The three-dimensional(3D) Pd-based nanoflower structures,assembled from two-dimensional(2D)nanosheets,are characterized by their stable and ordered configurations.These structures have been extensively designed as ano...The three-dimensional(3D) Pd-based nanoflower structures,assembled from two-dimensional(2D)nanosheets,are characterized by their stable and ordered configurations.These structures have been extensively designed as anode materials for fuel cells.However,the exploration of trimetallic nanoflowers with porous architectures remains limited.In this study,we present a straightforward one-step solvothermal method for the synthesis of trimetallic Pd Cu Ni porous nanoflowers(PNFs).Leveraging several unique advantages,such as an open superstructure,high porosity,and enhanced electronic interactions among the trimetals,the resulting Pd Cu Ni PNFs demonstrate significantly improved electrochemical performance,with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction(EOR)and the ethylene glycol oxidation reaction(EGOR),respectively.Furthermore,the Pd Cu Ni PNFs exhibit optimized d-band centers and the most negative onset oxidation potential,indicating enhanced antitoxicity and stability.This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.展开更多
Ammonia borane(AB)is a promising hydrogen storage medium widely used for hydrogen generation,but its slow hydrolysis kinetics limits its applications.Medium/high-entropy materials(M/HEMs)have emerged as efficient cata...Ammonia borane(AB)is a promising hydrogen storage medium widely used for hydrogen generation,but its slow hydrolysis kinetics limits its applications.Medium/high-entropy materials(M/HEMs)have emerged as efficient catalysts due to their complementary elemental and structural properties.We developed a deposition in-situ reduction(D-ISR)approach for the rapid synthesis of single-phase medium/high-entropy oxides(M/HEOs)at room temperature,along with establishing general criteria for M/HEOs synthesis based on component properties.Deposition facilitates the incorporation of active elements(Ti/Zr/V/Cr/Nb),which significantly enhance the enthalpy-driven force of the dynamic oxidation(DO)process via an“active element coordination”strategy,thereby overcoming low-temperature solid solubility limitations.Nine-component HEOs and large-scale experiments confirm the universality and mass-production potential of the D-ISR approach.CoCuNiTi-O/AC synthesized via this strategy exhibits pronounced crystal distortion and disorder(Co–O coordination number=10.2),enhancing the Co–O coordination environment and mitigating Ostwald ripening.This leads to high activity and significantly enhanced structural stability,achieving a turnover frequency of 236.6 min^(-1)for ammonia borane hydrolysis,15 times higher than Co-O/AC and surpassing the most non-noble catalysts.These observations highlight an efficient M/HEOs synthesis methodology that advances M/HEMs applications in nanoenergy.展开更多
Uronic acids are prevalent components of crucial glycoconjugates,pivotal in various biological processes.In nature,NDP-uronic acids,the nucleosides-activated uronic acids,serve as glycosylation donors catalyzed by uro...Uronic acids are prevalent components of crucial glycoconjugates,pivotal in various biological processes.In nature,NDP-uronic acids,the nucleosides-activated uronic acids,serve as glycosylation donors catalyzed by uronosyltransferases(UATs)to construct glycans containing uronic acids.Despite their biological importance,the synthesis of naturally occurring NDP-uronic acids on a large scale remains challenging.Here,we developed an oxidation reaction insertion strategy for the efficient synthesis of NDP-uronic acids,and 11 NDP-uronic acids were successfully prepared in good yield and on a large scale.The prepared NDP-uronic acids can be used to explore new uronosyltransferases and synthesize uronic acids containing carbohydrates for fundamental research.展开更多
This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hy...This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies（i.e.,nanorods,nanosheets,and nanocubes） were successfully synthesized,and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors.The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures（≤ 140℃）.Nanorods can be synthesized in CoCl2 solution,while Co（NO3）2 solution promotes the formation of nanosheets.Further increasing the synthesis temperature（higher than 140 ℃） results in the formation of nanocubes in either Co（NO3）2 or CoCl2 solution.The reaction time only affects the size of the obtained nanoparticles.The presence of CTAB could improve the uniformity and dispersion of particles.Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co^（3＋） on the surface,much higher reducibility,and better oxygen desorption capacity.展开更多
Minimizing the thermal expansion coefficient(TEC)mismatch between the cathode and electrolyte in solid oxide fuel cells is crucial for achieving stable,durable operation and high performance.Recently,materials with ne...Minimizing the thermal expansion coefficient(TEC)mismatch between the cathode and electrolyte in solid oxide fuel cells is crucial for achieving stable,durable operation and high performance.Recently,materials with negative thermal expansion(NTE)have at-tracted significant attention as effective additives for tailoring the thermomechanical properties of electrodes and enhancing cell durability.In this work,for the first time,single-phase NTE perovskite Sm_(0.85)Zn_(0.15)MnO_(3−δ)(SZM15)was successfully synthesized via the sol-gel method,eliminating the unwanted ZnO phase typically observed in materials obtained through the conventional solid-state reaction route.The sol-gel approach proved highly advantageous,offering low cost,robustness,excellent chemical homogeneity,precise compositional control,and high phase purity.After optimization of synthesis parameters,a negative TEC of approximately−6.5×10^(−6)K^(−1)was achieved in the 400-850℃range.SZM15 was then incorporated as an additive(10wt%-50wt%)into a SmBa0.5Sr0.5CoCuO_(5+δ)(SBSCCO)cathode to tune the thermomechanical properties with a La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(0.2)O_(3−δ)(LSGM)electrolyte,achieving a minimal TEC mismatch of only 1%.Notably,the SBSCCO+10wt%SZM15 composite cathode exhibited the lowest polarization resistance of 0.019Ω·cm^(2)at 900℃,showing approximately 70%lower than that of the pristine cathode.Excellent long-term stability after 100 h of operation was achieved.In addition,a high peak power density of 680 mW·cm^(−2)was achieved in a Ni-YSZ(yttria-stabilized zirconia)|YSZ|Ce_(0.9)Gd_(0.1)O_(2−δ)(GDC10)|SBSCCO+10wt%SZM15 anode-supported fuel cell at 850℃,highlighting the effectiveness of incorporating NTE materials as a promising strategy for regulating the thermomechanical properties and improving the long-term stability of intermediate temperature solid oxide fuel cells(IT-SOFCs).展开更多
