Chlorotrifluoroethylene(CTFE)is a vital fluorinated olefinic monomer produced through the catalytic hydrodechlorination of trichlorotrifluoroethane(CFC-113),an eco-friendly process.However,hydrodechlorination catalyst...Chlorotrifluoroethylene(CTFE)is a vital fluorinated olefinic monomer produced through the catalytic hydrodechlorination of trichlorotrifluoroethane(CFC-113),an eco-friendly process.However,hydrodechlorination catalysts for olefin production often suffer from poor stability.The Pd/AC catalyst and Pd-Cu/AC catalyst prepared by co-impregnation method exhibited poor stability,Pd-Cu/AC catalyst with CFC-113 conversion dropping to around 37%after 50 h of hydrodechlorination reaction.Brunauer-Emmett-Teller,transmission electron microscopy,X-ray photoelectron spectroscopy,and X-ray diffraction of fresh and deactivated Pd/AC catalysts indicate that the deactivation of Pd/AC catalysts is due to high-temperature agglomeration of Pd.Comparative analysis of fresh and deactivated Pd-Cu/AC catalysts using Brunauer-Emmett-Teller,transmission electron microscopy,and thermogravimetric analysis techniques revealed decreased dispersion of active sites,reduced surface area,catalyst aggregation deactivation,and a significant decrease in Cu content.Furthermore,the results of NH3-TPD revealed that the acid sites of the catalyst increased significantly.X-ray diffraction spectra indicated the formation of new species,basic copper chloride(Cu_(2)(OH)_(3)Cl),during the reaction.As the reaction progressed,these new species agglomerated,leading to a gradual loss of catalyst activity.Moreover,the deactivated catalyst was successfully reactivated using a simple alkaline washing method.展开更多
Machine learning(ML)integrated with density functional theory(DFT)calculations have recently been used to accelerate the design and discovery of single-atom catalysts(SACs)by establishing deep structure–activity rela...Machine learning(ML)integrated with density functional theory(DFT)calculations have recently been used to accelerate the design and discovery of single-atom catalysts(SACs)by establishing deep structure–activity relationships.The traditional ML models are always difficult to identify the structural differences among the single-atom systems with different modification methods,leading to the limitation of the potential application range.Aiming to the structural properties of several typical two-dimensional MA_(2)Z_(4)-based single-atom systems(bare MA_(2)Z_(4)and metal single-atom doped/supported MA_(2)Z_(4)),an improved crystal graph convolutional neural network(CGCNN)classification model was employed,instead of the traditional machine learning regression model,to address the challenge of incompatibility in the studied systems.The CGCNN model was optimized using crystal graph representation in which the geometric configuration was divided into active layer,surface layer,and bulk layer(ASB-GCNN).Through ML and DFT calculations,five potential single-atom hydrogen evolution reaction(HER)catalysts were screened from chemical space of 600 MA_(2)Z_(4)-based materials,especially V_(1)/HfSn_(2)N_(4)(S)with high stability and activity(Δ_(GH*)is 0.06 eV).Further projected density of states(pDOS)analysis in combination with the wave function analysis of the SAC-H bond revealed that the SAC-dz^(2)orbital coincided with the H-s orbital around the energy level of−2.50 eV,and orbital analysis confirmed the formation ofσbonds.This study provides an efficient multistep screening design framework of metal single-atom catalyst for HER systems with similar two-dimensional supports but different geometric configurations.展开更多
A series of carboxylated long chain polyethylene glycols(abbreviated as PEGCOOH) has been synthesized and used to support chloroplatinic acid.These supported catalysts were then tested for their efficiency in the hydr...A series of carboxylated long chain polyethylene glycols(abbreviated as PEGCOOH) has been synthesized and used to support chloroplatinic acid.These supported catalysts were then tested for their efficiency in the hydrosilylation of alkenes.The factors affecting their catalytic properties,e.g.relative molecular mass of polyethylene glycol,reaction temperature,platinum content,and type of alkenes,have been studied.It was found that the activity of the platinum catalyst decreased with increasing length of the polyethylene glycol chain,and increased with reaction temperature.Moreover,these catalysts could be reused several times without a noticeable decrease in activity or selectivity.The reaction pathway leading to excellent selectivity for the β-adduct of hydrosilylation of alkenes with triethoxysilane catalyzed by this catalysis system was discussed.展开更多
Electrocatalytic oxygen evolution reaction(OER)has been recognized as the bottleneck of overall water splitting,which is a promising approach for sustainable production of H_(2).Transition metal(TM)hydroxides are the ...Electrocatalytic oxygen evolution reaction(OER)has been recognized as the bottleneck of overall water splitting,which is a promising approach for sustainable production of H_(2).Transition metal(TM)hydroxides are the most conventional and classical non-noble metal-based electrocatalysts for OER,while TM basic salts[M^(2+)(OH)_(2-x)(A_(m^(-))_(x/m),A=CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)]consisting of OH−and another anion have drawn extensive research interest due to its higher catalytic activity in the past decade.In this review,we summarize the recent advances of TM basic salts and their application in OER and further overall water splitting.We categorize TM basic salt-based OER pre-catalysts into four types(CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)according to the anion,which is a key factor for their outstanding performance towards OER.We highlight experimental and theoretical methods for understanding the structure evolution during OER and the effect of anion on catalytic performance.To develop bifunctional TM basic salts as catalyst for the practical electrolysis application,we also review the present strategies for enhancing its hydrogen evolution reaction activity and thereby improving its overall water splitting performance.Finally,we conclude this review with a summary and perspective about the remaining challenges and future opportunities of TM basic salts as catalysts for water electrolysis.展开更多
Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a hi...Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a high content of P(which exists as PO3-),and therefore have been recognized as highly efficient catalysts for oxygen evolution reaction(OER)and the bottleneck of electrochemical water splitting.Furthermore,TMMPs can also contribute to hydrogen evolution reaction(HER)in alkaline and neutral media by facilitating water dissociation,and thus,overall water splitting can be achieved using this kind of material.In this timely review,we summarize the recent advances in the synthesis of TMMPs and their applications in OER and HER.We present a brief introduction of the structure and synthetic strategies of TMMPs in the first two parts.Then,we review the latest progress made in research on TMMPs as OER,HER,and overall water-splitting electrocatalysts.In this part,the intrinsic activity of TMMPs as well as the current strategy for improving the catalytic activity will be discussed systematically.Finally,we present the future opportunities and the remaining challenges for the application of TMMPs in the electrocatalysis field.展开更多
The overall performance of metal catalysts can be efficiently adjusted by modifying carbon carriers with different valence sulfur precursors.The wet impregnation technique successfully prepared carbon material carrier...The overall performance of metal catalysts can be efficiently adjusted by modifying carbon carriers with different valence sulfur precursors.The wet impregnation technique successfully prepared carbon material carriers doped with varying sources of sulfur(Na_(2)SO_(4),NaHSO_(3),Na_(2)S·9H_(2)O).Palladium carbon catalysts doped with different sulfur precursors had been prepared with the aid of the liquid-phase reduction method of the selective hydrogenation of o-chloronitrobenzene(o-CNB)to o-chloroaniline(o-CAN).The catalyst prepared for Na_(2)S·9H_(2)O as a precursor has excellent performance,and the selectivity for o-CAN is more than 99.9%at 100%conversion.In addition,the characterization results show that with the decrease of S valence,the electronic effect between S and Pd increases,and the outer electron shift of Pd increases,which reduces the adsorption and dissociation ability of Pd to hydrogen,resulting in excellent selectivity.The effects provided a good idea for the hydrogenation of o-CNB and a different point of view on sulfur doping in a variety of hydrogenation reactions.展开更多
In the search of alternative resources to make commodity chemicals and transportation fuels for a low carbon future,lignocellulosic biomass with over 180-billion-ton annual production rate has been identified as a pro...In the search of alternative resources to make commodity chemicals and transportation fuels for a low carbon future,lignocellulosic biomass with over 180-billion-ton annual production rate has been identified as a promising feedstock.This review focuses on the state-of-the-art catalytic transformation of lignocellulosic biomass into value-added chemicals and fuels.Following a brief introduction on the structure,major resources and pretreatment methods of lignocellulosic biomass,the catalytic conversion of three main components,i.e.,cellulose,hemicellulose and lignin,into various compounds are comprehensively discussed.Either in separate steps or in one-pot,cellulose and hemicellulose are hydrolyzed into sugars and upgraded into oxygen-containing chemicals such as 5-HMF,furfural,polyols,and organic acids,or even nitrogen-containing chemicals such as amino acids.On the other hand,lignin is first depolymerized into phenols,catechols,guaiacols,aldehydes and ketones,and then further transformed into hydrocarbon fuels,bioplastic precursors and bioactive compounds.The review then introduces the transformations of whole biomass via catalytic gasification,catalytic pyrolysis,as well as emerging strategies.Finally,opportunities,challenges and prospective of woody biomass valorization are highlighted.展开更多
The depolymerization and upgrading of lignin from raw biomass,while keeping cellulose intact is important in biorefinery and various metal-based catalysts have been used in reductive catalytic fractionation,a key meth...The depolymerization and upgrading of lignin from raw biomass,while keeping cellulose intact is important in biorefinery and various metal-based catalysts have been used in reductive catalytic fractionation,a key method in"lignin-first"strategy,Recently,we found that a core-shell structured Co@CoO catalyst with CoO shell as the real active site had excellent performance in the hydrogenolysis of 5-hydromethylfurfural to 2,5-dimethylfuran due to its unique ability to dissociate H_(2)and yield active H^(δ-)species(Xiang et al.,2022).In this work,we report a one-pot depolymerization and upgrading of lignocellulose to alkylcyclohexanols,a flavour precursor,with intact cellulose over this unique core-shell structured catalyst,Co@CoO.Lignin model compounds(β-O-4,4-O-5,α-O-4)were first used to clarify the activity of Co@CoO catalyst.Then,the one-pot conversion of various organosolv lignin(birch,pine and poplar)to alkylcyclohexanols was realized with the mass yield of alkylcyclohexanols up to25.8 wt%from birch lignin under the reaction condition of 210℃,1 MPa H_(2),16 h.Finally,the corresponding woody sawdusts were used as feedstocks and found that the Co@CoO catalyst indeed preferentially depolymerized and upgraded the lignin part and obtained the same alkylcyclohexanols products with the retention of cellulose-rich pulp.The collected alkylcyclohexanols were further esterified to obtain valueadded esters,which can be used as flavors.This work will inspire the design of new efficient metal oxide catalysts in lignin fractionation and depolymerization to high-value-added chemicals with intact cellulose.展开更多
Carbon is a normally used adsorbent for removal of heavy metal ion in aqueous solutions,but the efficient adsorbent needs intensive modification by heteroatom doped or supported noble metals that cause severe pollutio...Carbon is a normally used adsorbent for removal of heavy metal ion in aqueous solutions,but the efficient adsorbent needs intensive modification by heteroatom doped or supported noble metals that cause severe pollution and easy leaching of active components during use.In this paper,the role of intrinsic defects on Hg^(2+)adsorption for carbon adsorbent was investigated.The maximum adsorbing capacity of defectrich carbon has been improved up to 433 mg·g^(-1)which is comparable to most of the modified carbon adsorbents via supported metal chloride or noble metal components.The basicity is increased with the content of defective sites and the strong chemical bonding can be formed via electron transformation between the defect sites with adsorbed Hg^(2+).The present study gives a direction to explore cheap and easily scale-up high-performance mercury adsorbents by simply tuning the intrinsic defective structure of carbon without the necessity to support metal or other organic compounds.展开更多
Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) throu...Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.展开更多
