5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high in...5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high internal phase emulsions(Pickering HIPEs)as template and functional metal-organic frameworks(MOFs,UiO-66-SO;H and UiO-66-NH;)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process,which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF.The effects of the emulsion parameters including the amount of surfactant(ranging from 0.5%to 2.0%(mass)),the internal phase volume fraction(ranging from 75%to 90%)and the acid/base Pickering particles mass ratio(ranging from 0:6 to 6:0)on the morphology and catalytic performance of solid catalyst were systematically researched.The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion,and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield.The highest 5-HMF yield,about 40.5%,can be obtained by using polymer/MOFs composite as catalyst(Poly-P12,the pore size of(53.3±11.3)μm,the acid density of 1.99 mmol·g^(-1)and the base density of 1.13 mol·g^(-1))under the optimal reaction conditions(130℃,3 h).Herein,the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method,which provided a favorable experimental basis and theoretical reference for achieving efficient production of high addedvalue product from abundant biomass.展开更多
The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile...The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile wet-chemical method to prepare ~1.0 nm Au Pd NCs supported on amine-functionalized carbon blacks. The Au Pd NCs exhibit a specific activity of 5.98 mA cm_(AuPd)^(-2)and mass activity of 5.25 A mg_(auPd)^(-1) for ethanol electrooxidation, which are far better than those of commercial Pd/C catalysts(1.74 mAcm_(AuPd)^(-2) and 0.54 A mg_(Pd)^(-1) ). For formic acid dehydrogenation, the Au Pd NCs have an initial turn over frequency of 49339 h^(-1) at 298 K without any additive, which is much higher than those obtained for most of reported Au Pd catalysts. The reported synthesis may represent a facile and low-cost approach to prepare other ultrasmall metal NCs with high catalytic activities for various applications.展开更多
A bifunctional heterogeneous catalyst containing two mutually incompatible acidic and basic sites, which exhibits cooperative catalytic behavior in the aldol condensation of acetone and various aldehydes, was synthesi...A bifunctional heterogeneous catalyst containing two mutually incompatible acidic and basic sites, which exhibits cooperative catalytic behavior in the aldol condensation of acetone and various aldehydes, was synthesized by postgrafting of 1,5,7- triazabicyclo[4.4.0] dec-5-ene （TBD, a sterically hindered organic base） onto AI-MCM-41 molecular sieve. 2009 Xiao Bing Lu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
Water management within the membrane electrode assemblies(MEAs)of electrochemical hydrogen compressors(EHCs)plays a crucial role in optimizing overall performance,particularly under low relative humidity(RH),where the...Water management within the membrane electrode assemblies(MEAs)of electrochemical hydrogen compressors(EHCs)plays a crucial role in optimizing overall performance,particularly under low relative humidity(RH),where the anode side tends to dry out.Hollow mesoporous silica nanoparticles functionalized with amino groups(HMSNs-NH_(2))were integrated into the anode catalyst layers of EHCs to establish humidity-independent proton pathways through acid-base interactions with Nafion ionomers.These acid-base pairs between grafted–NH_(2)and sulfonic acid groups create continuous“proton highways”,enabling efficient conduction via the Grotthuss mechanism even at 50%RH.With only 2.5 wt%HMSNs-NH_(2)in the anode catalyst layer,hydrogen was compressed to 0.9 MPa in 60±3 s at 50%RH,representing a 55%reduction in compression time compared to MEAs with conventional Pt/C catalyst layers under the same conditions.This work overcomes the critical water-management bottleneck in EHCs,advancing the deployment of hydrogen energy technologies in arid environments.展开更多
Carbon nanotubes/graphene hybrid materials with excellent physicochemical properties can be widely ap-plied in the fields of energy storage,electrocatalysis,sensing,etc.Reducing the self-stacking and achiev-ing covale...Carbon nanotubes/graphene hybrid materials with excellent physicochemical properties can be widely ap-plied in the fields of energy storage,electrocatalysis,sensing,etc.Reducing the self-stacking and achiev-ing covalent interaction between carbon nanotubes and graphene are important to ensure a stable hi-erarchical architecture and effective mass transfer.Herein,we propose a one-step strategy to synthesize 3D interconnected carbon nanotubes/graphene hybrids on the easy-to-remove biomass-derived substrate.The calcined natural cuttlebone as bi-functional catalyst precursor can simultaneously grow carbon nan-otubes and graphene by one-step chemical vapor deposition without the addition of extra metal catalysts,while the interconnected structure can act as the porous template for graphene growth.The simultane-ous growth process can obtain covalent bonding between carbon nanotubes and graphene,while the crystalline quality and interlayer space can be adjusted by different carbon sources and growth parame-ters(e.g.,temperature).The one-step grown carbon nanotubes/graphene hybrids with seamless interfaces and hierarchical interconnected 3D structure can effectively enhance the electron transfer as well as the electrolyte infiltration efficiency.When utilized as lithium-ion batteries(LIBs)anode,a high specific ca-pacity(544 mAh g^(-1) at 0.1 A g^(-1)),good rate capability(200 mAh g^(-1) at 6.4 A g^(-1) with an ultrashort charge time of 113 s),and excellent cyclic stability can be achieved.This simple and one-step carbon nanotubes/graphene hybrids fabrication strategy can be easily scale-up and applied in various fields.展开更多