A new technique -- the direct partial oxidation of methane to synthesis gas using lattice oxygen in molten salts medium has been introduced. Using CeO2 as the oxygen carrier, thermodynamic data were calculated in the ...A new technique -- the direct partial oxidation of methane to synthesis gas using lattice oxygen in molten salts medium has been introduced. Using CeO2 as the oxygen carrier, thermodynamic data were calculated in the reaction process, and the results indicated that direct partial oxidation of methane to synthesis gas using lattice oxygen of cerium oxide is feasible in theory. In a stainless steel reactor, the effects of temperature and varying amounts of γ-Al2O3 supported CeO2 on cn4 conversion, H2 and CO selectivity, were investigated, respectively. The results show that 10% CeO2/γ-Al2O3 has the maximal reaction activity at a temperature of 865 ℃ and above, the H2/CO ratio in the gas that has been produced reaches 2 and the CH4 conversion, H2 and CO selectivity reached the following percentages： i.e. 61%, 89%, and 91% at 870 ℃, respectively. In addition, increase of reaction temperature is favorable for the partial oxidation of methane.展开更多
Mesoporous CeO2-MnOx binary oxides with different Mn/Ce molar ratios were prepared by hydrothermal synthesis and characterized by scanning electron microscopy （SEM）, N2 sorption, X-ray diffraction （XRD）, X-ray pho...Mesoporous CeO2-MnOx binary oxides with different Mn/Ce molar ratios were prepared by hydrothermal synthesis and characterized by scanning electron microscopy （SEM）, N2 sorption, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and H2 temperature-programmed reduction （H2-TPR）. The characterization results indicated that the CeO2-MnOx catalysts exhibited flower-like microspheres with high specific surface areas, and partial Mn cations could be incorporated into CeO2 lattice to form solid solution. The CeO2-MnOx catalysts showed better catalytic activity for CO oxidation than that prepared by the coprecipitation method. Furthermore, the CeO2-MnOx catalyst with Mn/Ce molar ratio of 1 in the synthesis gel （Ce-Mn-1） exhibited the best catalytic activity, over which the conversion of CO could achieve 90% at 135 ℃. This was ascribed to presence of more Mn species with higher oxida- tion state on the surface and the better reducibility over the Ce-Mn-I catalyst than other CeO2-MnOx catalysts.展开更多
In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x ...In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.展开更多
The valorization of nitrous oxide(N_(2)O)as an oxygen atom donor presents an attractive opportunity for green chemistry applications,leveraging both its industrial abundance and thermodynamically favorable oxidation p...The valorization of nitrous oxide(N_(2)O)as an oxygen atom donor presents an attractive opportunity for green chemistry applications,leveraging both its industrial abundance and thermodynamically favorable oxidation potential.However,practical implementation has been constrained by the inherent kinetic inertness and poor coordinating ability of N_(2)O.While prior studies achieved N_(2)O-mediated conversion of aryl halides to phenols,such transformations necessitated stoichiometric chemical reductants and elevated pressure(2 atm),posing challenges in operational safety and process scalability.This study focuses on an electrochemical strategy that enables efficient oxygen atom transfer under ambient pressure through controlled current application.This methodology facilitates the selective transformation of aryl iodides to phenols without external reducing agents,establishing an environmentally benign synthetic pathway.By replacing traditional chemical reductants with electrons as the sole reducing equivalent,our approach addresses critical sustainability challenges in aromatic oxygenation chemistry while maintaining operational simplicity under mild conditions.展开更多
Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Rama...Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Raman spectroscopy. The results showed that all the samples held the structure of MCM-48, and Ce could enter the framework of MCM-48. However, when Ce/Si molar ratio in the sampies was high （0.04 or 0.059）, there were CeO2 crystallites as secondary phase in the extraframework of MCM-48. Ce-doped MCM-48 was a very efficient catalyst for the oxidation of cyclohexane in a solvent-free system with oxygen as an oxidant. In the conditions of 0.5 MPa 02 and 413 K for 5 h, the conversion of cyclohexane was 8.1% over Ce-MCM-48-0.02, the total selectivity of cyclohexanol and cyclohaxnone was 98.7%. With an increase of Ce content, the conversion of cyclohexane and the selectivity to cyclohexanol decreased somewhat, but the selectivity to cyclohexanone increased.展开更多
Cerium oxide nanoparticles(CeO_(2)NPs)have attracted great interest recently in the field of cosmetics due to their excellent biomedical properties to treat diseases caused by reactive oxygen species(ROS).However,a re...Cerium oxide nanoparticles(CeO_(2)NPs)have attracted great interest recently in the field of cosmetics due to their excellent biomedical properties to treat diseases caused by reactive oxygen species(ROS).However,a realizable synthesis approach for the large-scale synthesis of CeO_(2)NPs reaching the quality requirements of cosmetic grade is still in desperate demand.This work reports a robust solvothermal approach for the mass production of self-assembled CeO_(2)microsphere(SA CeO_(2))up to 1000 g at a time.Depending on the concentration of initial precursors,the re sulting particle sizes can be precisely tuned to obtain micro spherical samples of SA CeO_(2)-145 nm,SA CeO_(2)-420 nm and SA CeO_(2)-680 nm.Typically,the mesoporous SA CeO_(2)-420 nm with the largest specific surface area exhibits greatly enhanced number of oxygen vacancies(Ce^(3+)cations)proved by X-ray photoelectro n spectro scopy and electron paramagnetic resonance analysis.Moreover,Turbiscan stability test reveals the superior physical stability of SA CeO_(2)-420 nm suspension based on multiple light scattering technology,which contributes to reduced in-vitro cytotoxicity assessed via MTT viability assay.Therefore,SA CeO_(2)-420 nm exhibits excellent antioxidant performance with a high DPPH free radical scavenging ratio of more than 90% at a low concentration below 1 mg/mL.Importantly,SA CeO_(2)-420 nm can effectively inhibit the in-vitro release of reactive oxygen species in mitochondria caused by UVB irradiation in HaCaT cells,exerting good antioxidant activity at the cellular level.As a consequence,a significant increase in skin color and brightness can be observed after 28 d of application of the emulsion containing SA CeO_(2)-420 nm,demonstrating the potential whitening effect.This work provides a facile and readily scalable synthetic strategy of CeO_(2)microsphere and subsequently offers an innovative avenue for their cosmetic application.展开更多