Solar-driven photo-thermal catalytic CO_(2)methanation reaction is a promising technology to alleviate the problems posed by greenhouse gases emissions.However,designing advanced photo-thermal catalysts remains a rese...Solar-driven photo-thermal catalytic CO_(2)methanation reaction is a promising technology to alleviate the problems posed by greenhouse gases emissions.However,designing advanced photo-thermal catalysts remains a research challenge for CO_(2)methanation reaction.In this work,a series of ABO3(A=lanthanide,B=transition metal)perovskite catalysts with Ce-substituted LaNiO3(La_(1-x)Ce_(x)NiO_(3),x=0,0.2,0.5,0.8,1)were synthesized for CO_(2)methanation.The La_(0.2)Ce_(0.8)NiO_(3) exhibited the highest CH_(4) formation rate of 258.9 mmol·g^(-1)·hcat-1,CO_(2)conversion of 55.4%and 97.2%CH_(4) selectivity at 300℃with the light intensity of 2.9 W·cm^(-2).Then the catalysts were thoroughly analyzed by physicochemical structure and optical properties characterizations.The partial substitution of the A-site provided more active sites for the adsorption and activation of CO_(2)/H_(2).The sources of the active sites were considered to be the oxygen vacancies(O_(v))created by lattice distortions due to different species of ions(La^(3+),Ce^(4+),Ce^(3+))and exsolved Ni0 by H_(2)reduction.The catalysts have excellent light absorption absorbance and low electron-hole(e^(-)/h^(+))recombination rate,which greatly contribute to the excellent performance in photo-thermal synergistic catalysis(PTC)CO_(2)methanation.The results of in situ irradiated electron paramagnetic resonance spectrometer(ISI-EPR)and ISI-X-ray photoelectron spectroscopy(XPS)indicated that the aggregation of unpaired electrons near the defects and Ni metal(from La and Ce ions to Ov and Ni0)accelerated adsorption and activation of CO_(2)/H_(2).At last,the catalyst properties and structure were correlated with the proposed reaction mechanism from the in situ diffuse reflection infrared Fourier transform spectrum(DRIFTS)measurements.The in situ precipitation of the B-site enhanced the dispersion of Ni,while its enriched photoelectrons upon illumination further promote hydrogen dissociation.More H^(*)spillover accelerated the rate-determining step(RDS)of HCOO*hydrogenation.This work provides the theoretical basis for the development of catalysts and industrial application.展开更多
Using cetyl-trimethyl-ammonium bromide (CTMAB) as the template agent and tetraethylorthosilicate (TEOS) as the silica source, the MCM-41 mesoporous materials were synthesized with La or Ce incorporated in the fram...Using cetyl-trimethyl-ammonium bromide (CTMAB) as the template agent and tetraethylorthosilicate (TEOS) as the silica source, the MCM-41 mesoporous materials were synthesized with La or Ce incorporated in the framework under hydrothermal conditions. The structure and the state of La or Ce were investigated through the analyses of XRD, nitrogen adsorption-desorption, FT-IR, and UV-Vis. XRD and N2 adsorption-desorption results showed that Ln-MCM-41 exhibited the loss of the lattice ordering of the MCM-41 construct, and larger unit cell parameter and pore diameter than pure silica MCM-41. The FT-IR and UV-Vis results indicated the presence of isolated tetra-coordinated La or Ce ions in the framework and other Ln species dispersed highly on the Ln-MCM-41 surface simultaneously. Furthermore, their catalytic behaviors in the oxidation of styrene were studied using H2O2 as the oxidant. The La-MCM-41 catalysts exhibited high reactivity and the reactivity increased with the increase of the La content in the La-MCM-41 samples. On the contrary, Ce-MCM-41 catalysts showed low reactivity in the oxidation of styrene and the conversion of styrene decreased with the increase of the Ce content in the Ce-MCM-41 samples.展开更多
A series of high surface area graphitic carbon materials (HSGCs) were prepared by ball-milling method. Effect of the graphitic degree of HSGCs on the catalytic performance of Ba-Ru-K/HSGC-x (x is the ball-milling t...A series of high surface area graphitic carbon materials (HSGCs) were prepared by ball-milling method. Effect of the graphitic degree of HSGCs on the catalytic performance of Ba-Ru-K/HSGC-x (x is the ball-milling time in hour) catalysts was studied using ammonia synthesis as a probe reaction. The graphitic degree and pore structure of HSGC-x supports could be successfully tuned via the variation of ball-milling time. Ru nanoparticles of different Ba-Ru-K/HSGC-x catalysts are homogeneously distributed on the supports with the particle sizes ranging from 1.6 to 2.0 nm. The graphitic degree of the support is closely related to its facile electron transfer capability and so plays an important role in improving the intrinsic catalytic performance of Ba-Ru-K/HSGC-x catalyst.展开更多
To search the new effective nitrogen reduction reaction(NRR)electrocatalyst is very important for the ammonia-based industry.Herein,we reported the design of a novel NRR electrocatalyst with Ru NPs loaded on oxygen-va...To search the new effective nitrogen reduction reaction(NRR)electrocatalyst is very important for the ammonia-based industry.Herein,we reported the design of a novel NRR electrocatalyst with Ru NPs loaded on oxygen-vacancy TiO2(Ru/TiO2-Vo).Structural characterizations revealed that oxygen vacancy was loaded in the matrix of Ru/TiO2-Vo.Electrocatalytic results indicated that Ru/TiO2-Vo showed good NRR performance(2.11μg h^-1 cm^-2).Contrast tests showed that NRR property of Ru/TiO2-Vo was much better than those of Ru/TiO-12(B)(0.53μg hcm^-2)and Ru/P25(0.42μg h^-1 cm^-2).Furthermore,density functional theory calculation results indicated catalytic mechanism of NRR and rate-determining step(*N2+1/2 H2→*N+*NH)was the potential-determining step with the overpotential requirement of 0.21 V.A combination of electronic structure analysis and catalytic measurement shed light on the synergistic effect of Ru and oxygen vacancy on the NRR performance.展开更多
Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Rama...Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Raman spectroscopy. The results showed that all the samples held the structure of MCM-48, and Ce could enter the framework of MCM-48. However, when Ce/Si molar ratio in the sampies was high (0.04 or 0.059), there were CeO2 crystallites as secondary phase in the extraframework of MCM-48. Ce-doped MCM-48 was a very efficient catalyst for the oxidation of cyclohexane in a solvent-free system with oxygen as an oxidant. In the conditions of 0.5 MPa 02 and 413 K for 5 h, the conversion of cyclohexane was 8.1% over Ce-MCM-48-0.02, the total selectivity of cyclohexanol and cyclohaxnone was 98.7%. With an increase of Ce content, the conversion of cyclohexane and the selectivity to cyclohexanol decreased somewhat, but the selectivity to cyclohexanone increased.展开更多
