Ce-O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe2CuO4, CuO and alpha-Fe2O3 phases...The solid structures and thermostabilities of Cu-Fe-O and Cu-Fe-Ce-O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe2CuO4, CuO and alpha-Fe2O3 phases in Cu-Fe-O with the granula of less than 13 nm. With the catalyst pretreatment temperature rising, the crystallite of Fe2CuO4 in the catalysts grows up and that of CuO disappears gradually. The presence of Ce leads to the increase of Cu2+ concentration, inhibits the crystal growth of CuO and Fe2CuO4 in the catalyst except that of Fe2O3, and eliminates the difference for reductive reaction of oxygen in Fe-O and Cu-O. At 800 degrees C, the crystal growth of Fe2O3 in Cu-Fe-Ce-O is slower than that in Cu-Fe-O, i.e., CeO2 in Cu-Fe-Ce-O inhibits the growth of Fe2O3 phase effectively, and enhances the thermostability of catalysts so as to avoid the sintering of active elements in catalysts. CeO2 promotes the reducibility of catalysts at lower temperature.展开更多
基金supported by the National Natural Science Foundation of China(No.22101289)Hundred Talents Programs in Chinese Academy of Science,and the Ningbo S&T Innovation 2025 Major Special Program(No.2022Z205).
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR),driven by renewable energy,offers a promising solution to mitigate increasing CO_(2) emissions and establish a carbon-neutral cycle.Copper is a highly selective and active catalyst for CO_(2)RR but suffers from structural reconstruction challenges.Hybrid organic/inorganic materials address these issues by offering customizable compositions and interfaces.Recently,Buonsanti’s team developed hybrid Cu@AlOx nanocrystals with tunable alumina shells via a colloidal atomic layer deposition approach,achieving stable and selective methane production during CO_(2)RR.Mechanistic studies reveal that the alumina shell stabilizes oxidized copper species through Cu^(2+)-O-Al motifs coordinated with AlO_(4) Lewis acid sites,reducing copper dissolution and structural reconstruction.This study provides key insights into the mechanism underlying stabilization,highlighting the critical role of Lewis acidity in preserving the structural integrity of the catalyst.This highlight review aims to inspire the development of other high-performance and stable catalysts through colloidal atomic layer deposition strategies.
文摘The 2-methylpyrazine was synthesized by catalytic reaction of ethylene diamine and propylene glycol at 380 ℃. The alumina supported copper catalysts with promoter were prepared by impregnation method, characterized by ICP-AES, BET and TPR. The results demonstrated that the dehydrogenation was improved by addition of chromium promoter. The selectivity of 2-methylpyrazine reached 84.75%, while the conversions of reactants were also enhanced.
基金supported by the National Basic Research Program of China(Grant 2018YFA0702001)the National Natural Science Foundation of China(Grants 22225901,21975237 and 51702312)+5 种基金the Fundamental Research Funds for the Central Universities(Grant WK2340000101)the USTC Research Funds of the Double First-Class Initiative(Grant YD2340002007 and YD9990002017)the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization(Grant RERU2022007)the China Postdoctoral Science Foundation(Grants 2023M733371,2022M723032,and 2023T160617)the Natural Science Foundation Youth Project of Anhui Province(2308085QB37)the China National Postdoctoral Program for Innovative Talents(BX2023341).
文摘Copper(Cu)is considered to be the most effective catalyst for electrochemical conversion of carbon dioxide(CO_(2))into value-added hydrocarbons,but its stability still faces considerable challenge.Here,we report the poisoning effect of carbon deposition during CO_(2)reduction on the active sites of Cu electrodea critical deactivation factor that is often overlooked.We find that,*C,an intermediate toward methane formation,could desorb on the electrode surface to form carbon species.We reveal a strong correlation between the formation of methane and the carbon deposition,and the reaction conditions favoring methane production result in more carbon deposition.The deposited carbon blocks the active sites and consequently causes rapid deterioration of the catalytic performance.We further demonstrate that the carbon deposition can be mitigated by increasing the roughness of the electrode and increasing the pH of the electrolyte.This work offers a new guidance for designing more stable catalysts for CO_(2)reduction.
基金supported by the National Key R&D Program of China(No.2023YFA1507902)the National Natural Science Foundation of China(Nos.21721004 and 21878288)+1 种基金the science and technology bureau of Dalian city(No.2021RT04)the Strategic Priority Research Program of the Chinese Academy of Sciences(No.XDB17020100).