Two kinds of bi-functional transition metal doped mesoporous materials(Fe-HMS and Fe-MCM-41) are prepared using one-step hydrothermal method and then treated with hydrochloric acid ethanol solution.The N2 adsorption a...Two kinds of bi-functional transition metal doped mesoporous materials(Fe-HMS and Fe-MCM-41) are prepared using one-step hydrothermal method and then treated with hydrochloric acid ethanol solution.The N2 adsorption and HRTEM results show that both of Fe-HMS and Fe-MCM-41 possess mesoporous structure. The UV–vis results suggest that the Fe species are mainly located within the framework. The basicity of as-prepared samples was studied by temperature programmed desorption using CO2 as probe molecule(CO2-TPD). The catalytic performance of Fe-HMS and Fe-MCM-41 in CO2 cycloaddition largely depends on the amount of the accessible basic sites. The acid–base active sites, framework Fe and PDDA species cooperatively catalyze the CO2 cycloaddition for the production of cyclic carbonates under the condition without any co-catalyst. The conversion of epichlorohydrin(ECH) is 97.4% and the selectivity of chloropropene carbonate is 92.9% under optimal conditions. The approximate rate constant of cycloaddition reaction of CO2 with ECH under optimum reaction temperature is calculated. It is worth noting that the Fe-HMS material shows superior reusability than Fe-MCM-41. In addition, this work provides a facile way on the synthesis of bi-functional acid–base heterogeneous catalyst with outstanding catalytic performance for the fixation of CO2.展开更多
There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNT...There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNTs composite have gained increasing attention. In this paper, the 3-D hollow sphere MnO_2 nanotube-supported Co_3O_4 nanoparticles and its carbon nanotubes hybrid material(Co_3 O_4/MnO_2-CNTs) have been synthesized via a simple co-precipitation method combined with post-heat treatment. The morphology and composition of the catalysts are thoroughly analyzed through SEM, TEM, TEM-mapping, XRD, EDX and XPS. In comparison with the commercial 20% Pt/C, Co_3O_4/MnO_2,bare MnO_2 nanotubes and CNTs, the hybrid Co_3O_4/MnO_2-CNTs-350 exhibits perfect bi-functional catalytic activity toward oxygen reduction reaction and oxygen evolution reaction under alkaline condition(0.1 M KOH). Therefore, high cell performances are achieved which result in an appropriate open circuit voltage(～1.47 V),a high discharge peak power density(340 mW cm^(-2)) and a large specific capacity(775 mAh g^(-1) at 10 mA cm^(-2)) for the primary Zn-air battery, a small charge-discharge voltage gap and a high cycle-life(504 cycles at 10 mA cm^(-2) with 10 min per cycle) for the rechargeable Zn-air battery. In particular, the simple synthesis method is suitable for a large-scale production of this bifunctional material due to a green, cost effective and readily available process.展开更多
The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these c...The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.展开更多
This short review paper aims at assembling the present state of the art of the multiuses of metal oxides in heterogeneous catalysis, concerning liquid and gaseous phases of the reactant mixtures on solid catalysts. It...This short review paper aims at assembling the present state of the art of the multiuses of metal oxides in heterogeneous catalysis, concerning liquid and gaseous phases of the reactant mixtures on solid catalysts. It includes the description of the main types of metal oxide catalysts, of their various preparation procedures and of the main reactions catalysed by them (acid-base type, selective and total oxidations, bi-functional catalysis, photocatalysis, biomass treatments, environmental catalysis and some of the numerous industrial applications). Challenges and prospectives are also discussed.展开更多
Direct aldol reactions of aldehydes and ketones can proceed smoothly in the presence of a catalytic amount of naphthol/sodium naphtholate（5 mol%） to afford the corresponding products with yields up to 98%.Such a bif...Direct aldol reactions of aldehydes and ketones can proceed smoothly in the presence of a catalytic amount of naphthol/sodium naphtholate（5 mol%） to afford the corresponding products with yields up to 98%.Such a bifunctional catalyst is more moderate than strong acid or base employed in direct aldol reactions.展开更多
A Brønsted acid-base bifunctional metal-organic framework(MOF)catalyst,PCN-700-AB[A=Brønsted acid site,TPDC-(COOH)_(2)[(1,1′∶4′,1″-terphenyl)-2,2″,4,4″-tetracarboxylic acid]and B=Brønsted basic si...A Brønsted acid-base bifunctional metal-organic framework(MOF)catalyst,PCN-700-AB[A=Brønsted acid site,TPDC-(COOH)_(2)[(1,1′∶4′,1″-terphenyl)-2,2″,4,4″-tetracarboxylic acid]and B=Brønsted basic site,BDC-NH_(2)],was designed precisely and synthesized successfully through sequential installation of Brønsted acid and base functionalities in a crystalline zirconium(Zr)-MOF.The installation underwent single-crystal-to-singlecrystal transformation throughout the process;hence,the structure of the bifunctional catalyst could be characterized accurately via single-crystal X-ray crystallography.The bifunctional MOF catalyst obtained exhibited excellent acid-base catalytic activity for a cascade of one-pot deacetalization-Knoevenagel condensation reaction.The work presented here could be considered as a promising solution to incorporate multifunctional components readily,especially the hostile aspects,into one MOF structure.展开更多
A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation(HDO)of phenol.The Ni dispersibility and particle sizes were shown to be directly related ...A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation(HDO)of phenol.The Ni dispersibility and particle sizes were shown to be directly related to the porosity and crystal sizes of the parent zeolites,which further influenced the catalytic performances.The large pores and small crystal sizes of the parent zeolites were beneficial for dispersing Ni and forming small Ni particles,and the corresponding Ni/zeolite catalyst exhibited a higher phenol conversion and selectivity towards hydrocarbons.Importantly,the Ni/HIM-5 bi-functional catalyst exhibited a high activity(98.3%)and high selectivity for hydrocarbons(98.8%)when heated at 220°C for 1 h and is thus a new potential catalyst for the HDO of phenolics to form hydrocarbons in the aqueous phase.展开更多
Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organ...Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organic coordination catalysts showed satisfactory ability of TH in the secondary alcohols,but most of them could not effectively employ the cheaper primary alcohols as hydrogen donors.Furthermore,they commonly contained high metal contents,which also led to low catalytic efficiency in significant measure.In this work,we constructed a novel magnesium single-atom catalyst(Mg-NC)with merely 0.37 wt%Mg by means of a combined self-assembly and pyrolysis strategy.The characterization results indicated that Mg was atomically dispersed and it was coordinated with four pyridinic-N in Mg-NC.Due to the obvious electron transfer from Mg to its coordinated pyridinic-N,Mg–N_(4)active centers displayed high Lewis acid-base strength with abundant content,which brought remarkable catalytic activity.When Mg-NC was used for the TH of 5-hydroxymethylfurfural(HMF)in ethanol(EtOH),2,5-bis(hydroxymethyl)furan(BHMF)yield was up to 96.3%with high productivity of 19.85 molBHMF mol_(Mg)^(−1)h^(−1)at 150°C for 5 h.More interestingly,the process of TH over Mg-NC in EtOH was proved to proceed via the hydrogen radical mechanism.Additionally,Mg-NC exhibited powerful catalytic universality;it could not only utilize other primary alcohols(such as n-propanol and n-butanol)as hydrogen donors,but also catalyze the TH of other carbonyl compounds(such as furfural,5-methylfurfural,benzaldehyde,cyclohexanone,and levulinic acid).Overall,this work offered some important clues and references to reinforce the hydrogen-supplying ability of primary alcohols in the TH of various biomass-derived carbonyl compounds to high-value fine chemicals.展开更多
Amorphous aluminophosphate(AlP) and metal-aluminophosphates(MAlPs, where M = 2.5 mol%Cu, Zn, Cr, Fe, Ce, or Zr) were prepared by coprecipitation method. Their surface properties and catalytic activity for the synthesi...Amorphous aluminophosphate(AlP) and metal-aluminophosphates(MAlPs, where M = 2.5 mol%Cu, Zn, Cr, Fe, Ce, or Zr) were prepared by coprecipitation method. Their surface properties and catalytic activity for the synthesis of jasminaldehyde through the aldol condensation of nheptanal and benzaldehyde were investigated. The nitrogen adsorption-desorption isotherms showed that the microporosity exhibited by the aluminophosphate was changed to a mesoporous and macroporous structure which depended on the metal incorporated, with a concomitant change in the surface area. Temperature-programmed desorption of NHand COrevealed that the materials possessed both acidic and basic sites. The acidic strength of the material was either increased or decreased depending on the nature of the metal. The basicity was increased compared to AlP. All the materials were X-ray amorphous and powder X-ray diffraction studies indicated the absence of metal oxide phases. The Fourier transform infrared analysis confirmed the presence of phosphate groups and also the absence of any M-O moieties in the materials. The selected organic reaction occurred only in the presence of the AlP and MAlPs. The selectivity for the jasminaldehyde product was up to 75% with a yield of 65%. The best conversion of nheptanal with a high selectivity to jasminaldehyde was obtained with FeAlP as the catalyst, and this material was characterized to have less weak acid sites and more basic sites.展开更多
The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dp...The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.展开更多
The catalytic performance of Pt-based catalysts for the total oxidation of hydrocarbons was investigated.The activity of supported Pt catalysts(Pt/Al2O3,Pt/ZrO2,Pt/TiO2,and Pt/H-ZSM-5)depends on the metal oxide suppor...The catalytic performance of Pt-based catalysts for the total oxidation of hydrocarbons was investigated.The activity of supported Pt catalysts(Pt/Al2O3,Pt/ZrO2,Pt/TiO2,and Pt/H-ZSM-5)depends on the metal oxide support.Pt/Al2O3 showed the highest catalytic activity when the catalysts were aged at 750°C for 50 h in air.The activity of Pt/Al2O3 was dependent on the valence state of the Pt surface.Pt/Al2O3 with the Pt surface in the metallic state was more active than with the surface in the cationic state.The surface density of acid and basic sites on the Al2O3 support controlled the valence state of the Pt surface and stability of the Pt particles in the highly dispersed state,respectively.展开更多
The rational design and preparation of promising cathode electrocatalysts with excellent activity and strong stability for metal-air batteries is a huge challenge.In this work,we innovate an approach of combining solv...The rational design and preparation of promising cathode electrocatalysts with excellent activity and strong stability for metal-air batteries is a huge challenge.In this work,we innovate an approach of combining solvothermal with high-temperature pyrolysis utilizing zeolitic imidazolate framework(ZIF)-8 and ZIF-67 as the template to synthesize a novel hybrid material of hierarchical porous yolk-shell Co-N-C polyhedron nanocatalysts engaged in graphene nanopocket(yolk-shell Co-N-C@GNP).The obtained catalyst exhibits prominent bifunctional electrocatalytic performance for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)in the alkaline condition,in which the half-wave potential is 0.86 V for ORR,and the over-potential for OER is 0.42 V at 10 mA·cm^(-2).The rechargeable aqueous Zn-air battery fabricated with yolk-shell Co-N-C@GNP cathode deliveries an open circuit voltage(OCV)of 1.60 V,a peak power density of 236.2 mW·cm^(-2),and excellent cycling stability over 94 h at 5 mA·cm^(-2).The quasi-solid-state Zn-air battery(ZAB)using yolk-shell Co-N-C@GNP displays a high OCV of 1.40 V and a small voltage gap of 0.88 V in continuous cycling tests at 2 mA·cm^(-2).This work provides a valuable thought to focus attention on the design of high-efficient bifunctional catalysts with hierarchical porous yolk-shell framework and high-density metal active sites for metal-air battery technologies.展开更多