Paramagnetic polymer microspheres were synthesized by the inverse suspension polymerizationmethod through polymerization of glycidyl methacrylate,ally glycidyl ether and methacrylamide onthe surface of silica‐coated ...Paramagnetic polymer microspheres were synthesized by the inverse suspension polymerizationmethod through polymerization of glycidyl methacrylate,ally glycidyl ether and methacrylamide onthe surface of silica‐coated Fe3O4nanoparticles using N,N’‐methylene‐bis(acrylamide)as across‐linking agent.Penicillin G acylase(PGA)was covalently immobilized on the surface of theparamagnetic microspheres by reacting the amino groups of the PGA molecules with the epoxygroups of the paramagnetic polymer microspheres.The effect of the SiO2coating and the amount ofparamagnetic Fe3O4nanoparticles on the initial activity and the operational stability of the immobilizedPGA was investigated.The results indicated that SiO2played an important role in the polymerization process and paramagnetic polymer microspheres with a SiO2‐coated Fe3O4nanoparticles mass content of7.5%are an optimal support material for PGA immobilization.Immobilized PGA on the paramagnetic polymer microspheres shows a high initial activity of430U/g(wet)and retains99%of its initial activity after recycling10times.Furthermore,immobilized PGA exhibits high thermal stability,pH stability and excellent reusability,which can be rapidly recycled by the aid of magnet.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.展开更多
Efficient conversion of lignin to aromatic hydrocarbons via depolymerization and subsequent hydrodeoxygenation is important.Previously,we found that NbOx species played a key role in the activation and cleavage of C-O...Efficient conversion of lignin to aromatic hydrocarbons via depolymerization and subsequent hydrodeoxygenation is important.Previously,we found that NbOx species played a key role in the activation and cleavage of C-O bonds in lignin and its model compounds.In this study,commercial niobic acid(HY-340),niobium phosphate(NbPO-CBMM)and lab-made layered niobium oxide(Nb2O5-Layer)were chosen as supports to study the effect of Brosted and Lewis acids on the activation of C-O bonds in lignin conversion.A variety of Ru-loaded,Nb-based catalysts with different Ru particle sizes were prepared and applied to the conversion of p-cresol.The results show that all the Ru/Nb-based catalysts produce high mole yields of C7-C9 hydrocarbons(82.3%-9.1%).What's more,Ru/Nb2O5-Layer affords the best mole yield of C7-C9 hydrocarbons and selectivity for C7-C9 aromatic hydrocarbons,of up to 99.1% and 88.0%,respectively.Moreover,it was found that Lewis acid sites play important roles in the depolymerization of enzymatic lignin into phenolic monomers and the cleavage of the C-O bond of phenols.Additionally,the electronic state and particle size of Ru are significant factors which influence the selectivity for aromatic hydrocarbons.A partial positive charge on the metallic Ru surface and a smaller Ru particle size are beneficial in improving the selectivity for aromatic hydrocarbons.展开更多
Supported coupling catalysts for CS2 removal were prepared with different activated carbons originated from wood,coconut shell and coal as supports,and their catalytic activities for CS2 removal were tested at ambient...Supported coupling catalysts for CS2 removal were prepared with different activated carbons originated from wood,coconut shell and coal as supports,and their catalytic activities for CS2 removal were tested at ambient temperature.The textural and surface properties of the activated carbons were characterized by nitrogen adsorption,temperature-programmed desorption(TPD)and Boehm titration.The activated carbon support with meso-and macropores,and oxygen-functional groups performs higher CS2 removal ability at ambient temperature.The effects of flow rate,CS2 inlet concentration,temperature and relative humidity on CS2 removal were also investigated.High efficient removal is obtained at temperature of 50-C,space velocity of 2000 h-1,inlet CS2 concentration of 500 mgS/m3 and relative humidity of 20%with the breakthrough sulfur capacity up to 4.3 gS/gCat and working sulfur capacity up to 7 gS/gCat.展开更多
LaMnO3was prepared by citrate sol‐gel,coprecipitation,hard template,and hydrothermal methods,respectively,and its catalytic performance for the combustion of vinyl chloride was investigated.N2adsorption‐desorption,X...LaMnO3was prepared by citrate sol‐gel,coprecipitation,hard template,and hydrothermal methods,respectively,and its catalytic performance for the combustion of vinyl chloride was investigated.N2adsorption‐desorption,X‐ray diffraction(XRD),Raman spectroscopy(Raman),O2temperature programmed desorption(O2‐TPD),H2temperature programmed surface reaction(H2‐TPR)and X‐ray photoelectron spectroscopy(XPS)were used to characterize the physicochemical properties of the LaMnO3samples.The preparation methods had obvious effects on the distribution of oxygen and manganese species on the catalyst surface.The reaction followed the suprafacial mechanism;the activity corresponded with the high amount of Mn4+and adsorbed oxygen species.LaMnO3prepared by the citrate sol‐gel method had the best performance for vinyl chloride combustion with T90of182°C.The optimal activity was attributed to the improved redox capability of Mn4+/Mn3+.More available adsorbed oxygen and Mn4+species on the surface were mainly responsible for the remarkable enhancement of the catalytic activity.展开更多
基金supported by the National Natural Science Foundation of China(22008212,22078292,21902124)Natural Science Basic Research Planning Shaanxi Province of China(2017ZDJC-29)+2 种基金Key Research and Development Project of Shaanxi Province(2018ZDXM-GY-173)China Postdoctoral Science Foundation(2019 M663848)Open cooperative innovation fund of Xi'an Institute of modern chemistry(SYJJ48).
文摘Chlorotrifluoroethylene(CTFE)is a vital fluorinated olefinic monomer produced through the catalytic hydrodechlorination of trichlorotrifluoroethane(CFC-113),an eco-friendly process.However,hydrodechlorination catalysts for olefin production often suffer from poor stability.The Pd/AC catalyst and Pd-Cu/AC catalyst prepared by co-impregnation method exhibited poor stability,Pd-Cu/AC catalyst with CFC-113 conversion dropping to around 37%after 50 h of hydrodechlorination reaction.Brunauer-Emmett-Teller,transmission electron microscopy,X-ray photoelectron spectroscopy,and X-ray diffraction of fresh and deactivated Pd/AC catalysts indicate that the deactivation of Pd/AC catalysts is due to high-temperature agglomeration of Pd.Comparative analysis of fresh and deactivated Pd-Cu/AC catalysts using Brunauer-Emmett-Teller,transmission electron microscopy,and thermogravimetric analysis techniques revealed decreased dispersion of active sites,reduced surface area,catalyst aggregation deactivation,and a significant decrease in Cu content.Furthermore,the results of NH3-TPD revealed that the acid sites of the catalyst increased significantly.X-ray diffraction spectra indicated the formation of new species,basic copper chloride(Cu_(2)(OH)_(3)Cl),during the reaction.As the reaction progressed,these new species agglomerated,leading to a gradual loss of catalyst activity.Moreover,the deactivated catalyst was successfully reactivated using a simple alkaline washing method.
