Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin f...Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin first”strategy,corn straw is converted to valuable chemicals including lignin monomers,furfural and 5-methoxymethylfurfural via a two steps process.The key of this research lies in the development of a green and low-cost catalytic process utilizing magnetic Raney Ni catalyst and high boiling point ethylene glycol.The utilization of neat ethylene glycol as the sole slovent under atmospheric conditions obviates the need for additional additives,thereby facilitating the entire process to be conducted in glass flasks and rendering it highly convenient for scaling up.In the initial step,depolymerization of corn straw lignin resulted in a monomer yield of 18.1 wt%.Subsequently,in a dimethyl carbonate system,the carbohydrate component underwent complete conversion in a one-pot process,yielding furfural and 5-methoxymethylfurfural as the primary products with an impressive yield of 47.7%.展开更多
Catalytic destruction is an ascendant technology for the abatement of volatile organic compounds(VOCs)originating fromsolvent-based industrial processes.The varied composition tends to influence each VOC’s catalytic ...Catalytic destruction is an ascendant technology for the abatement of volatile organic compounds(VOCs)originating fromsolvent-based industrial processes.The varied composition tends to influence each VOC’s catalytic behavior in the reaction mixture.We investigated the catalytic destruction of multi-component VOCs including dichloromethane(DCM)and ethyl acetate(EA),as representatives from pharmaceutical waste gases,over co-supported HxPO_(4)-RuOx/CeO_(2) catalyst.A mutual inhibitory effect relating to concentrations because of competitive adsorption was verified in the binary VOCs oxidation and EA posed a more negative effect on DCM oxidation owing to EA’s superior adsorption capacity.Preferential adsorption of EA on acidic sites(HxPO_(4)/CeO_(2))promoted DCM activation on basic sites(O^(2−))and the dominating EA oxidation blocked DCM’s access to oxidation centers(RuOx/CeO_(2)),resulting in boosted monochloromethane yield and increased chlorine deposition for DCM oxidation.The impaired redox ability of Ru species owing to chlorine deposition in turn jeopardized deep oxidation of EA and its by-products,leading to increased gaseous by-products such as acetic acid originating fromEA pyrolysis.Notably,DCM at low concentration slightly promoted EA conversion at low temperatures with or without water,consistent with the enhanced EA adsorption in co-adsorption analyses.This was mainly due to that DCM impeded the shielding effect of hydrolysate deposition from rapid EA hydrolysis depending on the decreased acidity.Moreover,water benefited EA hydrolysis but decreased CO_(2) selectivity while the generated water derived from EA was likely to affect DCM transformation.This work may provide theoretical guidance for the promotion of applied catalysts toward industrial applications.展开更多
BiVO_(4)porous spheres modified by ZnO were designed and synthesized using a facile two-step method.The resulting ZnO/BiVO_(4)composite catalysts have shown remarkable efficiency as piezoelectric catalysts for degradi...BiVO_(4)porous spheres modified by ZnO were designed and synthesized using a facile two-step method.The resulting ZnO/BiVO_(4)composite catalysts have shown remarkable efficiency as piezoelectric catalysts for degrading Rhodamine B(RhB)unde mechanical vibrations,they exhibit superior activity compared to pure ZnO.The 40wt%ZnO/BiVO_(4)heterojunction composite displayed the highest activity,along with good stability and recyclability.The enhanced piezoelectric catalytic activity can be attributed to the form ation of an I-scheme heterojunction structure,which can effectively inhibit the electron-hole recombination.Furthermore,hole(h+)and superoxide radical(·O_(2)^(-))are proved to be the primary active species.Therefore,ZnO/BiVO_(4)stands as an efficient and stable piezoelectric catalyst with broad potential application in the field of environmental water pollution treatment.展开更多
Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully...Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully synthesized via the sol–gel method and tested for their catalytic performance for simultaneous degradation of benzene and toluene.The CuMn_(2)O_(4)sample exhibited the best catalytic performance,the conversion of benzene reached 100%at 350℃,and toluene conversion reached 100%at 250℃.XRD,N_(2)adsorption-desorption,HRTEM-EDS,ED-XRF,Raman spectroscopy,H_(2)-TPR,NH_(3)-TPD,O_(2)-TPD and XPS were used to characterize the physical and chemical properties of MMn_(2)O_(4)catalysts.The excellent redox properties,high concentration of surface Mn4+,and adsorption of oxygen species over the CuMn_(2)O_(4)sample facilitated the simultaneous and efficient removal of benzene and toluene.Additionally,in situ DRIFTS illustrated the intermediate species and reaction mechanism for the synergetic catalytic oxidation of benzene and toluene.Notably,as an effective catalytic material,spinel oxide exhibited excellent synergistic degradation performance for benzene and toluene,providing some insight for the development of efficient multicomponent VOC catalysts.展开更多
Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,t...Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.展开更多
The integration of surface filtration and catalytic decomposition functions in catalytic bags enables the synergistic removal of multiple pollutants(such as dust,nitrogen oxide,acid gases,and dioxins)in a single react...The integration of surface filtration and catalytic decomposition functions in catalytic bags enables the synergistic removal of multiple pollutants(such as dust,nitrogen oxide,acid gases,and dioxins)in a single reactor,thus effectively reducing the cost and operational difficulties associated with flue gas treatment.In this study,Mn-Ce-Sm-Sn(MCSS)catalysts were prepared and loaded onto hightemperature resistant polyimide(P84)filter through ultrasonic impregnation to create composite catalytic filter.The results demonstrate that the NO conversion rates of the composite catalytic filter consistently achieve above 95%within the temperature range of 160-260℃,with a chlorobenzene T_(90)value of 230℃.The ultrasonic impregnation method effectively loaded the catalyst onto the filter,ensuring high dispersion both on the surface and inside the filter.This increased exposure of catalyst active sites enhances the catalytic activity of the composite catalytic filter.Additionally,increasing the catalyst loading leads to a gradual decrease in permeability,an increase in pressure drops and the long residence time of the flue gas,thereby improving catalytic activity.Compared to ordinary impregnation methods,ultrasonic impregnation improves the bonding strength between the catalyst and filter,as well as the permeability of the composite catalytic filter under the same loading conditions.Overall,this study presents a novel approach to prepare composite catalytic filter for the simultaneous removal of NO and chlorobenzene at low temperatures.展开更多