A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR s...A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selec- tivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied.展开更多
Alkali metal pollutants are often regarded as toxic agents for the catalytic hydrodeoxygenation(HDO)of biomass,hindering the conversion of biomass towards higher-value hydrocarbon fuels.In this study,a series of Pt/WO...Alkali metal pollutants are often regarded as toxic agents for the catalytic hydrodeoxygenation(HDO)of biomass,hindering the conversion of biomass towards higher-value hydrocarbon fuels.In this study,a series of Pt/WO_(x)catalysts for HDO with varying K contents were synthesized,and an intriguing effect of K on activity was observed.The introduced K+occupies the H position of the hydroxyl group,poisoning Brùnsted acid sites(BAS);however,it regulates the adsorption of olefin intermediates,consequently facilitating the whole HDO reaction.Notably,dissociated hydrogen species on the metal sites can spillover to adjacent WO_(x)sites,liberating the hydroxyl group poisoned by K and thus operando forming BAS again(back to 84%of the K-free catalyst),which safeguards the dehydration step from alkali metal severe poisoning.By comparing the catalytic behavior on WO_(x)with non-reducible acidic Si-Al zeolite supports,we demonstrate that this‘deliverance effect'depends on the reducibility of the supports.The optimal 0.2 Pt0.8K/WO_(x)catalyst exhibited 2.6 times higher catalytic activity than 0.2 Pt/WO_(x),which also finds its applicability on other noble metals like Ru and Pd,achieving excellent yields across various lignin derivatives.This work not only reports an efficient K-doped Pt catalyst design for HDO reaction but also provides a more comprehensive understanding of the catalytic role of K additives on acid and metal sites.展开更多
The chemical transformation of CO2 and epoxides into cyclic carbonates has been receiving much attention and is one of the successful examples for CO2 utilization as carbon resource.Many catalysts containing halide an...The chemical transformation of CO2 and epoxides into cyclic carbonates has been receiving much attention and is one of the successful examples for CO2 utilization as carbon resource.Many catalysts containing halide anions have been explored and exhibit excellent catalytic activity.However,halogen salt is generally toxic and corrosive to reactors.From a green chemistry perspective,it is more attractive to develop a halogen-free catalyst with excellent performance.Herein,a review of recent research progress of halogen-free catalysts in the cycloaddition of CO2 and epoxide is presented.According to previous experimental and theoretical works,two possible strategies for achieving the halogen-free process were summarized.The relationship between catalytic activity and catalyst structure,the mechanism of CO2 activation should be both studied deeply combined with experimental results and DFT calculation,which can guide the design of new catalysts and realize halogen-free process under mild reaction conditions.展开更多
基金financially supported by the National Natural Science Foundation of China(No.21606100)the Natural Science Foundation of Jiangsu Province(No.BK20180850)+1 种基金the China Postdoctoral Science Foundation(Nos.2019M651740 and 2019T120397)the Young Talent Cultivate Programme of Jiangsu University。
文摘5-Hydroxymethylfurfural(5-HMF),as a key platform compound for the conversion of biomass to various biomass-derived chemicals and biofuels,has been attracted extensive attention.In this research,using Pickering high internal phase emulsions(Pickering HIPEs)as template and functional metal-organic frameworks(MOFs,UiO-66-SO;H and UiO-66-NH;)/Tween 85 as co-stabilizers to synthesis the dual acid-base bifunctional macroporous polymer catalyst by one-pot process,which has excellent catalytic activity in the cascade reaction of converting cellulose to 5-HMF.The effects of the emulsion parameters including the amount of surfactant(ranging from 0.5%to 2.0%(mass)),the internal phase volume fraction(ranging from 75%to 90%)and the acid/base Pickering particles mass ratio(ranging from 0:6 to 6:0)on the morphology and catalytic performance of solid catalyst were systematically researched.The results of catalytic experiments suggested that the connected large pore size of catalyst can effectively improve the cellulose conversion,and the synergistic effect of acid and base active sites can effectively improve the 5-HMF yield.The highest 5-HMF yield,about 40.5%,can be obtained by using polymer/MOFs composite as catalyst(Poly-P12,the pore size of(53.3±11.3)μm,the acid density of 1.99 mmol·g^(-1)and the base density of 1.13 mol·g^(-1))under the optimal reaction conditions(130℃,3 h).Herein,the polymer/MOFs composite with open-cell structure was prepared by the Pickering HIPEs templating method,which provided a favorable experimental basis and theoretical reference for achieving efficient production of high addedvalue product from abundant biomass.
基金supported by the National Natural Science Foundation of China (51901083)the Fundamental Research Funds for the Central Universities。
文摘The synthesis of ultrasmall metal nanoclusters(NCs) with high catalytic activities is of great importance for the development of clean and renewable energy technologies but remains a challenge. Here we report a facile wet-chemical method to prepare ~1.0 nm Au Pd NCs supported on amine-functionalized carbon blacks. The Au Pd NCs exhibit a specific activity of 5.98 mA cm_(AuPd)^(-2)and mass activity of 5.25 A mg_(auPd)^(-1) for ethanol electrooxidation, which are far better than those of commercial Pd/C catalysts(1.74 mAcm_(AuPd)^(-2) and 0.54 A mg_(Pd)^(-1) ). For formic acid dehydrogenation, the Au Pd NCs have an initial turn over frequency of 49339 h^(-1) at 298 K without any additive, which is much higher than those obtained for most of reported Au Pd catalysts. The reported synthesis may represent a facile and low-cost approach to prepare other ultrasmall metal NCs with high catalytic activities for various applications.