基金supported by the National Key R&D Program of China(2021YFA1500900)National Natural Science Foundation of China(U21A20298,22141001).
文摘Machine learning(ML)integrated with density functional theory(DFT)calculations have recently been used to accelerate the design and discovery of single-atom catalysts(SACs)by establishing deep structure–activity relationships.The traditional ML models are always difficult to identify the structural differences among the single-atom systems with different modification methods,leading to the limitation of the potential application range.Aiming to the structural properties of several typical two-dimensional MA_(2)Z_(4)-based single-atom systems(bare MA_(2)Z_(4)and metal single-atom doped/supported MA_(2)Z_(4)),an improved crystal graph convolutional neural network(CGCNN)classification model was employed,instead of the traditional machine learning regression model,to address the challenge of incompatibility in the studied systems.The CGCNN model was optimized using crystal graph representation in which the geometric configuration was divided into active layer,surface layer,and bulk layer(ASB-GCNN).Through ML and DFT calculations,five potential single-atom hydrogen evolution reaction(HER)catalysts were screened from chemical space of 600 MA_(2)Z_(4)-based materials,especially V_(1)/HfSn_(2)N_(4)(S)with high stability and activity(Δ_(GH*)is 0.06 eV).Further projected density of states(pDOS)analysis in combination with the wave function analysis of the SAC-H bond revealed that the SAC-dz^(2)orbital coincided with the H-s orbital around the energy level of−2.50 eV,and orbital analysis confirmed the formation ofσbonds.This study provides an efficient multistep screening design framework of metal single-atom catalyst for HER systems with similar two-dimensional supports but different geometric configurations.
基金Supported by the Educational Commission of Zhejiang Province of China (Y201017419)Zhejiang Province Program(2008C14041)
文摘A series of carboxylated long chain polyethylene glycols(abbreviated as PEGCOOH) has been synthesized and used to support chloroplatinic acid.These supported catalysts were then tested for their efficiency in the hydrosilylation of alkenes.The factors affecting their catalytic properties,e.g.relative molecular mass of polyethylene glycol,reaction temperature,platinum content,and type of alkenes,have been studied.It was found that the activity of the platinum catalyst decreased with increasing length of the polyethylene glycol chain,and increased with reaction temperature.Moreover,these catalysts could be reused several times without a noticeable decrease in activity or selectivity.The reaction pathway leading to excellent selectivity for the β-adduct of hydrosilylation of alkenes with triethoxysilane catalyzed by this catalysis system was discussed.
基金supported by the financial support from Natural Science Foundation of China(Nos.21871065,22209129 and 22071038)High-Level Innovation and Entrepreneurship(QCYRCXM-2022-123)+1 种基金support from the“Young Talent Support Plan”of Xi’an Jiaotong University(HG6J024)“Young Talent Lift Plan”of Xi’an city(095920221352).
文摘Electrocatalytic oxygen evolution reaction(OER)has been recognized as the bottleneck of overall water splitting,which is a promising approach for sustainable production of H_(2).Transition metal(TM)hydroxides are the most conventional and classical non-noble metal-based electrocatalysts for OER,while TM basic salts[M^(2+)(OH)_(2-x)(A_(m^(-))_(x/m),A=CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)]consisting of OH−and another anion have drawn extensive research interest due to its higher catalytic activity in the past decade.In this review,we summarize the recent advances of TM basic salts and their application in OER and further overall water splitting.We categorize TM basic salt-based OER pre-catalysts into four types(CO_(3)^(2−),NO_(3)^(−),F^(−),Cl^(−)according to the anion,which is a key factor for their outstanding performance towards OER.We highlight experimental and theoretical methods for understanding the structure evolution during OER and the effect of anion on catalytic performance.To develop bifunctional TM basic salts as catalyst for the practical electrolysis application,we also review the present strategies for enhancing its hydrogen evolution reaction activity and thereby improving its overall water splitting performance.Finally,we conclude this review with a summary and perspective about the remaining challenges and future opportunities of TM basic salts as catalysts for water electrolysis.
基金the Natural Science Foundation of China(Grant Nos.21871065,22209129,and 22071038)the Heilongjiang Touyan Team(HITTY-20190033)+3 种基金High-Level Innovation and Entrepreneurship(QCYRCXM-2022-123)the Talent Project of Qinchuangyuan and Interdisciplinary Research Foundation of HIT(IR2021205)Professor Li acknowledges the financial support from the“Young Talent Support Plan”of Xi'an Jiaotong University(HG6J024)the“Young Talent Lift Plan”of Xi'an city(095920221352).
文摘Sustainable production of H2 through electrochemical water splitting is of great importance in the foreseeable future.Transition-metal metaphosphates(TMMPs)have a three-dimensional(3D)open-framework structure and a high content of P(which exists as PO3-),and therefore have been recognized as highly efficient catalysts for oxygen evolution reaction(OER)and the bottleneck of electrochemical water splitting.Furthermore,TMMPs can also contribute to hydrogen evolution reaction(HER)in alkaline and neutral media by facilitating water dissociation,and thus,overall water splitting can be achieved using this kind of material.In this timely review,we summarize the recent advances in the synthesis of TMMPs and their applications in OER and HER.We present a brief introduction of the structure and synthetic strategies of TMMPs in the first two parts.Then,we review the latest progress made in research on TMMPs as OER,HER,and overall water-splitting electrocatalysts.In this part,the intrinsic activity of TMMPs as well as the current strategy for improving the catalytic activity will be discussed systematically.Finally,we present the future opportunities and the remaining challenges for the application of TMMPs in the electrocatalysis field.