Although solar steam generation strategy is efficient in desalinating seawater,it is still challenging to achieve continuous solar-thermal desalination of seawater and catalytic degradation of organic pollutants.Herei...Although solar steam generation strategy is efficient in desalinating seawater,it is still challenging to achieve continuous solar-thermal desalination of seawater and catalytic degradation of organic pollutants.Herein,dynamic regulations of hydrogen bonding networks and solvation structures are realized by designing an asymmetric bilayer membrane consisting of a bacterial cellulose/carbon nanotube/Co_(2)(OH)_(2)CO_(3)nanorod top layer and a bacterial cellulose/Co_(2)(OH)_(2)CO_(3)nanorod(BCH)bottom layer.Crucially,the hydrogen bonding networks inside the membrane can be tuned by the rich surface–OH groups of the bacterial cellulose and Co_(2)(OH)_(2)CO_(3)as well as the ions and radicals in situ generated during the catalysis process.Moreover,both SO_(4)^(2−)and HSO_(5)−can regulate the solvation structure of Na^(+)and be adsorbed more preferentially on the evaporation surface than Cl^(−),thus hindering the de-solvation of the solvated Na^(+)and subsequent nucleation/growth of NaCl.Furthermore,the heat generated by the solar-thermal energy conversion can accelerate the reaction kinetics and enhance the catalytic degradation efficiency.This work provides a flow-bed water purification system with an asymmetric solar-thermal and catalytic membrane for synergistic solar thermal desalination of seawater/brine and catalytic degradation of organic pollutants.展开更多
MnCeO_(x)/P84 catalytic filters with spherical,flower-like,cubic and rod-like catalytic interfaces were synthesized respectively,and their catalytic activities in the NH_(3)-SCR reaction were investigated.The MnCeO_(x...MnCeO_(x)/P84 catalytic filters with spherical,flower-like,cubic and rod-like catalytic interfaces were synthesized respectively,and their catalytic activities in the NH_(3)-SCR reaction were investigated.The MnCeO_(x)/P84 catalytic filter with spherical catalytic interfaces(recorded as S-MnCeO_(x)/P84)exhibits the best catalytic denitration performance.The NO_(x)removal efficiency of S-MnCeO_(x)/P84 reaches the highest value of 98.6%at 160℃when the catalyst loading is 100 g/m^(2).At the same time,S-MnCeO_(x)/P84 exhibits good SO_(2)resistance and stability,achieving a NO_(x)removal rate of 83%at 190℃with 30 ppm SO_(2).The characterization results illustrate that the MnCeO_x active component in S-MnCeO_(x)/P84 is present in weak crystalline states,tightly wrapped around the surface of the filter fiber,and uniformly dispersed,and the mesopore is the main pore structure of the S-MnCeO_(x)/P84,which can provide a channel for the catalytic reaction to proceed.At the same time,transmission electron microscopy(TEM)characterization shows that y-MnO_(2)is the main form of MnO_(2)in the S-MnCeO_(x)/P84.Further analysis of H_(2)temperature programmed reduction(H_(2)-TPR).NH_(3)temperature programmed desorption(NH_(3)-TPD)and in-situ diffuse reflectance infrared spectra(DRIFTS)show that S-MnCeO_(x)/P84 has good redox ability at 100-200℃and has abundant Lewis acid sites and Bronsteds acid sites,which provides an important guarantee for its superior low-temperature NH_(3)-SCR denitration performance.展开更多
China possesses abundant heavy oil resources,yet faces challenges such as high viscosity,underdeveloped production technologies,and elevated development cost.Although the in-situ catalytic viscosity-reduction technolo...China possesses abundant heavy oil resources,yet faces challenges such as high viscosity,underdeveloped production technologies,and elevated development cost.Although the in-situ catalytic viscosity-reduction technology can address certain technical,environmental,and cost problems during the extraction process,the catalysts often suffer from poor stability and low catalytic efficiency.In this study,a green and simple room-temperature stirring method was employed to synthesize a class of highly efficient and stable 2D MOF catalysts,which possess the capability to conduct in-situ catalytic pyrolysis of heavy oil and reduce the viscosity.Under the condition of 160℃,a catalyst concentration of 0.5 wt%,and a hydrogen donor(tetralin)concentration of 2 wt%,the viscosity-reduction rate of Fe-MOF is as high as 89.09%,and it can decrease the asphaltene content by 8.42%.In addition,through the structural identification and analysis of crude oil asphaltenes,the causes for the high viscosity of heavy oil are explained at the molecular level.Through the analysis of catalytic products and molecular dynamics simulation,the catalytic mechanism is studied.It is discovered that Fe-MOF can interact with heavy oil macromolecules via coordination and pore-channel effects,facilitating their cracking and dispersal.Furthermore,synergistic interactions between Fe-MOF and the hydrogen donor facilitates hydrogenation reactions and enhances the viscosity-reducing effect.This study provides a novel strategy for boosting heavy oil recovery and underscores the potential of 2D MOFs in catalytic pyrolysis applications.展开更多
The efficient mineralization of phenol and its derivatives in wastewater remains a great challenge.In this study,the bimetallic CuCeO_(2)-BTC was screened from a series of MOFs-derived MCeO_(2)-BTC(M=La,Cu,Co,Fe,and M...The efficient mineralization of phenol and its derivatives in wastewater remains a great challenge.In this study,the bimetallic CuCeO_(2)-BTC was screened from a series of MOFs-derived MCeO_(2)-BTC(M=La,Cu,Co,Fe,and Mn)catalysts,and the influence of the Cu/Ce ratio on phenol removal by catalytic ozonation was carefully examined.The results indicate that Cu_(2)Ce_(1)O_(y)-BTC was the best among the Cu_(x)Ce_(1)O_(y)-BTC(x=0,1,2,and 3)catalysts,with a phenol mineralization efficiency reaching close to 100%within 200 min,approximately 30.1%higher than CeO_(2)-BTC/O_(3)and 70.3%higher than O_(3)alone.The order of mineralization efficiency of phenol was Cu_(2)Ce_(1)O_(y)-BTC>Cu_(3)Ce_(1)O_(y)-BTC>Cu_(1)Ce_(1)O_(y)-BTC>CeO_(2)-BTC.CeO_(2)-BTC exhibited a broccoli-like morphology,and Cu_(x)Ce_(1)O_(y)-BTC(x=1,2,and 3)exhibited an urchin-like morphology.Compared with Cu_(x)Ce_(1)O_(y)-BTC(x=0,1,and 3),Cu_(2)Ce_(1)O_(y)-BTC exhibited a larger specific surface area and pore volume.This characteristic contributed to the availability of more active sites for phenol degradation.The redox ability was greatly enhanced as well.Besides,the surface of Cu_(2)Ce_(1)O_(y)-BTC exhibited a higher concentration of Ce^(3+)species and hydroxyl groups,which facilitated the dissociation of ozone and the generation of active radicals.Based on the results of radical quenching experiments and the intermediates detected by LC-MS,a potential mechanism for phenol degradation in the Cu_(2)Ce_(1)O_(y)-BTC/O_(3)system was postulated.This study offers novel perspectives on the advancement of MOFs-derived catalysts for achieving the complete mineralization of phenol in wastewater through catalytic ozonation.展开更多
By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68...By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68H_(2)O(1)has been successfully obtained via one-pot method and systematically characterized by IR,XPS,solid UV spectra,PXRD pattern,and TGA analysis.The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate.The catalytic oxidation of sulfides by 1 are carried out,which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion(100%)and high selectivity(100%).展开更多