Cobalt pentlandite(Co9S8)is a promising non-precious catalyst due to its superior oxygen reduction reaction activity and excellent stability.However,its oxygen reduction reaction catalytic activity has traditionally b...Cobalt pentlandite(Co9S8)is a promising non-precious catalyst due to its superior oxygen reduction reaction activity and excellent stability.However,its oxygen reduction reaction catalytic activity has traditionally been limited to the four-electron pathway because of strong*OOH intermediate adsorption.In this study,we synthesized electron-deficient Co9S8 nanocrystals with an increased number of Co^(3+)states compared to conventional Co9S8.This was achieved by incorporating a high density of surface ligands in small-sized Co9S8nanocrystals,which enabled the transition of the electrochemical reduction pathway from four-electron oxygen reduction reaction to two-electron oxygen reduction reaction by decreasing*OOH adsorption strength.As a result,the Co^(3+)-enriched Co9S8 nanocrystals exhibited a high onset potential of 0.64 V(vs RHE)for two-electron oxygen reduction reaction,achieving H_(2)O_(2) selectivity of 70-80%over the potential range from 0.05 to 0.6 V.Additionally,these nanocrystals demonstrated a stable H_(2)O_(2) electrosynthesis at a rate of459.12 mmol g^(-1) h^(-1) with a H_(2)O_(2) Faradaic efficiency over 90%under alkaline conditions.This study provides insights into nanoscale catalyst design for modulating electrochemical reactions.展开更多
Against the backdrop of increasingly prominent global energy shortages and environmental issues,the development of efficient energy conversion and storage technologies has become crucial.Zero-dimensional(0D)metal oxid...Against the backdrop of increasingly prominent global energy shortages and environmental issues,the development of efficient energy conversion and storage technologies has become crucial.Zero-dimensional(0D)metal oxide composites exhibit significant application value in the field of energy chemistry due to their unique properties,such as quantum size effect and high specific surface area.From a broad perspective,this paper reviews the main synthesis methods of these composites,including sol-gel method,hydrothermal/solvothermal method,precipitation method,and template method,while analyzing the characteristics of each method.It further discusses their applications in photocatalytic hydrogen production,fuel cells,lithium-ion batteries,and supercapacitors.Additionally,the current challenges,such as material dispersibility and interface bonding,are pointed out,and future development directions are prospected,aiming to provide references for related research.展开更多
The research of superior water oxidation electrodes is essential for the green energy in the form of hydrogen by way of electrolytic water splitting, and still remains challenging. Based upon dealloying foam, Fe-Ni hy...The research of superior water oxidation electrodes is essential for the green energy in the form of hydrogen by way of electrolytic water splitting, and still remains challenging. Based upon dealloying foam, Fe-Ni hydroxide nanosheets network structure is designed on the surface of Fe-Ni alloy foam. The ratio of Ni/Fe elements was adjusted to realize the optimal catalytic activities for oxygen evolution reaction（OER） and hydrogen evolution reaction（HER）. The obtained electrode of Fe-Ni hydroxide nanosheets/Fe-Ni alloy foam-60% Fe（FN LDH/FNF-60, 60 is the percentage of Fe content） possess low overpotential of 261 mV to reach 10 mA/cm;, small Tafel slope（85.5 mV/dec）, and superior long-term stability（remaining 10 mA/cm;for over 14 h without attenuation） toward OER in 1.0 mol/L KOH.Moreover, an alkaline water electrolyzer is constructed with the FN LDH/FNF-60 as anode and Ni（OH）;/Fe-Ni alloy foam-25% Fe(Ni（OH）;/FNF-25) as cathode, which displays superior electrolytic performance（affording 10 mA/cm;at 1.62 V） and lasting durability.展开更多
A new crown ether appended Fe（Ⅲ） porphyrin complex was prepared by sulfuryl chloride appended benzo-15-crown-5 to the meso position of meso-5,10,15,20-tetra（4-hydrophenyl）porphyrin,and it was applied to catalytic...A new crown ether appended Fe（Ⅲ） porphyrin complex was prepared by sulfuryl chloride appended benzo-15-crown-5 to the meso position of meso-5,10,15,20-tetra（4-hydrophenyl）porphyrin,and it was applied to catalytic oxidation of cyclohexene with molecular oxygen without reductant,showing a remarkable catalytic activity（conversion is up to 94%） and selectivity for 2-cyclohexen-1-ol（73%）.展开更多
Vanadium‐chromium oxides(VCrO)were usually prepared by high‐temperature solid‐state reactions;however,mixed phases were frequently produced and the morphology of the products was not well controlled.In this work,we...Vanadium‐chromium oxides(VCrO)were usually prepared by high‐temperature solid‐state reactions;however,mixed phases were frequently produced and the morphology of the products was not well controlled.In this work,we prepared amorphous VCrO precursors by using V2O5 and CrO3 and alcohols or mixtures of alcohol and water via solvothermal reaction at 180°C.The precursors were then calcined under nitrogen at various temperatures.The products were characterized by powder X‐ray diffraction,transmission electron microscopy,and X‐ray photoelectron spectroscopy.It was revealed that pure‐phase nanocrystalline orthorhombic CrVO4 was obtained when methanol or methanol/water was used as the solvothermal medium and the precursor was calcined at 700°C.The size of the CrVO4 crystals was around 500 nm when methanol was used,whereas it reduced significantly to less than 50 nm when a mixture of methanol and water was used.The sizes could be effectively tuned from 10 to 50 nm by varying the methanol/water volume ratio.To the best of our knowledge,this is the first report on the synthesis of pure‐phase CrVO4 nanocrystals.The nano‐CrVO4 showed almost the highest catalytic activity for the ammoxidation of 2,6‐dichlorotoluene to 2,6‐dichlorobenzonitrile among the reported bi‐component composite oxides,owing to its smaller particle size,larger specific surface area,and more exposed active centers.展开更多