文摘N-participated lignin depolymerization is of great importance for the transformation of waste lignin into value-added chemicals.The vast majority of developed strategies employ organic amines as nitrogen source,and considerablemethods rely on excessive use of strong base,which suffers severe environmental issues.Herein,benzonitrile derivatives are synthesized from oxidized ligninβ-O-4 model compounds in the presence of solid nitrogen source(NH_(4))_(2)CO_(3)under mild,base-free conditions over commercially available copper catalyst.Mechanism studies suggest the transformation undergoes a one-pot,highly coupled cascade reaction path involving oxidative C-C bond cleavage and in-situ formation of C≡N bond.Of which,Cu(OAc)2 catalyzes the transfer of hydrogen from C_(β)(C_(β)-H)to C_(α),leading to the cleavage of C_(α)-C_(β)bonds to offer benzaldehyde derivative,this intermediate then reacts in-situ with(NH_(4))_(2)CO_(3)to afford the targeted aromatic nitrile product.Tetrabutylammonium iodide(TBAI),acting as a promoter,plays a key role in breaking the C_(α)-C_(β)bonds to form the intermediate benzaldehyde derivative.With this protocol,the feasibility of the production of value-added syringonitrile from birchwood lignin has been demonstrated.This transformation provides a sustainable approach to benzonitrile chemicals from renewable source of lignin.
基金Project supported by National Natural Science Foundation of China(21773288,51902093)National Key Basic Research Program of China(2017YFA0403402)。
文摘In this work,tungsten oxide with different concentrations(0,0.4 at%,2.0 at%and 3.2 at%)was introduced to the ceria nanorods via a deposition-precipitation(DP)approach,and copper species of ca.10 at%were sequentially anchored onto the modified ceria support by a similar DP route.The aim of the study was to investigate the effect of the amount of tungsten oxide(0,0.4 at%,2.0 at%,and 3.2 at%)modifier on the copper-ceria catalysts for CO oxidation reaction and shed light on the structure-activity relationship.By the aids of multiple characterization techniques including N2 adsorption,high-resolution transmission electron microscopy(HRTEM),powder X-ray diffraction(XRD),X-ray absorption fine structure(XAFS),and temperature-programmed reduction by hydrogen(H2-TPR)in combination with the catalytic performance for CO oxidation reaction,it is found that the copper-ceria samples maintain the crystal structure of the fluorite fcc CeO2 phase with the same nanorod-like morphology with the introduction of tungsten oxide,while the textural properties(the surface area,pore volume and pore size)of ceria support and copper-ceria catalysts are changed,and the oxidation states of copper and tungsten are kept the same as Cu2+and W6+before and after the reaction,but the introduction of tungsten oxide(WO3)significantly changes the metal-support interaction(transfer the CuOx clusters to Cu-[Ox]-Ce species),which delivers to impair the catalytic activity of copper-ceria catalysts for CO oxidation reaction.
文摘Copolymerization of ethylene with carbon monoxide was pertormed with Cu catalyst systems. Novel catalystsystems based on Cu (Cu(CH_3COO)_2/ligand/acid) were firstly reported for the copolymerization of ethylene with carbonmonoxide, in which the ligand was a bidentate phosphorus chelating ligand. The experimental results showed that this kindof Cu catalyst system exhibited high activity. When DPPP (1, 3-bis(diphenylphosphine)propane) and CH_3COOH were usedas ligand and acid, the corresponding catalyst system had the best activity of 108.1 g copolymer/(gCu·h). The novel Cu catalyst system had the advantages of high stability and low cost.
基金financial support from National Natural Science Foundation of China(22125202,21932004,22101128)Natural Science Foundation of Jiangsu Province(BK20220033)。
文摘Plasmon-induced hot-electron transfer from metal nanostructures is being intensely pursed in current photocatalytic research,however it remains elusive whether molecular-like metal clusters with excitonic behavior can be used as light-harvesting materials in solar energy utilization such as photocatalytic methanol steam reforming.In this work,we report an atomically precise Cu_(13)cluster protected by dual ligands of thiolate and phosphine that can be viewed as the assembly of one top Cu atom and three Cu_(4)tetrahedra.The Cu_(13)H_(10)(SR)_(3)(PR’_(3))_(7)(SR=2,4-dichlorobenzenethiol,PR’_(3)=P(4-FC_(6)H_(4))_(3))cluster can give rise to highly efficient light-driven activity for methanol steam reforming toward H_(2)production.