Quantitatively mapping enzyme sequence-catalysis landscapes remains a critical challenge in understanding enzyme function,evolution,and design.In this study,we leveraged emerging microfluidic technology to measure cat...Quantitatively mapping enzyme sequence-catalysis landscapes remains a critical challenge in understanding enzyme function,evolution,and design.In this study,we leveraged emerging microfluidic technology to measure catalytic constants-kcat and KM-for hundreds of diverse orthologs and mutants of adenylate kinase(ADK).We dissected this sequence-catalysis landscape's topology,navigability,and mechanistic underpinnings,revealing catalytically heterogeneous neighborhoods organized by domain architecture.展开更多
Catalytic electron donor-acceptor(EDA) complex photochemistry has recently emerged as a popular and sustainable alternative to photoredox synthetic methods. Yet, the catalytic EDA strategy is still in its infancy for ...Catalytic electron donor-acceptor(EDA) complex photochemistry has recently emerged as a popular and sustainable alternative to photoredox synthetic methods. Yet, the catalytic EDA strategy is still in its infancy for organic synthesis due to the challenges of designing novel catalytic paradigm and expanding the substrate and reaction scope. Here, we disclose a catalytic EDA/Cu cooperative strategy by employing Na I as a catalytic donor for copper-catalyzed radical asymmetric carbocyanation. A diverse range of synthetically useful chiral benzyl nitriles are produced with high enantioselectivities. This synergetic EDA/copper catalysis enables the decarboxylative cyanation without request of any photoredox catalysts, further expanding the synthetic potential of catalytic EDA chemistry in organic synthesis.展开更多
The practical application of lithium-sulfur(Li-S)batteries is hindered by the sluggish redox kinetics of sulfur,significant volume expansion,and the shuttle effect of lithium polysulfides(LiPSs).To address these chall...The practical application of lithium-sulfur(Li-S)batteries is hindered by the sluggish redox kinetics of sulfur,significant volume expansion,and the shuttle effect of lithium polysulfides(LiPSs).To address these challenges,this study utilizes hollow carbon spheres(HCS)as a matrix,incorporating a heterojunction of transition metal sulfides(CoS_(2)/MoS_(2))as the sulfur host.The HCS,with their ultrahigh specific surface area,effectively mitigate structural damage to the cathode caused by sulfur’s volume expansion during charge and discharge cycles.Meanwhile,the CoS_(2)/MoS_(2)heterojunction provides abundant chemical adsorption and reaction sites,which accelerate the redox kinetics of sulfur and alleviating the shuttle effect of LiPSs.Density functional theory(DFT)calculations reveal that the coupling effect at the CoS_(2)/MoS_(2)heterointerface significantly enhances charge transfer and adsorption interactions between CoS_(2)/MoS_(2)and LiPSs.Experimental results demonstrate that Li-S batteries with S/CoS_(2)/MoS_(2)@HCS composites as the cathode exhibit an exceptionally low capacity decay rate of only 0.023%per cycle after 1200 cycles at 2.0 C.Even with high sulfur loading(7.9 mg cm^(−2))and a low electrolyte-to-sulfur(E/S)ratio(6.0μL mg^(−1)),the battery achieves an outstanding areal capacity of 6.86 mA h cm^(−2).This study develops a highly efficient CoS_(2)/MoS_(2)heterojunction within HCS for the adsorption and conversion of LiPSs,providing valuable insights into the design of high-performance cathode materials for Li-S batteries.展开更多
Copper extraction from chalcopyrite is challenging,because acid dissolution is slow,occurring incongruently via a complex three-step reaction mechanism.Silver has been known to catalyse copper extraction from chalcopy...Copper extraction from chalcopyrite is challenging,because acid dissolution is slow,occurring incongruently via a complex three-step reaction mechanism.Silver has been known to catalyse copper extraction from chalcopyrite since the 1970's;yet the mechanism remains controversial.Microcharacterisation of experimental products obtained under optimal leaching conditions(50-150μm chalcopyrite grains in ferric/ferrous-sulfate solution with a redox potential around 500 mV vs.Ag/AgCl,approximately 1ppm Ag;[Ag]6.4×10^(−6)mol/L;70℃;4 days)highlights the heterogeneity of the reaction:µm-thick layers of a porous copper-sulfide with variable composition formed both in cracks within,and on the surface of the chalcopyrite grains.There is no evidence for formation of Ag-rich phases(Ag_(2)S_((s)),Ag_((s)^(0))).The fundamental three-step reaction mechanism remains the same with or without added silver;silver merely accelerates the initial dissolution step.An integrated model for the catalytic effect of silver is proposed that incorporates recent advances in the reactivity of sulfide minerals.The initial reaction follows a‘Fluid-Induced Solid State Diffusion Mechanism’,where diffusion of Fe in the chalcopyrite lattice is driven towards the surface by its rapid removal into solution,resulting in a Fe-deficient surface layer.The large Ag+ion,relative to Cu+/Fe3+,diffuses into this Fe-deficient surface layer and accelerates chalcopyrite dissolution in the subsequent step,whereby chalcopyrite is replaced by copper sulfides via an interface coupled dissolution reprecipitation reaction as a consequence of the sulfide-rich micro-environment at the mineral surface.Effective Ag+recycling is key to the catalytic effect of silver,and occurs as a result of the strong affinity of Ag+for bisulfide ligands accumulating at the surface of dissolving chalcopyrite.展开更多
A novel tetra-europium(III)-containing antimonotungstate,Na_(8.2)[H_(2)N(CH_(3))_(2)]_(9)[Na_(10.8)(tar)_(4)(H_(2)O)_(20)(Eu_(2)Sb_(2)W_(21)O_(72))_(2)]·44.5H_(2)O(EuSbW,H_(4)tar=dl-tartaric acid),has been synthe...A novel tetra-europium(III)-containing antimonotungstate,Na_(8.2)[H_(2)N(CH_(3))_(2)]_(9)[Na_(10.8)(tar)_(4)(H_(2)O)_(20)(Eu_(2)Sb_(2)W_(21)O_(72))_(2)]·44.5H_(2)O(EuSbW,H_(4)tar=dl-tartaric acid),has been synthesized and characterized.The dimeric polyoxoanion of EuSbW consists of two Dawson-like{Eu_(2)Sb_(2)W_(21)}units bridged by four dl-tartaric acid ligands.The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different{Eu_(2)Sb_(2)W_(21)}units,thereby forming the dimeric structure.EuSbW represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two{Eu_(2)Sb_(2)W_(21)}units.Additionally,EuSbW exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols,achieving 100%conversion and>99%selectivity for various thioethers,and 85–100%conversion with 90–99%selectivity for diverse alcohols under mild conditions.展开更多