Here, Pd Ru nanoparticle networks（NPNs） with various compositions were synthesized through an inexpensive method in water as a green solvent, at different ratios of the H;PdCl;and RuCl;precursors. This is a fast, ro...Here, Pd Ru nanoparticle networks（NPNs） with various compositions were synthesized through an inexpensive method in water as a green solvent, at different ratios of the H;PdCl;and RuCl;precursors. This is a fast, room temperature and surfactant free strategy which is able to form high surface area metal nanosponges with a three-dimensional（3D） porous structure. The structure of as-prepared nanosponges was characterized using the techniques of field emission scanning electron microscopy（FESEM）, energy dispersive spectroscopy（EDS） and cyclic voltammetry（CV）. Then, the electrocatalytic activities of Pd Ru NPNs towards formic acid oxidation were examined by electrochemical measurements including CV,chronoamperometry, and electrochemical impedance spectroscopy（EIS）. Based on studies, it was found that the current density of formic acid oxidation（FAO） is strongly dependent on the composition of Pd Ru NPNs. The best performance was realized for Pd;Ru;NPNs compared to monometallic Pd counterpart and other bimetallic NPNs which might be ascribed to the role of Ru in the decrease of CO adsorption strength on the catalyst and consequently the priority of formic acid oxidation through the direct pathway. The Pd;Ru;NPNs also showed the maximum current density and stability in chronoamperometric measurements. In addition, comparative studies were performed between as-prepared NPNs and CNTs-supported Pd nanoparticles（Pd NPs/CNTs）. The present results demonstrated the unique structural advantages of NPNs compared to individual Pd NPs supported on the CNT which leads to the promising performance of NPNs as supportless catalysts for the oxidation of formic acid.展开更多
Different sizes of layered CoOOH were synthesized by the molten-salt-assisted method at different temperatures.X-ray diffraction and scanning electron microscope studies reveal that CoOOH grew at(003)with increasing t...Different sizes of layered CoOOH were synthesized by the molten-salt-assisted method at different temperatures.X-ray diffraction and scanning electron microscope studies reveal that CoOOH grew at(003)with increasing temperature,and its size can reach dozens of microns.X-ray absorption near edge structure and XPS studies demonstrate that the Co valence state of CoOOH-750 is trivalent,and X-ray Absorption Fine Structure shows that it had a higher symmetry and lower disorder degree,indicating that CoOOH-750 has higher crystallinity and Co3+.The results of electrochemical tests show that CoOOH-750 exhibited the best oxygen-evolution-reaction(OER)catalytic activity.展开更多
A mechanochemical redox reaction between KMnO4 and CoCl2 was developed to obtain a CoxMn1-xOy catalyst with a specific surface area of 479 m^2 g^-1,which was higher than that obtained using a co-precipitation(CP)metho...A mechanochemical redox reaction between KMnO4 and CoCl2 was developed to obtain a CoxMn1-xOy catalyst with a specific surface area of 479 m^2 g^-1,which was higher than that obtained using a co-precipitation(CP)method(34 m2 g^-1),sol-gel(SG)method(72 m^2 g^-1),or solution redox process(131 m^2 g^-1).During catalytic combustion,this CoxMn1-xOy catalyst exhibited better activity(T100 for propylene=~200℃)than the control catalysts obtained using the SG(325℃)or CP(450℃)methods.The mechanical action,mainly in the form of kinetic energy and frictional heating,may generate a high degree of interstitial porosity,while the redox reaction could contribute to good dispersion of cobalt and manganese species.Moreover,the as-prepared CoxMn1-xOy catalyst worked well in the presence of water vapor(H2O 4.2%,>60 h)or SO2(100 ppm)and at high temperature(400℃,>60 h).The structure MnO2·(CoOOH)2.93 was suggested for the current CoxMn1-xOy catalyst.This catalyst could be extended to the total oxidation of other typical hydrocarbons(T90=150°C for ethanol,T90=225°C for acetone,T90=250℃for toluene,T90=120℃for CO,and T90=540℃for CH4).Scale-up of the synthesis of CoxMn1-xOy catalyst(1 kg)can be achieved via ball milling,which may provide a potential strategy for real world catalysis.展开更多
Oscillations in temperatures of catalyst bed as well as concentrations of gas phase species at the exit of reactor were observed during the partial oxidation of methane to synthesis gas over Ru/Al2O3 in the temperatur...Oscillations in temperatures of catalyst bed as well as concentrations of gas phase species at the exit of reactor were observed during the partial oxidation of methane to synthesis gas over Ru/Al2O3 in the temperature range of 600 to 850℃.XRD,H2-TPR and in situ Raman techniques was used to characterize the catalyst.Two types of ruthenium species,i.e.the ruthenium species weakly interacted with Al2O3 and that strongly interacted with the support,were identified by H2-TPR experiment.These species are responsible for two types of oscillation profiles observed during the reaction.The oscillations were the result of these ruthenium species switching cyclically between the oxidized state and the reduced state under the reaction condition.These cyclic transformations,in turn,were the result of temperature variations caused by the varying levels of the strongly exothermic CH4 combustion and the highly endothermic CH4 reforming(with H2O and CO2)reactions(or the less exothermic direct partial oxidation of methane to CO and H2),which were favored by the oxidized and the metallic sites,respectively.The major pathway of synthesis gas formation over the catalyst was via the combustion-reforming mechanism.展开更多
基金supported by the National Natural Science Foundation of China (No.52274304)。
文摘The three-dimensional(3D) Pd-based nanoflower structures,assembled from two-dimensional(2D)nanosheets,are characterized by their stable and ordered configurations.These structures have been extensively designed as anode materials for fuel cells.However,the exploration of trimetallic nanoflowers with porous architectures remains limited.In this study,we present a straightforward one-step solvothermal method for the synthesis of trimetallic Pd Cu Ni porous nanoflowers(PNFs).Leveraging several unique advantages,such as an open superstructure,high porosity,and enhanced electronic interactions among the trimetals,the resulting Pd Cu Ni PNFs demonstrate significantly improved electrochemical performance,with mass activities reaching 5.94 and 10.14 A/mg for the ethanol oxidation reaction(EOR)and the ethylene glycol oxidation reaction(EGOR),respectively.Furthermore,the Pd Cu Ni PNFs exhibit optimized d-band centers and the most negative onset oxidation potential,indicating enhanced antitoxicity and stability.This study not only provides a novel perspective on the synthesis of 3D porous nanomaterials but also highlights the potential application value of trimetallic nanoalloys in catalysis.