基金support by a Foundation for the Author of National Excellent Doctoral Dissertation of China(No.FANEDD,200759)the Outstanding Young Scientist Foundation of NSFC(No.20625414)
文摘A bifunctional heterogeneous catalyst containing two mutually incompatible acidic and basic sites, which exhibits cooperative catalytic behavior in the aldol condensation of acetone and various aldehydes, was synthesized by postgrafting of 1,5,7- triazabicyclo[4.4.0] dec-5-ene （TBD, a sterically hindered organic base） onto AI-MCM-41 molecular sieve. 2009 Xiao Bing Lu. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金supported by the National Natural Science Foundation of China(No.22208376,No.UA22A20429)the Fundamental Research Funds for the Central Universities(buctrc202118,No.25CX07002A)+1 种基金the Qingdao New Energy Shandong Laboratory Open Project(QNESL OP 202303)the Shandong Provincial Natural Science Foundation(ZR2024QB175 and ZR2023LFG005)。
文摘Water management within the membrane electrode assemblies(MEAs)of electrochemical hydrogen compressors(EHCs)plays a crucial role in optimizing overall performance,particularly under low relative humidity(RH),where the anode side tends to dry out.Hollow mesoporous silica nanoparticles functionalized with amino groups(HMSNs-NH_(2))were integrated into the anode catalyst layers of EHCs to establish humidity-independent proton pathways through acid-base interactions with Nafion ionomers.These acid-base pairs between grafted–NH_(2)and sulfonic acid groups create continuous“proton highways”,enabling efficient conduction via the Grotthuss mechanism even at 50%RH.With only 2.5 wt%HMSNs-NH_(2)in the anode catalyst layer,hydrogen was compressed to 0.9 MPa in 60±3 s at 50%RH,representing a 55%reduction in compression time compared to MEAs with conventional Pt/C catalyst layers under the same conditions.This work overcomes the critical water-management bottleneck in EHCs,advancing the deployment of hydrogen energy technologies in arid environments.
基金the financially supported from the National Nat-ural Science Foundation of China(Nos.21978178,22008157,and 21776187)the Distinguished Young Scholars for the Natural Science Foundation of Sichuan Province(No.2023NSFSC1915)。
文摘Carbon nanotubes/graphene hybrid materials with excellent physicochemical properties can be widely ap-plied in the fields of energy storage,electrocatalysis,sensing,etc.Reducing the self-stacking and achiev-ing covalent interaction between carbon nanotubes and graphene are important to ensure a stable hi-erarchical architecture and effective mass transfer.Herein,we propose a one-step strategy to synthesize 3D interconnected carbon nanotubes/graphene hybrids on the easy-to-remove biomass-derived substrate.The calcined natural cuttlebone as bi-functional catalyst precursor can simultaneously grow carbon nan-otubes and graphene by one-step chemical vapor deposition without the addition of extra metal catalysts,while the interconnected structure can act as the porous template for graphene growth.The simultane-ous growth process can obtain covalent bonding between carbon nanotubes and graphene,while the crystalline quality and interlayer space can be adjusted by different carbon sources and growth parame-ters(e.g.,temperature).The one-step grown carbon nanotubes/graphene hybrids with seamless interfaces and hierarchical interconnected 3D structure can effectively enhance the electron transfer as well as the electrolyte infiltration efficiency.When utilized as lithium-ion batteries(LIBs)anode,a high specific ca-pacity(544 mAh g^(-1) at 0.1 A g^(-1)),good rate capability(200 mAh g^(-1) at 6.4 A g^(-1) with an ultrashort charge time of 113 s),and excellent cyclic stability can be achieved.This simple and one-step carbon nanotubes/graphene hybrids fabrication strategy can be easily scale-up and applied in various fields.
基金financial support from the Program for New Century Excellent Talents in University(NCET-040270)。
文摘Two kinds of bi-functional transition metal doped mesoporous materials(Fe-HMS and Fe-MCM-41) are prepared using one-step hydrothermal method and then treated with hydrochloric acid ethanol solution.The N2 adsorption and HRTEM results show that both of Fe-HMS and Fe-MCM-41 possess mesoporous structure. The UV–vis results suggest that the Fe species are mainly located within the framework. The basicity of as-prepared samples was studied by temperature programmed desorption using CO2 as probe molecule(CO2-TPD). The catalytic performance of Fe-HMS and Fe-MCM-41 in CO2 cycloaddition largely depends on the amount of the accessible basic sites. The acid–base active sites, framework Fe and PDDA species cooperatively catalyze the CO2 cycloaddition for the production of cyclic carbonates under the condition without any co-catalyst. The conversion of epichlorohydrin(ECH) is 97.4% and the selectivity of chloropropene carbonate is 92.9% under optimal conditions. The approximate rate constant of cycloaddition reaction of CO2 with ECH under optimum reaction temperature is calculated. It is worth noting that the Fe-HMS material shows superior reusability than Fe-MCM-41. In addition, this work provides a facile way on the synthesis of bi-functional acid–base heterogeneous catalyst with outstanding catalytic performance for the fixation of CO2.