The reduction of nitrobenzene to aniline is very important for both pollution control and chemical synthesis.Nevertheless,difficulties still remain in developing a catalytic system having high efficiency and selectivi...The reduction of nitrobenzene to aniline is very important for both pollution control and chemical synthesis.Nevertheless,difficulties still remain in developing a catalytic system having high efficiency and selectivity for the production of aniline.Herein,it was found that PdO nanoparticles highly dispersed on TiO_(2)support(PdO/TiO_(2))functioned as a highly efficient catalyst for the reduction of nitrobenzene in the presence of NaBH4.Under favorable conditions,95%of the added nitrobenzene(1 mmol/L)was reduced within 1 min with an ultra-low apparent activation energy of 10.8 kJ/mol by using 0.5%PdO/TiO_(2)as catalysts and 2 mmol/L of NaBH4 as reductants,and the selectivity to aniline even reached up to 98%.The active hydrogen specieswere perceived as dominant species during the hydrogenation of nitrobenzene by the results of isotope labeling experiments and ESR spectroscopic.A mechanismwas proposed as follows:PdO activates the nitro groups and leads to in-situ generation of Pd,and the generated Pd acts as the reduction sites to produce active hydrogen species.In this catalytic system,nitrobenzene prefers to be adsorbed on the PdO nanoparticles of the PdO/TiO_(2)composite.Subsequently,the addition of NaBH_(4) results in in-situ generation of a Pd/PdO/TiO_(2)composite from the PdO/TiO_(2)composite,and the Pd nanoclusters would activate NaBH_(4) to generate active hydrogen species to attack the adsorbed nitro groups.This work will open up a new approach for the catalytic transfer hydrogenation of nitrobenzene to aniline in green chemistry.展开更多
Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor...Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor often fails to create a suitable structure for sodium-ion storage.Molecular-level control of graphitization with open channels for Na^(+)ions is crucial for high-performance hard carbon,whereas closed pores play a key role in improving the low-voltage(<0.1 V)plateau capacity of hard carbon anodes for SIBs.However,creation of these closed pores presents significant challenges.This work proposes a zinc gluconate-assisted catalytic carbonization strategy to regulate graphitization and create numerous nanopores simultaneously.As the temperature increases,trace amounts of zinc remain as single atoms in the hard carbon,featuring a uniform coordination structure.This mitigates the risk of electrochemically irreversible sites and enhances sodium-ion transport rates.The resulting hard carbon shows an excellent reversible capacity of 348.5 mAh g^(-1) at 30 mA g^(-1) and a high ICE of 92.84%.Furthermore,a sodium storage mechanism involving“adsorption-intercalation-pore filling”is elucidated,providing insights into the pore structure and dynamic pore-filling process.展开更多
The magnesium-based materials are acknowledged as one of the most promising solid-state hydrogen storage mediums,attributed to their superior hydrogen storage capacity.Nevertheless,challenges such as sluggish kinetics...The magnesium-based materials are acknowledged as one of the most promising solid-state hydrogen storage mediums,attributed to their superior hydrogen storage capacity.Nevertheless,challenges such as sluggish kinetics,thermodynamic stability,inadequate cycling stability,and difficulties in activation impede the commercial utilization of Mg-based composites.Research indicates that reducing material dimensions to the nanoscale represents an efficacious strategy to address these issues.In this work,we systematically analyze the impact of nanosizing on Mg-based composites from three perspectives:nano-substrate modulation,nano-catalyst construction,and nano-catalytic mechanism.This analysis aims to provide guidance for the optimization and development of nanosizing strategies.For the regulation of nanosizing of Mg-based composites,the nanosizing of multi-element micro-alloyed Mg-rich systems,the integrated synthesis of multi-element multi-component nano-catalysts,and the coexistence of multiple nano-catalytic mechanisms are proposed in the light of the current state of the art research,artificial intelligence technology,and advanced characterization technology to achieve efficient,multidimensional,and simultaneous regulation of the hydrogen storage performance of Mg-based composites.This paper also envisions future directions and potential applications,emphasizing the importance of interdisciplinary approaches that integrate material science,chemistry,and computational modeling to overcome existing limitations and unlock the full potential of Mg-based hydrogen storage technologies.展开更多
The selective catalytic deoxygenation of oxy-organics in Fischer-Tropsch mixed oil for its high value utilization is challenging.Herein,a BaCO_(3)/γ-Al_(2)O_(3) catalyst was prepared calciningγ-Al_(2)O_(3) with BaCO...The selective catalytic deoxygenation of oxy-organics in Fischer-Tropsch mixed oil for its high value utilization is challenging.Herein,a BaCO_(3)/γ-Al_(2)O_(3) catalyst was prepared calciningγ-Al_(2)O_(3) with BaCO_(3),and the acid-alkalinity of the catalyst was regulated by introducing alkaline Ba basic sties.In a co ntinuous fixed-bed reactor with a feed mass space velocity of 1 h~(-1)and reaction temperature of 330℃,BaCO_(3)/γ-Al_(2)O_(3) catalyst can efficiently catalyzed the deoxygenation removal of 1-octanol in Fischer-Tropsch C10mixture oil.It also inhibited the isomerization of 1-decene in the C10 mixture.The catalytic deoxygenation kinetics of 1-octanol were also studied.The reaction was endothermic with an activation energy of 64 kJ·mol^(-1)and a reaction order of 2.In addition,theoretical studies revealed the adsorption and activation of 1-decene on the Lewis acidic site and the alkaline Ba basic sites,1-decene was more easily underwent isomerization into 2-decene at Lewis acid sites.This research provides a useful method to enable the industrial application of catalytic deoxygenation of alcohols in Fischer-Tropsch synthetic oil.展开更多
基金supported by the Fundamental Research Funds for the Central Universities(QNTD202302)National Natural Science Foundation of China(22378024)the Foreign expert program(G2022109001L).
文摘Developing a cost-effective and environmentally friendly process for the production of valuable chemicals from abundant herbal biomass receives great attentions in recent years.Herein,taking advantage of the“lignin first”strategy,corn straw is converted to valuable chemicals including lignin monomers,furfural and 5-methoxymethylfurfural via a two steps process.The key of this research lies in the development of a green and low-cost catalytic process utilizing magnetic Raney Ni catalyst and high boiling point ethylene glycol.The utilization of neat ethylene glycol as the sole slovent under atmospheric conditions obviates the need for additional additives,thereby facilitating the entire process to be conducted in glass flasks and rendering it highly convenient for scaling up.In the initial step,depolymerization of corn straw lignin resulted in a monomer yield of 18.1 wt%.Subsequently,in a dimethyl carbonate system,the carbohydrate component underwent complete conversion in a one-pot process,yielding furfural and 5-methoxymethylfurfural as the primary products with an impressive yield of 47.7%.
基金supported by the National Natural Science Foundation of China (Nos.21906087 and 52070168)the Key R&D Plan of Zhejiang Province (No.2023C03127)the Fundamental Research Funds for the Central Universities (No.226-2022-00150).