基金the financial support from the National Natural Science Foundation of China(52171223)the Guangxi Science and Technology Major Project(No.AA24206007)。
文摘Ammonia borane(AB)is a promising hydrogen storage medium widely used for hydrogen generation,but its slow hydrolysis kinetics limits its applications.Medium/high-entropy materials(M/HEMs)have emerged as efficient catalysts due to their complementary elemental and structural properties.We developed a deposition in-situ reduction(D-ISR)approach for the rapid synthesis of single-phase medium/high-entropy oxides(M/HEOs)at room temperature,along with establishing general criteria for M/HEOs synthesis based on component properties.Deposition facilitates the incorporation of active elements(Ti/Zr/V/Cr/Nb),which significantly enhance the enthalpy-driven force of the dynamic oxidation(DO)process via an“active element coordination”strategy,thereby overcoming low-temperature solid solubility limitations.Nine-component HEOs and large-scale experiments confirm the universality and mass-production potential of the D-ISR approach.CoCuNiTi-O/AC synthesized via this strategy exhibits pronounced crystal distortion and disorder(Co–O coordination number=10.2),enhancing the Co–O coordination environment and mitigating Ostwald ripening.This leads to high activity and significantly enhanced structural stability,achieving a turnover frequency of 236.6 min^(-1)for ammonia borane hydrolysis,15 times higher than Co-O/AC and surpassing the most non-noble catalysts.These observations highlight an efficient M/HEOs synthesis methodology that advances M/HEMs applications in nanoenergy.
基金financially supported by National Natural Science Foundation of China(No.22207113 to J.Zhang)Guangdong Basic and Applied Basic Research Foundation(No.2021A1515110588to J.Zhang)Natural Science Foundation of Shanghai Municipality(No.22ZR1474000 to L.Wen)。
文摘Uronic acids are prevalent components of crucial glycoconjugates,pivotal in various biological processes.In nature,NDP-uronic acids,the nucleosides-activated uronic acids,serve as glycosylation donors catalyzed by uronosyltransferases(UATs)to construct glycans containing uronic acids.Despite their biological importance,the synthesis of naturally occurring NDP-uronic acids on a large scale remains challenging.Here,we developed an oxidation reaction insertion strategy for the efficient synthesis of NDP-uronic acids,and 11 NDP-uronic acids were successfully prepared in good yield and on a large scale.The prepared NDP-uronic acids can be used to explore new uronosyltransferases and synthesize uronic acids containing carbohydrates for fundamental research.
基金supported by the National Natural Science Foundation of China (51374004,51204083)the Candidate Talents Training Fund of Yun-nan Province (2012HB009,2014HB006)+2 种基金the Applied Basic Research Program of Yunnan Province (2014FB123)a School-Enterprise Cooperation Project from Jinchuan Corporation (Jinchuan 201115)the Talents Training Program of Kunming University of Science and Technology (KKZ3201352038)~~
文摘This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies（i.e.,nanorods,nanosheets,and nanocubes） were successfully synthesized,and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors.The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures（≤ 140℃）.Nanorods can be synthesized in CoCl2 solution,while Co（NO3）2 solution promotes the formation of nanosheets.Further increasing the synthesis temperature（higher than 140 ℃） results in the formation of nanocubes in either Co（NO3）2 or CoCl2 solution.The reaction time only affects the size of the obtained nanoparticles.The presence of CTAB could improve the uniformity and dispersion of particles.Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co^（3＋） on the surface,much higher reducibility,and better oxygen desorption capacity.
基金supported by the research project within the program“Excellence Initiative-Research University”for the AGH University of Krakow(IDUB AGH,Action 21)Kun Zheng acknowledges financial support from AGH University of Krakow(No.16.16.210.476).
文摘Minimizing the thermal expansion coefficient(TEC)mismatch between the cathode and electrolyte in solid oxide fuel cells is crucial for achieving stable,durable operation and high performance.Recently,materials with negative thermal expansion(NTE)have at-tracted significant attention as effective additives for tailoring the thermomechanical properties of electrodes and enhancing cell durability.In this work,for the first time,single-phase NTE perovskite Sm_(0.85)Zn_(0.15)MnO_(3−δ)(SZM15)was successfully synthesized via the sol-gel method,eliminating the unwanted ZnO phase typically observed in materials obtained through the conventional solid-state reaction route.The sol-gel approach proved highly advantageous,offering low cost,robustness,excellent chemical homogeneity,precise compositional control,and high phase purity.After optimization of synthesis parameters,a negative TEC of approximately−6.5×10^(−6)K^(−1)was achieved in the 400-850℃range.SZM15 was then incorporated as an additive(10wt%-50wt%)into a SmBa0.5Sr0.5CoCuO_(5+δ)(SBSCCO)cathode to tune the thermomechanical properties with a La_(0.8)Sr_(0.2)Ga_(0.8)Mg_(0.2)O_(3−δ)(LSGM)electrolyte,achieving a minimal TEC mismatch of only 1%.Notably,the SBSCCO+10wt%SZM15 composite cathode exhibited the lowest polarization resistance of 0.019Ω·cm^(2)at 900℃,showing approximately 70%lower than that of the pristine cathode.Excellent long-term stability after 100 h of operation was achieved.In addition,a high peak power density of 680 mW·cm^(−2)was achieved in a Ni-YSZ(yttria-stabilized zirconia)|YSZ|Ce_(0.9)Gd_(0.1)O_(2−δ)(GDC10)|SBSCCO+10wt%SZM15 anode-supported fuel cell at 850℃,highlighting the effectiveness of incorporating NTE materials as a promising strategy for regulating the thermomechanical properties and improving the long-term stability of intermediate temperature solid oxide fuel cells(IT-SOFCs).