基金financially supported by the National Natural Science Foundation of China(22078292,22008212,U20A20119,21776258)。
文摘The overall performance of metal catalysts can be efficiently adjusted by modifying carbon carriers with different valence sulfur precursors.The wet impregnation technique successfully prepared carbon material carriers doped with varying sources of sulfur(Na_(2)SO_(4),NaHSO_(3),Na_(2)S·9H_(2)O).Palladium carbon catalysts doped with different sulfur precursors had been prepared with the aid of the liquid-phase reduction method of the selective hydrogenation of o-chloronitrobenzene(o-CNB)to o-chloroaniline(o-CAN).The catalyst prepared for Na_(2)S·9H_(2)O as a precursor has excellent performance,and the selectivity for o-CAN is more than 99.9%at 100%conversion.In addition,the characterization results show that with the decrease of S valence,the electronic effect between S and Pd increases,and the outer electron shift of Pd increases,which reduces the adsorption and dissociation ability of Pd to hydrogen,resulting in excellent selectivity.The effects provided a good idea for the hydrogenation of o-CNB and a different point of view on sulfur doping in a variety of hydrogenation reactions.
文摘In the search of alternative resources to make commodity chemicals and transportation fuels for a low carbon future,lignocellulosic biomass with over 180-billion-ton annual production rate has been identified as a promising feedstock.This review focuses on the state-of-the-art catalytic transformation of lignocellulosic biomass into value-added chemicals and fuels.Following a brief introduction on the structure,major resources and pretreatment methods of lignocellulosic biomass,the catalytic conversion of three main components,i.e.,cellulose,hemicellulose and lignin,into various compounds are comprehensively discussed.Either in separate steps or in one-pot,cellulose and hemicellulose are hydrolyzed into sugars and upgraded into oxygen-containing chemicals such as 5-HMF,furfural,polyols,and organic acids,or even nitrogen-containing chemicals such as amino acids.On the other hand,lignin is first depolymerized into phenols,catechols,guaiacols,aldehydes and ketones,and then further transformed into hydrocarbon fuels,bioplastic precursors and bioactive compounds.The review then introduces the transformations of whole biomass via catalytic gasification,catalytic pyrolysis,as well as emerging strategies.Finally,opportunities,challenges and prospective of woody biomass valorization are highlighted.
基金supported financially by the National Natural Science Foundation of China(Nos.21832002,21808063,22002043,21872050)。
文摘The depolymerization and upgrading of lignin from raw biomass,while keeping cellulose intact is important in biorefinery and various metal-based catalysts have been used in reductive catalytic fractionation,a key method in"lignin-first"strategy,Recently,we found that a core-shell structured Co@CoO catalyst with CoO shell as the real active site had excellent performance in the hydrogenolysis of 5-hydromethylfurfural to 2,5-dimethylfuran due to its unique ability to dissociate H_(2)and yield active H^(δ-)species(Xiang et al.,2022).In this work,we report a one-pot depolymerization and upgrading of lignocellulose to alkylcyclohexanols,a flavour precursor,with intact cellulose over this unique core-shell structured catalyst,Co@CoO.Lignin model compounds(β-O-4,4-O-5,α-O-4)were first used to clarify the activity of Co@CoO catalyst.Then,the one-pot conversion of various organosolv lignin(birch,pine and poplar)to alkylcyclohexanols was realized with the mass yield of alkylcyclohexanols up to25.8 wt%from birch lignin under the reaction condition of 210℃,1 MPa H_(2),16 h.Finally,the corresponding woody sawdusts were used as feedstocks and found that the Co@CoO catalyst indeed preferentially depolymerized and upgraded the lignin part and obtained the same alkylcyclohexanols products with the retention of cellulose-rich pulp.The collected alkylcyclohexanols were further esterified to obtain valueadded esters,which can be used as flavors.This work will inspire the design of new efficient metal oxide catalysts in lignin fractionation and depolymerization to high-value-added chemicals with intact cellulose.
基金funded by the 2019“Rare Earth and Coal Chemical Industry”Key Science and Technology Project of Inner Mongolia Autonomous Region of China(2019ZD017)the National Natural Science Foundation of China(21908197,22108248,22208305)。
文摘Carbon is a normally used adsorbent for removal of heavy metal ion in aqueous solutions,but the efficient adsorbent needs intensive modification by heteroatom doped or supported noble metals that cause severe pollution and easy leaching of active components during use.In this paper,the role of intrinsic defects on Hg^(2+)adsorption for carbon adsorbent was investigated.The maximum adsorbing capacity of defectrich carbon has been improved up to 433 mg·g^(-1)which is comparable to most of the modified carbon adsorbents via supported metal chloride or noble metal components.The basicity is increased with the content of defective sites and the strong chemical bonding can be formed via electron transformation between the defect sites with adsorbed Hg^(2+).The present study gives a direction to explore cheap and easily scale-up high-performance mercury adsorbents by simply tuning the intrinsic defective structure of carbon without the necessity to support metal or other organic compounds.
基金supported by the financial support from the National Natural Science Foundation of China (21871065, 22071038, 22209129)the Heilongjiang Touyan Team (HITTY20190033)the Interdisciplinary Research Foundation of HIT (IR2021205)。
文摘Surface reconstruction of electrocatalysts has been widely witnessed during the electrochemical processes.Here,NiS_(2),NiSe_(2), and Se doped NiS_(2)(Se-NiS_(2)) are fabricated for oxygen evolution reaction(OER) through a mild sulfuration and/or selenylation process of Ni(OH)_(2) supported on carbon cloth(CC).Through careful in-situ Raman spectroscopy and ex-situ X-ray photoelectron spectroscopy,surface reconstruction of NiS_(2),NiSe_(2),and Se-NiS_(2) during the OER process has been revealed.A potentialdependent study shows that Se-NiS_(2) undergoes surface evolution at lower potentials and requires the lowest potential for conversion to NiOOH as a highly OER-active species,accompanied by the leaching of SO_(4)^(2-) and SeO_(4)^(2-) that can again be adsorbed on the catalyst surface to enhance the catalytic activity.Density functional theory(DFT) calculations confirm that Se-NiS_(2) is more susceptible to surface oxidation through the OER process.Therefore,Se-NiS_(2) exhibits outstanding OER activity and stability in alkaline conditions,requiring an overpotential of 343 mV at a current density of 50 mA cm^(-2).A novel insight is provided by our work in understanding the surface reconstruction and electrocatalytic mechanism of Ni-based chalcogenides.