文摘Catalytic destruction is an ascendant technology for the abatement of volatile organic compounds(VOCs)originating fromsolvent-based industrial processes.The varied composition tends to influence each VOC’s catalytic behavior in the reaction mixture.We investigated the catalytic destruction of multi-component VOCs including dichloromethane(DCM)and ethyl acetate(EA),as representatives from pharmaceutical waste gases,over co-supported HxPO_(4)-RuOx/CeO_(2) catalyst.A mutual inhibitory effect relating to concentrations because of competitive adsorption was verified in the binary VOCs oxidation and EA posed a more negative effect on DCM oxidation owing to EA’s superior adsorption capacity.Preferential adsorption of EA on acidic sites(HxPO_(4)/CeO_(2))promoted DCM activation on basic sites(O^(2−))and the dominating EA oxidation blocked DCM’s access to oxidation centers(RuOx/CeO_(2)),resulting in boosted monochloromethane yield and increased chlorine deposition for DCM oxidation.The impaired redox ability of Ru species owing to chlorine deposition in turn jeopardized deep oxidation of EA and its by-products,leading to increased gaseous by-products such as acetic acid originating fromEA pyrolysis.Notably,DCM at low concentration slightly promoted EA conversion at low temperatures with or without water,consistent with the enhanced EA adsorption in co-adsorption analyses.This was mainly due to that DCM impeded the shielding effect of hydrolysate deposition from rapid EA hydrolysis depending on the decreased acidity.Moreover,water benefited EA hydrolysis but decreased CO_(2) selectivity while the generated water derived from EA was likely to affect DCM transformation.This work may provide theoretical guidance for the promotion of applied catalysts toward industrial applications.
基金financially supported by the National Natural Science Foundation of China(No.22272151)Public Welfare Technology Application Research Project of Jinhua City,China(No.2023-4-022)。
文摘BiVO_(4)porous spheres modified by ZnO were designed and synthesized using a facile two-step method.The resulting ZnO/BiVO_(4)composite catalysts have shown remarkable efficiency as piezoelectric catalysts for degrading Rhodamine B(RhB)unde mechanical vibrations,they exhibit superior activity compared to pure ZnO.The 40wt%ZnO/BiVO_(4)heterojunction composite displayed the highest activity,along with good stability and recyclability.The enhanced piezoelectric catalytic activity can be attributed to the form ation of an I-scheme heterojunction structure,which can effectively inhibit the electron-hole recombination.Furthermore,hole(h+)and superoxide radical(·O_(2)^(-))are proved to be the primary active species.Therefore,ZnO/BiVO_(4)stands as an efficient and stable piezoelectric catalyst with broad potential application in the field of environmental water pollution treatment.
基金supported by the National Natural Science Foundation of China(Nos.22206146,22006079,and U21A20524)the Fundamental Research Funds for the Central Universities,the Youth Innovation Promotion Association of Chinese Academy of Sciences,the Fundamental Research Program of Shanxi Province(No.202103021223280)+1 种基金the Special Fund for Science and Technology Innovation Teams of Shanxi Province(No.202204051002026)the Natural Science Foundation of Shandong Province(No.ZR2021QB133).
文摘Owing to the complexity of multicomponent gases,developing multifunctional catalysts for synergistic removal of benzene and toluene remains challenging.The spinel MMn_(2)O_(4)(M=Co,Ni,or Cu)catalysts were successfully synthesized via the sol–gel method and tested for their catalytic performance for simultaneous degradation of benzene and toluene.The CuMn_(2)O_(4)sample exhibited the best catalytic performance,the conversion of benzene reached 100%at 350℃,and toluene conversion reached 100%at 250℃.XRD,N_(2)adsorption-desorption,HRTEM-EDS,ED-XRF,Raman spectroscopy,H_(2)-TPR,NH_(3)-TPD,O_(2)-TPD and XPS were used to characterize the physical and chemical properties of MMn_(2)O_(4)catalysts.The excellent redox properties,high concentration of surface Mn4+,and adsorption of oxygen species over the CuMn_(2)O_(4)sample facilitated the simultaneous and efficient removal of benzene and toluene.Additionally,in situ DRIFTS illustrated the intermediate species and reaction mechanism for the synergetic catalytic oxidation of benzene and toluene.Notably,as an effective catalytic material,spinel oxide exhibited excellent synergistic degradation performance for benzene and toluene,providing some insight for the development of efficient multicomponent VOC catalysts.
文摘Lithium-sulfur(Li-S)batteries have great promise for next-generation energy storage devices due to the high theoretical specific capacity(1675 mAh g^(-1))of sulfur with chemical conversion for charge storage.However,their practical use is hindered by the slow redox kinetics of sulfur and the“shuttle effect”arising from dissolved lithium polysulfides(LiPSs).In recent years,various carbon-based materials have served as sulfur hosts and catalysts for accelerating sulfur conversion redox kinetics and alleviating LiPS shuttling.However,they often suffer from irreversible passivation and structural changes that destroy their long-term performance.We consider the main problems limiting their stability,including excessive LiPS adsorption,passivation by insulating Li2S,and surface reconstruction,and clarify how these factors lead to capacity fade.We then outline effective strategies for achieving long-term sulfur catalysis,focusing on functional carbon,such as designing suitable carbon-supported catalyst interfaces,creating well-distributed active sites,adding cocatalysts to improve electron transfer,and using carbon-based protective layers to suppress unwanted side reactions.Using this information should enable the development of stable,high-activity catalysts capable of long-term operation under practical conditions in Li-S batteries.
基金Project supported by the National Key Research and Development Program of China(2021YFB3500600,2021YFB3500605)Natural Science Foundation of Jiangsu Province(BK20220365)+5 种基金Key R&D Program of Jiangsu Province(BE2022142)Natural Science Foundation of the Jiangsu Higher Education Institutions of China(22KJB610002)Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23_1419)Science and Technology Plan of Yangzhou(YZ2022030,YZ2023020)the State Key Laboratory of Clean and Efficient Coal-fired Power Generation and Pollution Control(D2022FK098)。
文摘The integration of surface filtration and catalytic decomposition functions in catalytic bags enables the synergistic removal of multiple pollutants(such as dust,nitrogen oxide,acid gases,and dioxins)in a single reactor,thus effectively reducing the cost and operational difficulties associated with flue gas treatment.In this study,Mn-Ce-Sm-Sn(MCSS)catalysts were prepared and loaded onto hightemperature resistant polyimide(P84)filter through ultrasonic impregnation to create composite catalytic filter.The results demonstrate that the NO conversion rates of the composite catalytic filter consistently achieve above 95%within the temperature range of 160-260℃,with a chlorobenzene T_(90)value of 230℃.The ultrasonic impregnation method effectively loaded the catalyst onto the filter,ensuring high dispersion both on the surface and inside the filter.This increased exposure of catalyst active sites enhances the catalytic activity of the composite catalytic filter.Additionally,increasing the catalyst loading leads to a gradual decrease in permeability,an increase in pressure drops and the long residence time of the flue gas,thereby improving catalytic activity.Compared to ordinary impregnation methods,ultrasonic impregnation improves the bonding strength between the catalyst and filter,as well as the permeability of the composite catalytic filter under the same loading conditions.Overall,this study presents a novel approach to prepare composite catalytic filter for the simultaneous removal of NO and chlorobenzene at low temperatures.