基金supported by National Natural Science Foundation of China (22033009, 22121002, 22238011)。
文摘To improve the electrocatalytic transformation of carbon dioxide (CO_(2)) to multi-carbon (C_(2+)) products is of great importance.Here we developed a nitrogen-doped Cu catalyst,by which the maximum C_(2+) Faradaic efficiency can reach 72.7%in flow-cell system,with the partial current density reaching 0.62 A cm^(-2).The in situ Raman spectra demonstrate that the *CO adsorption can be strengthened on such a N-doped Cu catalyst,thus promoting the *CO utilization in the subsequent C–C coupling step.Simultaneously,the water activation can be well enhanced by N doping on Cu catalyst.Owing to the synergistic effects,the selectivity and activity for C_(2+) products over the N-deoped Cu catalyst are much improved.
文摘Carbon dioxide capture and reduction(CCR)process emerges as an efficient catalytic strategy for CO_(2)capture and conversion to valuable chemicals.K-promoted Cu/Al_(2)O_(3)catalysts exhibited promising CO_(2)capture efficiency and highly selective conversion to syngas(CO+H_(2)).The dynamic nature of the Cu-K system at reaction conditions complicates the identification of the catalytically active phase and surface sites.The present work aims at more precise understanding of the roles of the potassium and copper and the contribution of the metal oxide support.Whileγ-Al_(2)O_(3)guarantees high dispersion and destabilisation of the potassium phase,potassium and copper act synergistically to remove CO_(2)from diluted streams and promote fast regeneration of the active phase for CO_(2)capture releasing CO while passing H_(2).A temperature of 350℃is found necessary to activate H_(2)dissociation and generate the active sites for CO_(2)capture.The effects of synthesis parameters on the CCR activity are also described by combination of ex-situ characterisation of the materials and catalytic testing.
基金Basic and Applied Basic Research Foundation of Guangdong Province,Grant/Award Numbers:2022B1515120084,2023A1515012776National Natural Science Foundation of China,Grant/Award Numbers:22172099,U21A20312Shenzhen Science and Technology Program,Grant/Award Number:RCYX20200714114535052。
文摘Strain engineering on metal-based catalysts has been utilized as an efficacious strategy to regulate the mechanism and pathways in various electrocatalytic reactions.However,controlling strain and establishing the strain-activity relationship still remain significant challenges.Herein,three different and continuous tensile strains(CuPd-1.90%,CuAu-3.37%,and CuAg-4.33%)are successfully induced by introducing heteroatoms with different atomic radius.The catalytic performances of CuPd-1.90%,CuAu-3.37%,and CuAg-4.33%display a positive correlation against tensile strains in electrochemical CO_(2) reduction reaction(CO_(2)RR).Specifically,CuAg-4.33%exhibits superior catalytic performance with a 77.9%Faradaic efficiency of multi-carbon products at−300mA cm^(-2) current density,significantly higher than those of pristine Cu(Cu-0%).Theoretical calculations and in situ spectroscopies verify that tensile strain can affect the d-band center of Cu,thereby altering the binding energy of*CO intermediates and Gibbs free energies of the C-C coupling procedure.This work might highlight a new method for precisely regulating the lattice strain of metallic catalysts in different electrocatalytic reactions.
基金Supported by the National-Natural Science Foundation of China （20936001）, the Natural Science Foundation of Guangdong Province, and the State Key Lab of Subtropical Building Science, South China University of Technology （x2yj C709028Z）.
文摘The copper based catalysts, CuO/T-Al2O3, CuO/y-Al2O3-cordierite （Cord） and CuO/Cord, were prepared by impregnation method. The catalytic activity of the catalysts was tested in absence and presence of water vapor,and the catalysts were characterized. Temperature program desorption （TPD） experiments or toluene and water on the catalysts were carried out. The influence of water vapor on the activity of the catalysts was discussed. Results showed that addition of the water vapor has a significant negative effect on the catalytic activity of the catalysts.The higher the concentration of the Water vapor in feed steam was, the lower the catalytic activity of the copper based catalysts became, which could be mainly ascribed to the competition of water molecules with toluene molecules for adsorption on the catalyst surfaces. TPD experiments showed that the strength of the interaction between water molecules and three catalysts followed the order： CuO/γ-Al2O3〉CuO/γ-Al2O3-Cord〉CuO/Cord. As a consequence of that, the degree of degradation in the catalytic activity of these three catalysts by the water vapor followed the order： CuO/γ-Al2O3〉CuO/y-Al2O3-Cord〉CuO/Cord. However, the negative effect of the water vapor was reversible.