基金supported by the National Natural Science Foundation of China(No.52076176)Fundamental Research Funds for the Central Universities(Nos.xzd012023037 and xzy022023034)Innovation Capability Support Program of Shaanxi(No.2023-CX-TD-26).
文摘Solar-driven photo-thermal catalytic CO_(2)methanation reaction is a promising technology to alleviate the problems posed by greenhouse gases emissions.However,designing advanced photo-thermal catalysts remains a research challenge for CO_(2)methanation reaction.In this work,a series of ABO3(A=lanthanide,B=transition metal)perovskite catalysts with Ce-substituted LaNiO3(La_(1-x)Ce_(x)NiO_(3),x=0,0.2,0.5,0.8,1)were synthesized for CO_(2)methanation.The La_(0.2)Ce_(0.8)NiO_(3) exhibited the highest CH_(4) formation rate of 258.9 mmol·g^(-1)·hcat-1,CO_(2)conversion of 55.4%and 97.2%CH_(4) selectivity at 300℃with the light intensity of 2.9 W·cm^(-2).Then the catalysts were thoroughly analyzed by physicochemical structure and optical properties characterizations.The partial substitution of the A-site provided more active sites for the adsorption and activation of CO_(2)/H_(2).The sources of the active sites were considered to be the oxygen vacancies(O_(v))created by lattice distortions due to different species of ions(La^(3+),Ce^(4+),Ce^(3+))and exsolved Ni0 by H_(2)reduction.The catalysts have excellent light absorption absorbance and low electron-hole(e^(-)/h^(+))recombination rate,which greatly contribute to the excellent performance in photo-thermal synergistic catalysis(PTC)CO_(2)methanation.The results of in situ irradiated electron paramagnetic resonance spectrometer(ISI-EPR)and ISI-X-ray photoelectron spectroscopy(XPS)indicated that the aggregation of unpaired electrons near the defects and Ni metal(from La and Ce ions to Ov and Ni0)accelerated adsorption and activation of CO_(2)/H_(2).At last,the catalyst properties and structure were correlated with the proposed reaction mechanism from the in situ diffuse reflection infrared Fourier transform spectrum(DRIFTS)measurements.The in situ precipitation of the B-site enhanced the dispersion of Ni,while its enriched photoelectrons upon illumination further promote hydrogen dissociation.More H^(*)spillover accelerated the rate-determining step(RDS)of HCOO*hydrogenation.This work provides the theoretical basis for the development of catalysts and industrial application.
基金Project supported by the National Basic Research Program of China (2004CB719500)the Commission of Science and Technology of Shanghai Municipality (03DJ14006)
文摘Using cetyl-trimethyl-ammonium bromide (CTMAB) as the template agent and tetraethylorthosilicate (TEOS) as the silica source, the MCM-41 mesoporous materials were synthesized with La or Ce incorporated in the framework under hydrothermal conditions. The structure and the state of La or Ce were investigated through the analyses of XRD, nitrogen adsorption-desorption, FT-IR, and UV-Vis. XRD and N2 adsorption-desorption results showed that Ln-MCM-41 exhibited the loss of the lattice ordering of the MCM-41 construct, and larger unit cell parameter and pore diameter than pure silica MCM-41. The FT-IR and UV-Vis results indicated the presence of isolated tetra-coordinated La or Ce ions in the framework and other Ln species dispersed highly on the Ln-MCM-41 surface simultaneously. Furthermore, their catalytic behaviors in the oxidation of styrene were studied using H2O2 as the oxidant. The La-MCM-41 catalysts exhibited high reactivity and the reactivity increased with the increase of the La content in the La-MCM-41 samples. On the contrary, Ce-MCM-41 catalysts showed low reactivity in the oxidation of styrene and the conversion of styrene decreased with the increase of the Ce content in the Ce-MCM-41 samples.
基金sponsored financially by the National Natural Science Foundation of China (No.91545103 and 21273071)the Science and Technology Commission of Shanghai Municipality (13JC1401902)
基金supported by the Natural Science Foundation of China(NSFC Grant No.20803064)the Natural Science Foundation of Zhejiang Provence(Y4090348 and LY12B03007)Qianjiang Talent Project in Zhejiang Province(2010R10039 and 2013R10056)
文摘A series of high surface area graphitic carbon materials (HSGCs) were prepared by ball-milling method. Effect of the graphitic degree of HSGCs on the catalytic performance of Ba-Ru-K/HSGC-x (x is the ball-milling time in hour) catalysts was studied using ammonia synthesis as a probe reaction. The graphitic degree and pore structure of HSGC-x supports could be successfully tuned via the variation of ball-milling time. Ru nanoparticles of different Ba-Ru-K/HSGC-x catalysts are homogeneously distributed on the supports with the particle sizes ranging from 1.6 to 2.0 nm. The graphitic degree of the support is closely related to its facile electron transfer capability and so plays an important role in improving the intrinsic catalytic performance of Ba-Ru-K/HSGC-x catalyst.
基金supported by the National Natural Science Foundation of China(Nos.21671172,21625604,21776251,21706229and Z86101001)Zhejiang Provincial Natural Science Foundation(No.LR19B010001)
文摘To search the new effective nitrogen reduction reaction(NRR)electrocatalyst is very important for the ammonia-based industry.Herein,we reported the design of a novel NRR electrocatalyst with Ru NPs loaded on oxygen-vacancy TiO2(Ru/TiO2-Vo).Structural characterizations revealed that oxygen vacancy was loaded in the matrix of Ru/TiO2-Vo.Electrocatalytic results indicated that Ru/TiO2-Vo showed good NRR performance(2.11μg h^-1 cm^-2).Contrast tests showed that NRR property of Ru/TiO2-Vo was much better than those of Ru/TiO-12(B)(0.53μg hcm^-2)and Ru/P25(0.42μg h^-1 cm^-2).Furthermore,density functional theory calculation results indicated catalytic mechanism of NRR and rate-determining step(*N2+1/2 H2→*N+*NH)was the potential-determining step with the overpotential requirement of 0.21 V.A combination of electronic structure analysis and catalytic measurement shed light on the synergistic effect of Ru and oxygen vacancy on the NRR performance.