基金Supported by the National Natural Science Foundation of China (No. 50574046, No. 50164002,)Science & Technology Foundation of Baoshan Iron and Steel Co. Ltd, Natural Science Foundation of Yunnan province (No. 2004E0058Q)School of High Learning Doctoral Subject Special Science and Research Foundation of Ministry of Education (No. 20040674005)
文摘A new technique -- the direct partial oxidation of methane to synthesis gas using lattice oxygen in molten salts medium has been introduced. Using CeO2 as the oxygen carrier, thermodynamic data were calculated in the reaction process, and the results indicated that direct partial oxidation of methane to synthesis gas using lattice oxygen of cerium oxide is feasible in theory. In a stainless steel reactor, the effects of temperature and varying amounts of γ-Al2O3 supported CeO2 on cn4 conversion, H2 and CO selectivity, were investigated, respectively. The results show that 10% CeO2/γ-Al2O3 has the maximal reaction activity at a temperature of 865 ℃ and above, the H2/CO ratio in the gas that has been produced reaches 2 and the CH4 conversion, H2 and CO selectivity reached the following percentages： i.e. 61%, 89%, and 91% at 870 ℃, respectively. In addition, increase of reaction temperature is favorable for the partial oxidation of methane.
基金supported by National Basic Research Program of China(2010CB732300,2013CB933201)National High Technology Research and Development Program of China(2011AA03A406,2012AA062703)+2 种基金the National Natural Science Foundation of China(21103048,21273150)Shu Guang Project of Shanghai Municipal Education CommissionShanghai Education Development Foundation(10SG30)
文摘Mesoporous CeO2-MnOx binary oxides with different Mn/Ce molar ratios were prepared by hydrothermal synthesis and characterized by scanning electron microscopy （SEM）, N2 sorption, X-ray diffraction （XRD）, X-ray photoelectron spectroscopy （XPS） and H2 temperature-programmed reduction （H2-TPR）. The characterization results indicated that the CeO2-MnOx catalysts exhibited flower-like microspheres with high specific surface areas, and partial Mn cations could be incorporated into CeO2 lattice to form solid solution. The CeO2-MnOx catalysts showed better catalytic activity for CO oxidation than that prepared by the coprecipitation method. Furthermore, the CeO2-MnOx catalyst with Mn/Ce molar ratio of 1 in the synthesis gel （Ce-Mn-1） exhibited the best catalytic activity, over which the conversion of CO could achieve 90% at 135 ℃. This was ascribed to presence of more Mn species with higher oxida- tion state on the surface and the better reducibility over the Ce-Mn-I catalyst than other CeO2-MnOx catalysts.
文摘In this paper, the partial oxidation of methane to synthesis gas using lattice oxygen of La1- SrxMO3-λ (M=Fe, x Mn) perovskite oxides instead of molecular oxygen was investigated. The redox circulation between 11% O2/Ar flow and 11% CH4/He flow at 900℃ shows that methane can be oxidized to CO and H2 with a selectivity of over 90.7% using the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite oxides in an appropriate reaction condition, while the lost lattice x oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of La1- SrxFeO3-λ (x≤0.2) perovskite x oxides instead of molecular oxygen to react with methane to synthesis gas in the redox mode.
基金National Natural Science Foundation of China(Project No.:52320105003,Project No.:52303019)the CAS-ANSO Co-funding Research Project(Project No.:CAS-ANSO-CF-2024)+2 种基金the National Key R&D Program of China(Project No.:2023YFC3707201)the Fundamental Research Funds for the Central Universities(Project No.:E3ET1803)China Postdoctoral Science Foundation(Project No:2024T170904)。
文摘The valorization of nitrous oxide(N_(2)O)as an oxygen atom donor presents an attractive opportunity for green chemistry applications,leveraging both its industrial abundance and thermodynamically favorable oxidation potential.However,practical implementation has been constrained by the inherent kinetic inertness and poor coordinating ability of N_(2)O.While prior studies achieved N_(2)O-mediated conversion of aryl halides to phenols,such transformations necessitated stoichiometric chemical reductants and elevated pressure(2 atm),posing challenges in operational safety and process scalability.This study focuses on an electrochemical strategy that enables efficient oxygen atom transfer under ambient pressure through controlled current application.This methodology facilitates the selective transformation of aryl iodides to phenols without external reducing agents,establishing an environmentally benign synthetic pathway.By replacing traditional chemical reductants with electrons as the sole reducing equivalent,our approach addresses critical sustainability challenges in aromatic oxygenation chemistry while maintaining operational simplicity under mild conditions.
基金the National Basic Research Program of China (2004CB719500)the Commission of Science and Technology of Shanghai Municipality (06DJ14006)Shanghai Municipal Education Commission (2008CG35)
文摘Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Raman spectroscopy. The results showed that all the samples held the structure of MCM-48, and Ce could enter the framework of MCM-48. However, when Ce/Si molar ratio in the sampies was high （0.04 or 0.059）, there were CeO2 crystallites as secondary phase in the extraframework of MCM-48. Ce-doped MCM-48 was a very efficient catalyst for the oxidation of cyclohexane in a solvent-free system with oxygen as an oxidant. In the conditions of 0.5 MPa 02 and 413 K for 5 h, the conversion of cyclohexane was 8.1% over Ce-MCM-48-0.02, the total selectivity of cyclohexanol and cyclohaxnone was 98.7%. With an increase of Ce content, the conversion of cyclohexane and the selectivity to cyclohexanol decreased somewhat, but the selectivity to cyclohexanone increased.