基金financial support from the National Natural Science Foundation of China (U1510120, 91645110)the Project of Introducing Overseas Intelligence High Education of China (2017-2018)+1 种基金the Graduate Thesis Innovation Foundation of Donghua University (EG2016034)the College of Environmental Science and Engineering, State Environmental Protection Engineering Center for Pollution Treatment and Control in Textile Industry, Donghua University
文摘There has been a continuous need for high active, excellently durable and low-cost electrocatalysts for rechargeable zinc-air batteries. Among many low-cost metal based candidates, transition metal oxides with the CNTs composite have gained increasing attention. In this paper, the 3-D hollow sphere MnO_2 nanotube-supported Co_3O_4 nanoparticles and its carbon nanotubes hybrid material(Co_3 O_4/MnO_2-CNTs) have been synthesized via a simple co-precipitation method combined with post-heat treatment. The morphology and composition of the catalysts are thoroughly analyzed through SEM, TEM, TEM-mapping, XRD, EDX and XPS. In comparison with the commercial 20% Pt/C, Co_3O_4/MnO_2,bare MnO_2 nanotubes and CNTs, the hybrid Co_3O_4/MnO_2-CNTs-350 exhibits perfect bi-functional catalytic activity toward oxygen reduction reaction and oxygen evolution reaction under alkaline condition(0.1 M KOH). Therefore, high cell performances are achieved which result in an appropriate open circuit voltage(～1.47 V),a high discharge peak power density(340 mW cm^(-2)) and a large specific capacity(775 mAh g^(-1) at 10 mA cm^(-2)) for the primary Zn-air battery, a small charge-discharge voltage gap and a high cycle-life(504 cycles at 10 mA cm^(-2) with 10 min per cycle) for the rechargeable Zn-air battery. In particular, the simple synthesis method is suitable for a large-scale production of this bifunctional material due to a green, cost effective and readily available process.
基金supported by Shanxi Province Science Foundation for Youths(202203021212300)Taiyuan University of Science and Technology Scientific Research Initial Funding(20212064)Outstanding Doctoral Award Fund in Shanxi Province(20222060).
文摘The nitrogen-coordinated metal single-atom catalysts(M−N−C SACs)with an ultra-high metal loading synthetized by direct high-temperature pyrolysis have been widely reported.However,most of metal single atoms in these catalysts were buried in the carbon matrix,resulting in a low metal utilization and inaccessibility for adsorption of reactants during the catalytic process.Herein,we reported a facile synthesis based on the hard-soft acid-base(HSAB)theory to fabricate Co single-atom catalysts with highly exposed metal atoms ligated to the external pyridinic-N sites of a nitrogen-doped carbon support.Benefiting from the highly accessible Co active sites,the prepared Co−N−C SAC exhibited a superior oxygen reduction reactivity comparable to that of the commercial Pt/C catalyst,showing a high turnover frequency(TOF)of 0.93 e^(−)·s^(-1)·site^(-1)at 0.85 V vs.RHE,far exceeding those of some representative SACs with a ultra-high metal content.This work provides a rational strategy to design and prepare M−N−C single-atom catalysts featured with high site-accessibility and site-density.
文摘This short review paper aims at assembling the present state of the art of the multiuses of metal oxides in heterogeneous catalysis, concerning liquid and gaseous phases of the reactant mixtures on solid catalysts. It includes the description of the main types of metal oxide catalysts, of their various preparation procedures and of the main reactions catalysed by them (acid-base type, selective and total oxidations, bi-functional catalysis, photocatalysis, biomass treatments, environmental catalysis and some of the numerous industrial applications). Challenges and prospectives are also discussed.
基金supported by the Natural Science Foundation of China(Nos.20872120 and 20572087)the Municipal Science Foundation of Chongqing City(No.2003-8118)+1 种基金the Ministry of Education,PR of China(No.106141)the Fundamental Research Funds for the Central Universities
文摘Direct aldol reactions of aldehydes and ketones can proceed smoothly in the presence of a catalytic amount of naphthol/sodium naphtholate（5 mol%） to afford the corresponding products with yields up to 98%.Such a bifunctional catalyst is more moderate than strong acid or base employed in direct aldol reactions.
基金R.C.and T.L.gratefully acknowledge the financial support from the National Key Research and Development Program of China(grant no.2018YFA0208600)National Natural Science Foundation of China(grant no.21871267,21802142,and 51572260)+1 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(XDB20000000)Key Research Program of Frontier Sciences,CAS(grant no.QYZDJ-SSW-SLH045).
文摘A Brønsted acid-base bifunctional metal-organic framework(MOF)catalyst,PCN-700-AB[A=Brønsted acid site,TPDC-(COOH)_(2)[(1,1′∶4′,1″-terphenyl)-2,2″,4,4″-tetracarboxylic acid]and B=Brønsted basic site,BDC-NH_(2)],was designed precisely and synthesized successfully through sequential installation of Brønsted acid and base functionalities in a crystalline zirconium(Zr)-MOF.The installation underwent single-crystal-to-singlecrystal transformation throughout the process;hence,the structure of the bifunctional catalyst could be characterized accurately via single-crystal X-ray crystallography.The bifunctional MOF catalyst obtained exhibited excellent acid-base catalytic activity for a cascade of one-pot deacetalization-Knoevenagel condensation reaction.The work presented here could be considered as a promising solution to incorporate multifunctional components readily,especially the hostile aspects,into one MOF structure.
基金This work was supported by the National Natural Science Foundation of China(Grant No.21908225)the National Key Research and Development Program of China(Grant No.2016YFB0600505)Youth Innovation Promotion Association,CAS(2014037).