基金the National Basic Research Program of China (2004CB719500)the Commission of Science and Technology of Shanghai Municipality (06DJ14006)Shanghai Municipal Education Commission (2008CG35)
文摘Cerium-doped MCM-48 molecular sieves were synthesized hydrothermally and characterized by X-ray diffraction, nitrogen adsorption, transmission electron microscope, FT-IR spectroscopy, UV-visible spectroscopy, and Raman spectroscopy. The results showed that all the samples held the structure of MCM-48, and Ce could enter the framework of MCM-48. However, when Ce/Si molar ratio in the sampies was high (0.04 or 0.059), there were CeO2 crystallites as secondary phase in the extraframework of MCM-48. Ce-doped MCM-48 was a very efficient catalyst for the oxidation of cyclohexane in a solvent-free system with oxygen as an oxidant. In the conditions of 0.5 MPa 02 and 413 K for 5 h, the conversion of cyclohexane was 8.1% over Ce-MCM-48-0.02, the total selectivity of cyclohexanol and cyclohaxnone was 98.7%. With an increase of Ce content, the conversion of cyclohexane and the selectivity to cyclohexanol decreased somewhat, but the selectivity to cyclohexanone increased.
基金This work was supported by the National Natural Science Foundation of China(91545103)Shu Guang Project of Shanghai Municipal Education Commission and Shanghai Education Development Foundation(10SG30)the Fundamental Research Funds for the Central Universities(222201717003)~~
文摘Paramagnetic polymer microspheres were synthesized by the inverse suspension polymerizationmethod through polymerization of glycidyl methacrylate,ally glycidyl ether and methacrylamide onthe surface of silica‐coated Fe3O4nanoparticles using N,N’‐methylene‐bis(acrylamide)as across‐linking agent.Penicillin G acylase(PGA)was covalently immobilized on the surface of theparamagnetic microspheres by reacting the amino groups of the PGA molecules with the epoxygroups of the paramagnetic polymer microspheres.The effect of the SiO2coating and the amount ofparamagnetic Fe3O4nanoparticles on the initial activity and the operational stability of the immobilizedPGA was investigated.The results indicated that SiO2played an important role in the polymerization process and paramagnetic polymer microspheres with a SiO2‐coated Fe3O4nanoparticles mass content of7.5%are an optimal support material for PGA immobilization.Immobilized PGA on the paramagnetic polymer microspheres shows a high initial activity of430U/g(wet)and retains99%of its initial activity after recycling10times.Furthermore,immobilized PGA exhibits high thermal stability,pH stability and excellent reusability,which can be rapidly recycled by the aid of magnet.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved.
基金supported by the National Natural Science Foundation of China(21832002,21872050,21808063)the Natural Science Foundation of Shanghai(18ZR1408500)~~
文摘Efficient conversion of lignin to aromatic hydrocarbons via depolymerization and subsequent hydrodeoxygenation is important.Previously,we found that NbOx species played a key role in the activation and cleavage of C-O bonds in lignin and its model compounds.In this study,commercial niobic acid(HY-340),niobium phosphate(NbPO-CBMM)and lab-made layered niobium oxide(Nb2O5-Layer)were chosen as supports to study the effect of Brosted and Lewis acids on the activation of C-O bonds in lignin conversion.A variety of Ru-loaded,Nb-based catalysts with different Ru particle sizes were prepared and applied to the conversion of p-cresol.The results show that all the Ru/Nb-based catalysts produce high mole yields of C7-C9 hydrocarbons(82.3%-9.1%).What's more,Ru/Nb2O5-Layer affords the best mole yield of C7-C9 hydrocarbons and selectivity for C7-C9 aromatic hydrocarbons,of up to 99.1% and 88.0%,respectively.Moreover,it was found that Lewis acid sites play important roles in the depolymerization of enzymatic lignin into phenolic monomers and the cleavage of the C-O bond of phenols.Additionally,the electronic state and particle size of Ru are significant factors which influence the selectivity for aromatic hydrocarbons.A partial positive charge on the metallic Ru surface and a smaller Ru particle size are beneficial in improving the selectivity for aromatic hydrocarbons.
基金financially supported by the National Basic Research Program of China(2010CB732300)the National Key Technologies R&D Program of China(2007BAJ03B01)
文摘Supported coupling catalysts for CS2 removal were prepared with different activated carbons originated from wood,coconut shell and coal as supports,and their catalytic activities for CS2 removal were tested at ambient temperature.The textural and surface properties of the activated carbons were characterized by nitrogen adsorption,temperature-programmed desorption(TPD)and Boehm titration.The activated carbon support with meso-and macropores,and oxygen-functional groups performs higher CS2 removal ability at ambient temperature.The effects of flow rate,CS2 inlet concentration,temperature and relative humidity on CS2 removal were also investigated.High efficient removal is obtained at temperature of 50-C,space velocity of 2000 h-1,inlet CS2 concentration of 500 mgS/m3 and relative humidity of 20%with the breakthrough sulfur capacity up to 4.3 gS/gCat and working sulfur capacity up to 7 gS/gCat.
基金supported by the National Basic Research Program of China (2013CB933201)the National Natural Science Foundation of China (21207037,21577035)the Commission of Science and Technology of Shanghai Municipality (15DZ1205305)~~
文摘LaMnO3was prepared by citrate sol‐gel,coprecipitation,hard template,and hydrothermal methods,respectively,and its catalytic performance for the combustion of vinyl chloride was investigated.N2adsorption‐desorption,X‐ray diffraction(XRD),Raman spectroscopy(Raman),O2temperature programmed desorption(O2‐TPD),H2temperature programmed surface reaction(H2‐TPR)and X‐ray photoelectron spectroscopy(XPS)were used to characterize the physicochemical properties of the LaMnO3samples.The preparation methods had obvious effects on the distribution of oxygen and manganese species on the catalyst surface.The reaction followed the suprafacial mechanism;the activity corresponded with the high amount of Mn4+and adsorbed oxygen species.LaMnO3prepared by the citrate sol‐gel method had the best performance for vinyl chloride combustion with T90of182°C.The optimal activity was attributed to the improved redox capability of Mn4+/Mn3+.More available adsorbed oxygen and Mn4+species on the surface were mainly responsible for the remarkable enhancement of the catalytic activity.