文摘The nano ZrO2-supported copper-based catalysts for methane combustion were investigated by means of N2 adsorption, TEM, XRD, H2-TPR techniques and the test of methane oxidation. Two kinds of ZrO2 were used as support, one （ZrO2-1） was obtained from the commercial ZrO2 and the other （ZrO2-2） was issued from the thermal decomposition of zirconium nitrate. It was found that the CuO/ZrO2-2 catalyst was more active than CuO/ZrO2-1. N2 adsorption, H2-TPR and XRD measurements showed that larger surface area, better reduction property, presence of tetragonal ZrO2 and higher dispersion of active component for CuO/ZrO2-2 than that of CuO/ZrO2-1. These factors could be the dominating reasons for its higher activity for methane combustion.
基金Project supported by National Natural Science Foundation of China(21066008,21266017)Inner Mongolia Science and Technology Plan Project(20101502)
文摘Rare earth-doped copper-manganese mixed oxide catalysts were prepared by coprecipitation and mechanical mixing using copper sulfate, manganese sulfate, and rare-earth oxides REO （REO indicates La2O3, CeO2, Y2O3, or Pr6O11） as raw materials. The samples were characterized by X-ray diffraction （XRD）, temperature-programmed reduction （TPR）, temperature-programmed reduc-tion of oxidized surfaces （s-TPR）, and temperature-programmed desorption （TPD）. Catalytic activities were tested for a water-gas shift reaction. Doping rare earth oxides did not alter the crystal structure of the original copper-manganese mixed oxides but changed the interplanar spacing, adsorption performance and reaction performance. Doping with La2O3 enhanced the activity and stability of Cu-Mn mixed oxides because of high copper distribution and fine reduction. Doping with CeO2 and Y2O3 also decreased the reduc-tion temperatures of the samples to different degrees while improving the dispersion of Cu on the surface, thus, catalytic activity was better than that of undoped Cu-Mn sample. The Pr6O11-doped sample was difficult to reduce, the dispersion of surface coppers was lowered, resulting in poor activity.
基金Project supported by the National Natural Science Foundation of China(21301107,21501109)the Excellent Young Scientists Fund from NSFC(21622106)+3 种基金the Taishan Scholar Project of Shandong Province of China,China Postdoctoral Science Foundation(2014M551891,2015T80706)Doctoral Funding of Shandong Province of China(BS2014CL008)Specialized Research Fund for the Doctoral Program of Higher Education(20130131120009)Postdoctoral Innovation Project Foundation of Shandong Province(201301008)
文摘Copper-ceria sheets catalysts with different loadings of copper（2 wt.%, 5 wt.% and 10 wt.%） supported on ceria nanosheets were synthesized via a depositioneprecipitation（DP） method. The prepared catalysts were systematically characterized with various structural and textural detections including X-ray diffraction（XRD）, Raman spectra, transmission electron microscopy（TEM）, X-ray absorption fine structure（XAFS）, and temperature-programmed reduction by hydrogen（H2-TPR）, and tested for the CO oxidation reaction. Notably, the sample containing 5 wt.% of Cu exhibited the best catalytic performance as a result of the highest number of active CuO species on the catalyst surface. Further increase of copper content strongly affects the dispersion of copper and thus leads to the formation of less active bulk CuO phase, which was verified by XRD and H2-TPR analysis. Moreover, on the basis of in-situ diffuse reflectance infrared Fourier transform spectroscopy（in-situ DRIFTS） results, the surface Cu~＋ species, which are derived from the reduction of Cu^（2＋）, are likely to play a crucial role in the catalyzing CO oxidation.Consequently, the superior catalytic performance of the copper-ceria sheets is mainly attributed to the highly dispersed CuOx cluster rather than Cu-[Ox]-Ce structure, while the bulk CuO phase is adverse to the catalytic activity of CO oxidation.
文摘Various Cu/ZnO/Al2O3 catalysts have been synthesized by different aluminum emulsions as aluminum sources and their pertormances tor methanol synthesis from syngas have been investigated. The influences of preparation methods of aluminum emulsions on physicochemical and catalytic properties of catalysts were studied by XRD, SEM, XPS,N2 adsorption-desorption techniques and methanol synthesis from syngas. The preparation methods of aluminum emulsions were found to influence the catalytic activity, CuO crystallite size, surface area and Cu0 surface area and reduction process. The results show that the catalyst CN using the aluminum source prepared by addition the ammonia into the aluminum nitrate （NP） exhibited the best catalytic performance for methanol synthesis from syngas.