基金Project supported by the National Natural Science Foundation of China(22301012)the R&D Program of Beijing Municipal Education Commission(KM202310011005)。
文摘Cerium oxide nanoparticles(CeO_(2)NPs)have attracted great interest recently in the field of cosmetics due to their excellent biomedical properties to treat diseases caused by reactive oxygen species(ROS).However,a realizable synthesis approach for the large-scale synthesis of CeO_(2)NPs reaching the quality requirements of cosmetic grade is still in desperate demand.This work reports a robust solvothermal approach for the mass production of self-assembled CeO_(2)microsphere(SA CeO_(2))up to 1000 g at a time.Depending on the concentration of initial precursors,the re sulting particle sizes can be precisely tuned to obtain micro spherical samples of SA CeO_(2)-145 nm,SA CeO_(2)-420 nm and SA CeO_(2)-680 nm.Typically,the mesoporous SA CeO_(2)-420 nm with the largest specific surface area exhibits greatly enhanced number of oxygen vacancies(Ce^(3+)cations)proved by X-ray photoelectro n spectro scopy and electron paramagnetic resonance analysis.Moreover,Turbiscan stability test reveals the superior physical stability of SA CeO_(2)-420 nm suspension based on multiple light scattering technology,which contributes to reduced in-vitro cytotoxicity assessed via MTT viability assay.Therefore,SA CeO_(2)-420 nm exhibits excellent antioxidant performance with a high DPPH free radical scavenging ratio of more than 90% at a low concentration below 1 mg/mL.Importantly,SA CeO_(2)-420 nm can effectively inhibit the in-vitro release of reactive oxygen species in mitochondria caused by UVB irradiation in HaCaT cells,exerting good antioxidant activity at the cellular level.As a consequence,a significant increase in skin color and brightness can be observed after 28 d of application of the emulsion containing SA CeO_(2)-420 nm,demonstrating the potential whitening effect.This work provides a facile and readily scalable synthetic strategy of CeO_(2)microsphere and subsequently offers an innovative avenue for their cosmetic application.
基金supported by the Korea Institute of Energy Technology Evaluation and Planning(KETEP)and the Ministry of Trade,Industry&Energy(MOTIE)of the Republic of Korea(no.20224000000020)supported by the MSIT(Ministry of Science and ICT),Korea,under the ICAN(ICT Challenge and Advanced Network of HRD)support program(IITP-2024-RS-2024-00437186)supervised by the IITP(Institute for Information&Communications Technology Planning&Evaluation)。
文摘Cobalt pentlandite(Co9S8)is a promising non-precious catalyst due to its superior oxygen reduction reaction activity and excellent stability.However,its oxygen reduction reaction catalytic activity has traditionally been limited to the four-electron pathway because of strong*OOH intermediate adsorption.In this study,we synthesized electron-deficient Co9S8 nanocrystals with an increased number of Co^(3+)states compared to conventional Co9S8.This was achieved by incorporating a high density of surface ligands in small-sized Co9S8nanocrystals,which enabled the transition of the electrochemical reduction pathway from four-electron oxygen reduction reaction to two-electron oxygen reduction reaction by decreasing*OOH adsorption strength.As a result,the Co^(3+)-enriched Co9S8 nanocrystals exhibited a high onset potential of 0.64 V(vs RHE)for two-electron oxygen reduction reaction,achieving H_(2)O_(2) selectivity of 70-80%over the potential range from 0.05 to 0.6 V.Additionally,these nanocrystals demonstrated a stable H_(2)O_(2) electrosynthesis at a rate of459.12 mmol g^(-1) h^(-1) with a H_(2)O_(2) Faradaic efficiency over 90%under alkaline conditions.This study provides insights into nanoscale catalyst design for modulating electrochemical reactions.
文摘Against the backdrop of increasingly prominent global energy shortages and environmental issues,the development of efficient energy conversion and storage technologies has become crucial.Zero-dimensional(0D)metal oxide composites exhibit significant application value in the field of energy chemistry due to their unique properties,such as quantum size effect and high specific surface area.From a broad perspective,this paper reviews the main synthesis methods of these composites,including sol-gel method,hydrothermal/solvothermal method,precipitation method,and template method,while analyzing the characteristics of each method.It further discusses their applications in photocatalytic hydrogen production,fuel cells,lithium-ion batteries,and supercapacitors.Additionally,the current challenges,such as material dispersibility and interface bonding,are pointed out,and future development directions are prospected,aiming to provide references for related research.
基金supported by the Science and Technology Planning Project of Guangdong Province,China(No.2017B090916002)Tip-top Scientific and Technical Innovative Youth Talents of Guangdong Special Support Program(No.2016TQ03N541)+2 种基金Guangdong Natural Science Funds for Distinguished Young Scholar(No.2017B030306001)the National Natural Science Foundation of China(No.91745203)Guangdong Innovative and Entrepreneurial Research Team Program(No.2014ZT05N200)
文摘The research of superior water oxidation electrodes is essential for the green energy in the form of hydrogen by way of electrolytic water splitting, and still remains challenging. Based upon dealloying foam, Fe-Ni hydroxide nanosheets network structure is designed on the surface of Fe-Ni alloy foam. The ratio of Ni/Fe elements was adjusted to realize the optimal catalytic activities for oxygen evolution reaction（OER） and hydrogen evolution reaction（HER）. The obtained electrode of Fe-Ni hydroxide nanosheets/Fe-Ni alloy foam-60% Fe（FN LDH/FNF-60, 60 is the percentage of Fe content） possess low overpotential of 261 mV to reach 10 mA/cm;, small Tafel slope（85.5 mV/dec）, and superior long-term stability（remaining 10 mA/cm;for over 14 h without attenuation） toward OER in 1.0 mol/L KOH.Moreover, an alkaline water electrolyzer is constructed with the FN LDH/FNF-60 as anode and Ni（OH）;/Fe-Ni alloy foam-25% Fe(Ni（OH）;/FNF-25) as cathode, which displays superior electrolytic performance（affording 10 mA/cm;at 1.62 V） and lasting durability.
基金the National Natural Science Foundation of China(No51063006)the Key Subject Foundation of Tianshui Normal University(NoTSA0818)for providing financial support for this project
文摘A new crown ether appended Fe（Ⅲ） porphyrin complex was prepared by sulfuryl chloride appended benzo-15-crown-5 to the meso position of meso-5,10,15,20-tetra（4-hydrophenyl）porphyrin,and it was applied to catalytic oxidation of cyclohexene with molecular oxygen without reductant,showing a remarkable catalytic activity（conversion is up to 94%） and selectivity for 2-cyclohexen-1-ol（73%）.