基金Financial support from the National Natural Science Foundation of China(51972016)the Fundamental Research Funds for the Central Universities(JD2417)is gratefully acknowledged.
文摘Although solar steam generation strategy is efficient in desalinating seawater,it is still challenging to achieve continuous solar-thermal desalination of seawater and catalytic degradation of organic pollutants.Herein,dynamic regulations of hydrogen bonding networks and solvation structures are realized by designing an asymmetric bilayer membrane consisting of a bacterial cellulose/carbon nanotube/Co_(2)(OH)_(2)CO_(3)nanorod top layer and a bacterial cellulose/Co_(2)(OH)_(2)CO_(3)nanorod(BCH)bottom layer.Crucially,the hydrogen bonding networks inside the membrane can be tuned by the rich surface–OH groups of the bacterial cellulose and Co_(2)(OH)_(2)CO_(3)as well as the ions and radicals in situ generated during the catalysis process.Moreover,both SO_(4)^(2−)and HSO_(5)−can regulate the solvation structure of Na^(+)and be adsorbed more preferentially on the evaporation surface than Cl^(−),thus hindering the de-solvation of the solvated Na^(+)and subsequent nucleation/growth of NaCl.Furthermore,the heat generated by the solar-thermal energy conversion can accelerate the reaction kinetics and enhance the catalytic degradation efficiency.This work provides a flow-bed water purification system with an asymmetric solar-thermal and catalytic membrane for synergistic solar thermal desalination of seawater/brine and catalytic degradation of organic pollutants.
基金Project supported by the National Natural Science Foundation of China(51902166)the Natural Science Foundation of Jiangsu Province(BK20190786)+1 种基金Jiangsu Collaborative Innovation Center of Atmospheric Environment and Equipment Technology(CICAEET)Jiangsu Key Laboratory of Atmospheric Environment Monitoring and Pollution Control。
文摘MnCeO_(x)/P84 catalytic filters with spherical,flower-like,cubic and rod-like catalytic interfaces were synthesized respectively,and their catalytic activities in the NH_(3)-SCR reaction were investigated.The MnCeO_(x)/P84 catalytic filter with spherical catalytic interfaces(recorded as S-MnCeO_(x)/P84)exhibits the best catalytic denitration performance.The NO_(x)removal efficiency of S-MnCeO_(x)/P84 reaches the highest value of 98.6%at 160℃when the catalyst loading is 100 g/m^(2).At the same time,S-MnCeO_(x)/P84 exhibits good SO_(2)resistance and stability,achieving a NO_(x)removal rate of 83%at 190℃with 30 ppm SO_(2).The characterization results illustrate that the MnCeO_x active component in S-MnCeO_(x)/P84 is present in weak crystalline states,tightly wrapped around the surface of the filter fiber,and uniformly dispersed,and the mesopore is the main pore structure of the S-MnCeO_(x)/P84,which can provide a channel for the catalytic reaction to proceed.At the same time,transmission electron microscopy(TEM)characterization shows that y-MnO_(2)is the main form of MnO_(2)in the S-MnCeO_(x)/P84.Further analysis of H_(2)temperature programmed reduction(H_(2)-TPR).NH_(3)temperature programmed desorption(NH_(3)-TPD)and in-situ diffuse reflectance infrared spectra(DRIFTS)show that S-MnCeO_(x)/P84 has good redox ability at 100-200℃and has abundant Lewis acid sites and Bronsteds acid sites,which provides an important guarantee for its superior low-temperature NH_(3)-SCR denitration performance.
基金supported by the National Natural Science Foundation of China(52174047)Sinopec Project(No.P23138).
文摘China possesses abundant heavy oil resources,yet faces challenges such as high viscosity,underdeveloped production technologies,and elevated development cost.Although the in-situ catalytic viscosity-reduction technology can address certain technical,environmental,and cost problems during the extraction process,the catalysts often suffer from poor stability and low catalytic efficiency.In this study,a green and simple room-temperature stirring method was employed to synthesize a class of highly efficient and stable 2D MOF catalysts,which possess the capability to conduct in-situ catalytic pyrolysis of heavy oil and reduce the viscosity.Under the condition of 160℃,a catalyst concentration of 0.5 wt%,and a hydrogen donor(tetralin)concentration of 2 wt%,the viscosity-reduction rate of Fe-MOF is as high as 89.09%,and it can decrease the asphaltene content by 8.42%.In addition,through the structural identification and analysis of crude oil asphaltenes,the causes for the high viscosity of heavy oil are explained at the molecular level.Through the analysis of catalytic products and molecular dynamics simulation,the catalytic mechanism is studied.It is discovered that Fe-MOF can interact with heavy oil macromolecules via coordination and pore-channel effects,facilitating their cracking and dispersal.Furthermore,synergistic interactions between Fe-MOF and the hydrogen donor facilitates hydrogenation reactions and enhances the viscosity-reducing effect.This study provides a novel strategy for boosting heavy oil recovery and underscores the potential of 2D MOFs in catalytic pyrolysis applications.
基金supported by the National Natural Science Foundation of China(No.22206013).
文摘The efficient mineralization of phenol and its derivatives in wastewater remains a great challenge.In this study,the bimetallic CuCeO_(2)-BTC was screened from a series of MOFs-derived MCeO_(2)-BTC(M=La,Cu,Co,Fe,and Mn)catalysts,and the influence of the Cu/Ce ratio on phenol removal by catalytic ozonation was carefully examined.The results indicate that Cu_(2)Ce_(1)O_(y)-BTC was the best among the Cu_(x)Ce_(1)O_(y)-BTC(x=0,1,2,and 3)catalysts,with a phenol mineralization efficiency reaching close to 100%within 200 min,approximately 30.1%higher than CeO_(2)-BTC/O_(3)and 70.3%higher than O_(3)alone.The order of mineralization efficiency of phenol was Cu_(2)Ce_(1)O_(y)-BTC>Cu_(3)Ce_(1)O_(y)-BTC>Cu_(1)Ce_(1)O_(y)-BTC>CeO_(2)-BTC.CeO_(2)-BTC exhibited a broccoli-like morphology,and Cu_(x)Ce_(1)O_(y)-BTC(x=1,2,and 3)exhibited an urchin-like morphology.Compared with Cu_(x)Ce_(1)O_(y)-BTC(x=0,1,and 3),Cu_(2)Ce_(1)O_(y)-BTC exhibited a larger specific surface area and pore volume.This characteristic contributed to the availability of more active sites for phenol degradation.The redox ability was greatly enhanced as well.Besides,the surface of Cu_(2)Ce_(1)O_(y)-BTC exhibited a higher concentration of Ce^(3+)species and hydroxyl groups,which facilitated the dissociation of ozone and the generation of active radicals.Based on the results of radical quenching experiments and the intermediates detected by LC-MS,a potential mechanism for phenol degradation in the Cu_(2)Ce_(1)O_(y)-BTC/O_(3)system was postulated.This study offers novel perspectives on the advancement of MOFs-derived catalysts for achieving the complete mineralization of phenol in wastewater through catalytic ozonation.