文摘A series of Ni/HZSM-5 and Ni/HIM-5 bi-functional catalysts were synthesized and applied to the aqueous-phase hydrodeoxygenation(HDO)of phenol.The Ni dispersibility and particle sizes were shown to be directly related to the porosity and crystal sizes of the parent zeolites,which further influenced the catalytic performances.The large pores and small crystal sizes of the parent zeolites were beneficial for dispersing Ni and forming small Ni particles,and the corresponding Ni/zeolite catalyst exhibited a higher phenol conversion and selectivity towards hydrocarbons.Importantly,the Ni/HIM-5 bi-functional catalyst exhibited a high activity(98.3%)and high selectivity for hydrocarbons(98.8%)when heated at 220°C for 1 h and is thus a new potential catalyst for the HDO of phenolics to form hydrocarbons in the aqueous phase.
基金financially supported by the National Natural Science Foundation of China(U22A20421)the Qinglan Project of Jiangsu Province,the 533 Talent Program of Huaian City,and the College Students’Innovative Entrepreneurial Training Plan Program of Jiangsu Province(X202510323027).
文摘Endogenous hydrogen systems,consisting of metal–organic coordination catalysts and alcohols,have been widely applied for the transfer hydrogenation(TH)of biomass-derived carbonyl compounds in recent years.Metal-organic coordination catalysts showed satisfactory ability of TH in the secondary alcohols,but most of them could not effectively employ the cheaper primary alcohols as hydrogen donors.Furthermore,they commonly contained high metal contents,which also led to low catalytic efficiency in significant measure.In this work,we constructed a novel magnesium single-atom catalyst(Mg-NC)with merely 0.37 wt%Mg by means of a combined self-assembly and pyrolysis strategy.The characterization results indicated that Mg was atomically dispersed and it was coordinated with four pyridinic-N in Mg-NC.Due to the obvious electron transfer from Mg to its coordinated pyridinic-N,Mg–N_(4)active centers displayed high Lewis acid-base strength with abundant content,which brought remarkable catalytic activity.When Mg-NC was used for the TH of 5-hydroxymethylfurfural(HMF)in ethanol(EtOH),2,5-bis(hydroxymethyl)furan(BHMF)yield was up to 96.3%with high productivity of 19.85 molBHMF mol_(Mg)^(−1)h^(−1)at 150°C for 5 h.More interestingly,the process of TH over Mg-NC in EtOH was proved to proceed via the hydrogen radical mechanism.Additionally,Mg-NC exhibited powerful catalytic universality;it could not only utilize other primary alcohols(such as n-propanol and n-butanol)as hydrogen donors,but also catalyze the TH of other carbonyl compounds(such as furfural,5-methylfurfural,benzaldehyde,cyclohexanone,and levulinic acid).Overall,this work offered some important clues and references to reinforce the hydrogen-supplying ability of primary alcohols in the TH of various biomass-derived carbonyl compounds to high-value fine chemicals.
基金Sud-Chemie India Ltd. Cochin for support to carry out some of the instrumental analysis work
文摘Amorphous aluminophosphate(AlP) and metal-aluminophosphates(MAlPs, where M = 2.5 mol%Cu, Zn, Cr, Fe, Ce, or Zr) were prepared by coprecipitation method. Their surface properties and catalytic activity for the synthesis of jasminaldehyde through the aldol condensation of nheptanal and benzaldehyde were investigated. The nitrogen adsorption-desorption isotherms showed that the microporosity exhibited by the aluminophosphate was changed to a mesoporous and macroporous structure which depended on the metal incorporated, with a concomitant change in the surface area. Temperature-programmed desorption of NHand COrevealed that the materials possessed both acidic and basic sites. The acidic strength of the material was either increased or decreased depending on the nature of the metal. The basicity was increased compared to AlP. All the materials were X-ray amorphous and powder X-ray diffraction studies indicated the absence of metal oxide phases. The Fourier transform infrared analysis confirmed the presence of phosphate groups and also the absence of any M-O moieties in the materials. The selected organic reaction occurred only in the presence of the AlP and MAlPs. The selectivity for the jasminaldehyde product was up to 75% with a yield of 65%. The best conversion of nheptanal with a high selectivity to jasminaldehyde was obtained with FeAlP as the catalyst, and this material was characterized to have less weak acid sites and more basic sites.
基金financially supported by the National Natural Science Foundation of China(Nos.21673077,21473058,and 21273077)
文摘The phosphine-functionalized phosphonium-based ionic liquids(dppm-Q, dppe-Q, dppp-Q and dppb-Q) as the bi-functional ligands enable the efficient one-pot tandem hydroformylationeacetalization. It was found that, in dppm-Q, dppe-Q, dppp-Q and dppb-Q, the incorporated phosphino-fragments were responsible for Rh-catalyzed hydroformylation and the phosphoniums were in charge of the subsequent acetalization as the Lewis acid catalysts. Moreover, the diphosphonium-based ionic liquid of dppb-DQ could be applied as a co-solvent to immobilize the Rh/dppb-Q catalytic system with the advantages of the improved catalytic performance, the available catalyst recyclability, and the wide generality for the substrates.
基金supported by the New Energy and Industrial Technology Development Organization(NEDO)
文摘The catalytic performance of Pt-based catalysts for the total oxidation of hydrocarbons was investigated.The activity of supported Pt catalysts(Pt/Al2O3,Pt/ZrO2,Pt/TiO2,and Pt/H-ZSM-5)depends on the metal oxide support.Pt/Al2O3 showed the highest catalytic activity when the catalysts were aged at 750°C for 50 h in air.The activity of Pt/Al2O3 was dependent on the valence state of the Pt surface.Pt/Al2O3 with the Pt surface in the metallic state was more active than with the surface in the cationic state.The surface density of acid and basic sites on the Al2O3 support controlled the valence state of the Pt surface and stability of the Pt particles in the highly dispersed state,respectively.