基金This work was financially supported by Guangdong Province Natural Science Foundation of China(000435), the Doctoral Program Foundation of the Ministry of Education (20010561003) Guangzhou Municipal Science and Technology Project(2001J1C0211)
文摘The performances of CO selective oxidation in hydrogen-rich gas over fourcatalytic systems of CuO/ZrO_2, CuO/MnO_2, CuO/CoO and CuO/CeO_2 were compared. The reducibility ofthese catalysts and the effect of CuO and CeO_2 molar ratio of CuO/CeO_2 catalysts on the activityof selective CO oxidation are investigated by XRD and TPR methods. The results show that thecatalysts with the exception of CuO/ZrO_2 have the interactions between CuO and CoO, CeO_2 or MnO_2,which result in a decrease in the reduction temperature. Among the catalysts studied, CuO/ZrO_2catalyst shows the lowest catalytic activity while CuO/CeO_2 catalyst exhibits the best catalyticperformance. The CuO(10%)/CeO_2 catalyst attains the highest CO conversion and selectivity at 140and 160℃. The addition of 9% H_2O in the reactant feed decreases the activity of CuO/CeO_2 catalystbut increases its CO selectivity.
基金supported by C1 Gas Refinery Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science,ICT & Future Planning (2015M3D3A1A01064908)
文摘Alcohol-assisted low-temperature methanol synthesis was conducted over Cu/ZnO;catalysts while varying the copper content（X）. Unlike conventional methanol synthesis, ethanol acted as both solvent and reaction intermediate in this reaction, creating a different reaction pathway. The formation of crystalline phases and characteristic morphology of the co-precipitated precursors during the co-precipitation step were important factors in obtaining an efficient Cu/ZnO catalyst with a high dispersion of metallic copper,which is one of the main active sites for methanol synthesis. The acidic properties of the Cu/ZnO catalyst were also revealed as important factors, since alcohol esterification is considered the rate-limiting step in alcohol-assisted low-temperature methanol synthesis. As a consequence, bifunctionality of the Cu/ZnO catalyst such as metallic copper and acidic properties was required for this reaction. In this respect, the copper content（X） strongly affected the catalytic activity of the Cu/ZnO;catalysts, and accordingly, the Cu/ZnO;.5 catalyst with a high copper dispersion and sufficient acid sites exhibited the best catalytic performance in this reaction.
基金Project supported by the National Natural Science Foundation (21076047)the Natural Science Foundation of Zhongkai University of Agriculture and Engineering (G3100026)
文摘High surface area CeO2 was prepared by the surfactant-assisted route and was employed as catalyst support. The 0-3 at.% Cu doped Cu-Ni/CeO2 catalysts with 10 wt.% and 15 wt.% of total metal loading were prepared by an impregnation-coprecipitation method. The influence of Cu atomic content on the catalytic performance was investigated on the steam reforming of ethanol （SRE） for H2 production and the catalysts were characterized by N2 adsorption, inductively coupled plasma （ICP）, X-ray diffraction （XRD）, transmission electron microscopy （TEM）, temperature-programmed rerduction （TPR） and H2-pulse chemisorption techniques. The activity and products distribution behaviors of the catalysts were significantly affected by the doped Cu molar content based on the promotion effect on the dispersion of NiO particles and the interactions between Cu-Ni metal and CeO2 support. Significant increase in the ethanol conversion and hydrogen selectivity were obtained when moderate Cu metal was doped into the Ni/CeO2 catalyst. Over both of the 10Ni98.5Cu1.5/CeO2 and 15Ni98.5Cu1.5/CeO2 catalysts, more than 80% of ethanol conversion and 60% of H2 selectivity were obtained in the ethanol steam-reforming when the reaction temperature was above 450 ℃.
文摘The solid structures and thermostabilities of Cu-Fe-O and Cu-Fe-Ce-O supported on alumina were studied by XRD, ESR, Mossbauer and TPR techniques. The studies indicate that there are Fe2CuO4, CuO and alpha-Fe2O3 phases in Cu-Fe-O with the granula of less than 13 nm. With the catalyst pretreatment temperature rising, the crystallite of Fe2CuO4 in the catalysts grows up and that of CuO disappears gradually. The presence of Ce leads to the increase of Cu2+ concentration, inhibits the crystal growth of CuO and Fe2CuO4 in the catalyst except that of Fe2O3, and eliminates the difference for reductive reaction of oxygen in Fe-O and Cu-O. At 800 degrees C, the crystal growth of Fe2O3 in Cu-Fe-Ce-O is slower than that in Cu-Fe-O, i.e., CeO2 in Cu-Fe-Ce-O inhibits the growth of Fe2O3 phase effectively, and enhances the thermostability of catalysts so as to avoid the sintering of active elements in catalysts. CeO2 promotes the reducibility of catalysts at lower temperature.