基金financially supported by the National Natural Science Foundation of China(No.22071043).
文摘By introduction of hydrogen peroxide into the reaction system of ZrOCl_(2)·8H_(2)O and K14[As_(2)W_(19)O_(67)(H_(2)O)],a novel polyoxometalate K_(8)Na_(19.5)H_(0.5)[Zr_(2)(O_(2))_(2)(β-AsVW_(10)O_(38))]4·68H_(2)O(1)has been successfully obtained via one-pot method and systematically characterized by IR,XPS,solid UV spectra,PXRD pattern,and TGA analysis.The analysis of X-ray crystallography exhibits that compound 1 crystallizes in the triclinic space group P-1 and presents a novel square-shaped Zr-substituted tetrameric polyoxometalate.The catalytic oxidation of sulfides by 1 are carried out,which demonstrate that 1 exhibits a good performance for the catalytic oxidation of sulfides to sulfones with high conversion(100%)and high selectivity(100%).
文摘Quantitatively mapping enzyme sequence-catalysis landscapes remains a critical challenge in understanding enzyme function,evolution,and design.In this study,we leveraged emerging microfluidic technology to measure catalytic constants-kcat and KM-for hundreds of diverse orthologs and mutants of adenylate kinase(ADK).We dissected this sequence-catalysis landscape's topology,navigability,and mechanistic underpinnings,revealing catalytically heterogeneous neighborhoods organized by domain architecture.
基金the National Natural Science Foundation of China (No. 22201087) for the financial support。
文摘Catalytic electron donor-acceptor(EDA) complex photochemistry has recently emerged as a popular and sustainable alternative to photoredox synthetic methods. Yet, the catalytic EDA strategy is still in its infancy for organic synthesis due to the challenges of designing novel catalytic paradigm and expanding the substrate and reaction scope. Here, we disclose a catalytic EDA/Cu cooperative strategy by employing Na I as a catalytic donor for copper-catalyzed radical asymmetric carbocyanation. A diverse range of synthetically useful chiral benzyl nitriles are produced with high enantioselectivities. This synergetic EDA/copper catalysis enables the decarboxylative cyanation without request of any photoredox catalysts, further expanding the synthetic potential of catalytic EDA chemistry in organic synthesis.
基金supported in part by the Institute for Advanced Study of Central South University and the High Performance Computing Center of Central South University。
文摘The practical application of lithium-sulfur(Li-S)batteries is hindered by the sluggish redox kinetics of sulfur,significant volume expansion,and the shuttle effect of lithium polysulfides(LiPSs).To address these challenges,this study utilizes hollow carbon spheres(HCS)as a matrix,incorporating a heterojunction of transition metal sulfides(CoS_(2)/MoS_(2))as the sulfur host.The HCS,with their ultrahigh specific surface area,effectively mitigate structural damage to the cathode caused by sulfur’s volume expansion during charge and discharge cycles.Meanwhile,the CoS_(2)/MoS_(2)heterojunction provides abundant chemical adsorption and reaction sites,which accelerate the redox kinetics of sulfur and alleviating the shuttle effect of LiPSs.Density functional theory(DFT)calculations reveal that the coupling effect at the CoS_(2)/MoS_(2)heterointerface significantly enhances charge transfer and adsorption interactions between CoS_(2)/MoS_(2)and LiPSs.Experimental results demonstrate that Li-S batteries with S/CoS_(2)/MoS_(2)@HCS composites as the cathode exhibit an exceptionally low capacity decay rate of only 0.023%per cycle after 1200 cycles at 2.0 C.Even with high sulfur loading(7.9 mg cm^(−2))and a low electrolyte-to-sulfur(E/S)ratio(6.0μL mg^(−1)),the battery achieves an outstanding areal capacity of 6.86 mA h cm^(−2).This study develops a highly efficient CoS_(2)/MoS_(2)heterojunction within HCS for the adsorption and conversion of LiPSs,providing valuable insights into the design of high-performance cathode materials for Li-S batteries.
基金supporting this work through an ARC linkage grant(LP190101230)Part of this work was funded by ARC DP220100500+2 种基金The authors acknowledge the use of the instruments and scientific and technical assistance at the Monash Centre for Electron Microscopy,Monash University,a Microscopy Australia(ROR:042mm0k03)facility supported by NCRISThis research used equipment funded by Australian Research Council grant(s)(LE200100132,LE110100223).
文摘Copper extraction from chalcopyrite is challenging,because acid dissolution is slow,occurring incongruently via a complex three-step reaction mechanism.Silver has been known to catalyse copper extraction from chalcopyrite since the 1970's;yet the mechanism remains controversial.Microcharacterisation of experimental products obtained under optimal leaching conditions(50-150μm chalcopyrite grains in ferric/ferrous-sulfate solution with a redox potential around 500 mV vs.Ag/AgCl,approximately 1ppm Ag;[Ag]6.4×10^(−6)mol/L;70℃;4 days)highlights the heterogeneity of the reaction:µm-thick layers of a porous copper-sulfide with variable composition formed both in cracks within,and on the surface of the chalcopyrite grains.There is no evidence for formation of Ag-rich phases(Ag_(2)S_((s)),Ag_((s)^(0))).The fundamental three-step reaction mechanism remains the same with or without added silver;silver merely accelerates the initial dissolution step.An integrated model for the catalytic effect of silver is proposed that incorporates recent advances in the reactivity of sulfide minerals.The initial reaction follows a‘Fluid-Induced Solid State Diffusion Mechanism’,where diffusion of Fe in the chalcopyrite lattice is driven towards the surface by its rapid removal into solution,resulting in a Fe-deficient surface layer.The large Ag+ion,relative to Cu+/Fe3+,diffuses into this Fe-deficient surface layer and accelerates chalcopyrite dissolution in the subsequent step,whereby chalcopyrite is replaced by copper sulfides via an interface coupled dissolution reprecipitation reaction as a consequence of the sulfide-rich micro-environment at the mineral surface.Effective Ag+recycling is key to the catalytic effect of silver,and occurs as a result of the strong affinity of Ag+for bisulfide ligands accumulating at the surface of dissolving chalcopyrite.
基金supported by the Natural Science Foundation of Jiangxi Province(20232ACB213005).