基金supported by the National Natural Science Foundation of China(21172269)Innovation Group of Hubei Natural Science Foundation(2018CFA023)Opening Project of Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education,Jianghan University(JDGD-201809)~~
文摘Vanadium‐chromium oxides(VCrO)were usually prepared by high‐temperature solid‐state reactions;however,mixed phases were frequently produced and the morphology of the products was not well controlled.In this work,we prepared amorphous VCrO precursors by using V2O5 and CrO3 and alcohols or mixtures of alcohol and water via solvothermal reaction at 180°C.The precursors were then calcined under nitrogen at various temperatures.The products were characterized by powder X‐ray diffraction,transmission electron microscopy,and X‐ray photoelectron spectroscopy.It was revealed that pure‐phase nanocrystalline orthorhombic CrVO4 was obtained when methanol or methanol/water was used as the solvothermal medium and the precursor was calcined at 700°C.The size of the CrVO4 crystals was around 500 nm when methanol was used,whereas it reduced significantly to less than 50 nm when a mixture of methanol and water was used.The sizes could be effectively tuned from 10 to 50 nm by varying the methanol/water volume ratio.To the best of our knowledge,this is the first report on the synthesis of pure‐phase CrVO4 nanocrystals.The nano‐CrVO4 showed almost the highest catalytic activity for the ammoxidation of 2,6‐dichlorotoluene to 2,6‐dichlorobenzonitrile among the reported bi‐component composite oxides,owing to its smaller particle size,larger specific surface area,and more exposed active centers.
文摘Here, Pd Ru nanoparticle networks（NPNs） with various compositions were synthesized through an inexpensive method in water as a green solvent, at different ratios of the H;PdCl;and RuCl;precursors. This is a fast, room temperature and surfactant free strategy which is able to form high surface area metal nanosponges with a three-dimensional（3D） porous structure. The structure of as-prepared nanosponges was characterized using the techniques of field emission scanning electron microscopy（FESEM）, energy dispersive spectroscopy（EDS） and cyclic voltammetry（CV）. Then, the electrocatalytic activities of Pd Ru NPNs towards formic acid oxidation were examined by electrochemical measurements including CV,chronoamperometry, and electrochemical impedance spectroscopy（EIS）. Based on studies, it was found that the current density of formic acid oxidation（FAO） is strongly dependent on the composition of Pd Ru NPNs. The best performance was realized for Pd;Ru;NPNs compared to monometallic Pd counterpart and other bimetallic NPNs which might be ascribed to the role of Ru in the decrease of CO adsorption strength on the catalyst and consequently the priority of formic acid oxidation through the direct pathway. The Pd;Ru;NPNs also showed the maximum current density and stability in chronoamperometric measurements. In addition, comparative studies were performed between as-prepared NPNs and CNTs-supported Pd nanoparticles（Pd NPs/CNTs）. The present results demonstrated the unique structural advantages of NPNs compared to individual Pd NPs supported on the CNT which leads to the promising performance of NPNs as supportless catalysts for the oxidation of formic acid.
基金This work was supported by“Transformational Technologies for Clean Energy and Demonstration”,Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA21080200).
文摘Different sizes of layered CoOOH were synthesized by the molten-salt-assisted method at different temperatures.X-ray diffraction and scanning electron microscope studies reveal that CoOOH grew at(003)with increasing temperature,and its size can reach dozens of microns.X-ray absorption near edge structure and XPS studies demonstrate that the Co valence state of CoOOH-750 is trivalent,and X-ray Absorption Fine Structure shows that it had a higher symmetry and lower disorder degree,indicating that CoOOH-750 has higher crystallinity and Co3+.The results of electrochemical tests show that CoOOH-750 exhibited the best oxygen-evolution-reaction(OER)catalytic activity.
文摘A mechanochemical redox reaction between KMnO4 and CoCl2 was developed to obtain a CoxMn1-xOy catalyst with a specific surface area of 479 m^2 g^-1,which was higher than that obtained using a co-precipitation(CP)method(34 m2 g^-1),sol-gel(SG)method(72 m^2 g^-1),or solution redox process(131 m^2 g^-1).During catalytic combustion,this CoxMn1-xOy catalyst exhibited better activity(T100 for propylene=~200℃)than the control catalysts obtained using the SG(325℃)or CP(450℃)methods.The mechanical action,mainly in the form of kinetic energy and frictional heating,may generate a high degree of interstitial porosity,while the redox reaction could contribute to good dispersion of cobalt and manganese species.Moreover,the as-prepared CoxMn1-xOy catalyst worked well in the presence of water vapor(H2O 4.2%,>60 h)or SO2(100 ppm)and at high temperature(400℃,>60 h).The structure MnO2·(CoOOH)2.93 was suggested for the current CoxMn1-xOy catalyst.This catalyst could be extended to the total oxidation of other typical hydrocarbons(T90=150°C for ethanol,T90=225°C for acetone,T90=250℃for toluene,T90=120℃for CO,and T90=540℃for CH4).Scale-up of the synthesis of CoxMn1-xOy catalyst(1 kg)can be achieved via ball milling,which may provide a potential strategy for real world catalysis.
基金supported by the Ministry of Science and Technology of China(2005CB221401)the National Natural Science Foundation of China(20873111)the Key Science&Technology Specific Projects of Fujian Province(2009HZ10102)
文摘Oscillations in temperatures of catalyst bed as well as concentrations of gas phase species at the exit of reactor were observed during the partial oxidation of methane to synthesis gas over Ru/Al2O3 in the temperature range of 600 to 850℃.XRD,H2-TPR and in situ Raman techniques was used to characterize the catalyst.Two types of ruthenium species,i.e.the ruthenium species weakly interacted with Al2O3 and that strongly interacted with the support,were identified by H2-TPR experiment.These species are responsible for two types of oscillation profiles observed during the reaction.The oscillations were the result of these ruthenium species switching cyclically between the oxidized state and the reduced state under the reaction condition.These cyclic transformations,in turn,were the result of temperature variations caused by the varying levels of the strongly exothermic CH4 combustion and the highly endothermic CH4 reforming(with H2O and CO2)reactions(or the less exothermic direct partial oxidation of methane to CO and H2),which were favored by the oxidized and the metallic sites,respectively.The major pathway of synthesis gas formation over the catalyst was via the combustion-reforming mechanism.