基金This study was supported by the National Natural Science Foundation of China(Nos.22008058 and 52074119)the Joint Funds of National Natural Science Foundation of China(No.U20A20280)+3 种基金the program for Innovative Teams of Outstanding Young and Middle-aged Researchers in the Higher Education Institutions of Hubei Province(No.T2021010)the Joint supported by Hubei Provincial Natural Science Foundation and Huangshi of China(No.2022CFD039)the Postgraduate Innovative Research Project of Hubei Normal University(Nos.20220512 and 20220552)College Students innovation and entrepreneurship training program of Hubei Province(No.S202210513055).
文摘The rational design and preparation of promising cathode electrocatalysts with excellent activity and strong stability for metal-air batteries is a huge challenge.In this work,we innovate an approach of combining solvothermal with high-temperature pyrolysis utilizing zeolitic imidazolate framework(ZIF)-8 and ZIF-67 as the template to synthesize a novel hybrid material of hierarchical porous yolk-shell Co-N-C polyhedron nanocatalysts engaged in graphene nanopocket(yolk-shell Co-N-C@GNP).The obtained catalyst exhibits prominent bifunctional electrocatalytic performance for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)in the alkaline condition,in which the half-wave potential is 0.86 V for ORR,and the over-potential for OER is 0.42 V at 10 mA·cm^(-2).The rechargeable aqueous Zn-air battery fabricated with yolk-shell Co-N-C@GNP cathode deliveries an open circuit voltage(OCV)of 1.60 V,a peak power density of 236.2 mW·cm^(-2),and excellent cycling stability over 94 h at 5 mA·cm^(-2).The quasi-solid-state Zn-air battery(ZAB)using yolk-shell Co-N-C@GNP displays a high OCV of 1.40 V and a small voltage gap of 0.88 V in continuous cycling tests at 2 mA·cm^(-2).This work provides a valuable thought to focus attention on the design of high-efficient bifunctional catalysts with hierarchical porous yolk-shell framework and high-density metal active sites for metal-air battery technologies.
基金Project supported by the Science and Technology Ministry of China (No. 2001CCA02700).
文摘A novel environmentally benign process for the synthesis of methyl N-phenyl carbamate (MPC) from methanol and phenylurea was studied. Effect of solvent and catalyst on the reaction behavior was investigated. The IR spectra of methanol and phenylurea dissolved in different solvents were also recorded. Compared with use of methanol as both a reactant and a solvent, phenylurea conversion and selectivity to MPC increased by using toluene, benzene or anisole as a solvent, while phenylurea conversion decreased slightly by using n-octane as a solvent. The phenylurea conversion declined nearly 50% when dimethyl sulfoxide (DMSO) was used as a reaction media, and MPC selec- tivity decreased as well. The catalytic reaction tests showed that a basic catalyst enhanced the selectivity to MPC while an acidic catalyst promoted the formation of methyl carbamate and aniline. Moderate degree of basicity showed the best catalytic performance in the cases studied.
基金supported by the“Leading Goose”R&D Program of Zhejiang(2023C01110)。
文摘Alkali metal pollutants are often regarded as toxic agents for the catalytic hydrodeoxygenation(HDO)of biomass,hindering the conversion of biomass towards higher-value hydrocarbon fuels.In this study,a series of Pt/WO_(x)catalysts for HDO with varying K contents were synthesized,and an intriguing effect of K on activity was observed.The introduced K+occupies the H position of the hydroxyl group,poisoning Brùnsted acid sites(BAS);however,it regulates the adsorption of olefin intermediates,consequently facilitating the whole HDO reaction.Notably,dissociated hydrogen species on the metal sites can spillover to adjacent WO_(x)sites,liberating the hydroxyl group poisoned by K and thus operando forming BAS again(back to 84%of the K-free catalyst),which safeguards the dehydration step from alkali metal severe poisoning.By comparing the catalytic behavior on WO_(x)with non-reducible acidic Si-Al zeolite supports,we demonstrate that this‘deliverance effect'depends on the reducibility of the supports.The optimal 0.2 Pt0.8K/WO_(x)catalyst exhibited 2.6 times higher catalytic activity than 0.2 Pt/WO_(x),which also finds its applicability on other noble metals like Ru and Pd,achieving excellent yields across various lignin derivatives.This work not only reports an efficient K-doped Pt catalyst design for HDO reaction but also provides a more comprehensive understanding of the catalytic role of K additives on acid and metal sites.
基金supported by the National Key Research and Development Program of China(2018YFB0605801)National Natural Science Foundation of China(21871277)Chinese Academy of Sciences(QYZDYSSW-SLH013).
文摘The chemical transformation of CO2 and epoxides into cyclic carbonates has been receiving much attention and is one of the successful examples for CO2 utilization as carbon resource.Many catalysts containing halide anions have been explored and exhibit excellent catalytic activity.However,halogen salt is generally toxic and corrosive to reactors.From a green chemistry perspective,it is more attractive to develop a halogen-free catalyst with excellent performance.Herein,a review of recent research progress of halogen-free catalysts in the cycloaddition of CO2 and epoxide is presented.According to previous experimental and theoretical works,two possible strategies for achieving the halogen-free process were summarized.The relationship between catalytic activity and catalyst structure,the mechanism of CO2 activation should be both studied deeply combined with experimental results and DFT calculation,which can guide the design of new catalysts and realize halogen-free process under mild reaction conditions.