文摘A novel tetra-europium(III)-containing antimonotungstate,Na_(8.2)[H_(2)N(CH_(3))_(2)]_(9)[Na_(10.8)(tar)_(4)(H_(2)O)_(20)(Eu_(2)Sb_(2)W_(21)O_(72))_(2)]·44.5H_(2)O(EuSbW,H_(4)tar=dl-tartaric acid),has been synthesized and characterized.The dimeric polyoxoanion of EuSbW consists of two Dawson-like{Eu_(2)Sb_(2)W_(21)}units bridged by four dl-tartaric acid ligands.The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different{Eu_(2)Sb_(2)W_(21)}units,thereby forming the dimeric structure.EuSbW represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two{Eu_(2)Sb_(2)W_(21)}units.Additionally,EuSbW exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols,achieving 100%conversion and>99%selectivity for various thioethers,and 85–100%conversion with 90–99%selectivity for diverse alcohols under mild conditions.
基金supported by the National Natural Science Foundation of China (No.22076052)the Natural Science Foundation of Hubei Province (Nos.2021CFB535 and 2020CFB437)+2 种基金the Knowledge Innovation Program of Wuhan-Basic Research (No.SZY23005)the Fundamental Research Funds for the Central Universities,South-Central Minzu University (No.CZQ22002)Wuhan University (No.2042020kf0036).
文摘The reduction of nitrobenzene to aniline is very important for both pollution control and chemical synthesis.Nevertheless,difficulties still remain in developing a catalytic system having high efficiency and selectivity for the production of aniline.Herein,it was found that PdO nanoparticles highly dispersed on TiO_(2)support(PdO/TiO_(2))functioned as a highly efficient catalyst for the reduction of nitrobenzene in the presence of NaBH4.Under favorable conditions,95%of the added nitrobenzene(1 mmol/L)was reduced within 1 min with an ultra-low apparent activation energy of 10.8 kJ/mol by using 0.5%PdO/TiO_(2)as catalysts and 2 mmol/L of NaBH4 as reductants,and the selectivity to aniline even reached up to 98%.The active hydrogen specieswere perceived as dominant species during the hydrogenation of nitrobenzene by the results of isotope labeling experiments and ESR spectroscopic.A mechanismwas proposed as follows:PdO activates the nitro groups and leads to in-situ generation of Pd,and the generated Pd acts as the reduction sites to produce active hydrogen species.In this catalytic system,nitrobenzene prefers to be adsorbed on the PdO nanoparticles of the PdO/TiO_(2)composite.Subsequently,the addition of NaBH_(4) results in in-situ generation of a Pd/PdO/TiO_(2)composite from the PdO/TiO_(2)composite,and the Pd nanoclusters would activate NaBH_(4) to generate active hydrogen species to attack the adsorbed nitro groups.This work will open up a new approach for the catalytic transfer hydrogenation of nitrobenzene to aniline in green chemistry.
基金supported by the National Natural Science Foundation of China(22209103)Science and Technology Commission of Shanghai Municipality(22010500400)Australian Research Council(FT180100705)。
文摘Hard carbons are promising anode materials for sodium-ion batteries(SIBs),but they face challenges in balancing rate capability,specific capacity,and initial Coulombic efficiency(ICE).Direct pyrolysis of the precursor often fails to create a suitable structure for sodium-ion storage.Molecular-level control of graphitization with open channels for Na^(+)ions is crucial for high-performance hard carbon,whereas closed pores play a key role in improving the low-voltage(<0.1 V)plateau capacity of hard carbon anodes for SIBs.However,creation of these closed pores presents significant challenges.This work proposes a zinc gluconate-assisted catalytic carbonization strategy to regulate graphitization and create numerous nanopores simultaneously.As the temperature increases,trace amounts of zinc remain as single atoms in the hard carbon,featuring a uniform coordination structure.This mitigates the risk of electrochemically irreversible sites and enhances sodium-ion transport rates.The resulting hard carbon shows an excellent reversible capacity of 348.5 mAh g^(-1) at 30 mA g^(-1) and a high ICE of 92.84%.Furthermore,a sodium storage mechanism involving“adsorption-intercalation-pore filling”is elucidated,providing insights into the pore structure and dynamic pore-filling process.
基金financially supported by the Key Research and Development Projects of Shaanxi Province(Grant Nos.2025CYYBXM-154 and 2024GX-YBXM-213)the Yulin Science and Technology Bureau(Grant Nos.2023-CXY-202 and 2024-CXY-154)the Technology Innovation Leading Program of Shaanxi(Programs 2023GXLH-068)。
文摘The magnesium-based materials are acknowledged as one of the most promising solid-state hydrogen storage mediums,attributed to their superior hydrogen storage capacity.Nevertheless,challenges such as sluggish kinetics,thermodynamic stability,inadequate cycling stability,and difficulties in activation impede the commercial utilization of Mg-based composites.Research indicates that reducing material dimensions to the nanoscale represents an efficacious strategy to address these issues.In this work,we systematically analyze the impact of nanosizing on Mg-based composites from three perspectives:nano-substrate modulation,nano-catalyst construction,and nano-catalytic mechanism.This analysis aims to provide guidance for the optimization and development of nanosizing strategies.For the regulation of nanosizing of Mg-based composites,the nanosizing of multi-element micro-alloyed Mg-rich systems,the integrated synthesis of multi-element multi-component nano-catalysts,and the coexistence of multiple nano-catalytic mechanisms are proposed in the light of the current state of the art research,artificial intelligence technology,and advanced characterization technology to achieve efficient,multidimensional,and simultaneous regulation of the hydrogen storage performance of Mg-based composites.This paper also envisions future directions and potential applications,emphasizing the importance of interdisciplinary approaches that integrate material science,chemistry,and computational modeling to overcome existing limitations and unlock the full potential of Mg-based hydrogen storage technologies.
基金supported by the Scientific and technological innovation project of Ningxia Coal Industry Co.,LTD,China Energy Investment(NXMY-24-36)。
文摘The selective catalytic deoxygenation of oxy-organics in Fischer-Tropsch mixed oil for its high value utilization is challenging.Herein,a BaCO_(3)/γ-Al_(2)O_(3) catalyst was prepared calciningγ-Al_(2)O_(3) with BaCO_(3),and the acid-alkalinity of the catalyst was regulated by introducing alkaline Ba basic sties.In a co ntinuous fixed-bed reactor with a feed mass space velocity of 1 h~(-1)and reaction temperature of 330℃,BaCO_(3)/γ-Al_(2)O_(3) catalyst can efficiently catalyzed the deoxygenation removal of 1-octanol in Fischer-Tropsch C10mixture oil.It also inhibited the isomerization of 1-decene in the C10 mixture.The catalytic deoxygenation kinetics of 1-octanol were also studied.The reaction was endothermic with an activation energy of 64 kJ·mol^(-1)and a reaction order of 2.In addition,theoretical studies revealed the adsorption and activation of 1-decene on the Lewis acidic site and the alkaline Ba basic sites,1-decene was more easily underwent isomerization into 2-decene at Lewis acid sites.This research provides a useful method to enable the industrial application of catalytic deoxygenation of alcohols in Fischer-Tropsch synthetic oil.
