Vinasse is the main residue generated during alcohol, sugar and blue rum production by fermentation process. This residue is effluent that could cause serious environmental pollution due to high organic load when is n...Vinasse is the main residue generated during alcohol, sugar and blue rum production by fermentation process. This residue is effluent that could cause serious environmental pollution due to high organic load when is not treated adequately. The aim of this work consists of evaluating the efficiency and application of heterogeneous photocatalysis with TiO2, followed by a biological treatment (activated sludge system) to reduce organic load in the referred effluent. Complete factorial designs indicated the best experimental conditions subsequent to photacatalytic and biological treatments providing a reduction of non-purgeable organic carbon (NPOC) as a variable response. After the photocatalytic process, the sample from the best experiment condition was treated by a biological process in order to verify the degradation efficiency of the effluent organic matter studied according to the hybrid system (Advanced Oxidation Process—Acti- vated Sludge System). This system, which presented more efficiency, had a photochemical treatment of 180 minutes carried out in aerated solutions, pH 9 and effluent in natura, while the biological treatment was performed at pH 8 and sludge concentration of 5 gL–1. The reduction of biochemical oxygen demand (BOD) was >80%.展开更多
The cycloaddition between CO_(2)and epoxides to produce cyclic carbonate is an attractive and efficiency pathway for the utilization of CO_(2)as C1 source.The development of catalyst to mediate cycloaddition between C...The cycloaddition between CO_(2)and epoxides to produce cyclic carbonate is an attractive and efficiency pathway for the utilization of CO_(2)as C1 source.The development of catalyst to mediate cycloaddition between CO_(2)and epoxides at low temperature and pressure is still a challenge.Herein,a series of polypyrazoles with glass transition temperature(T_(g))in the range of 42.3-52.5℃ were synthesized and served as catalyst to mediate the cycloaddition of CO_(2)and epoxides by the assistant of tetrabutylammonium bromide.The catalytic behaviors of polypyrazole on the model cycloaddition of CO_(2)to epichlorohydrin,including the reaction parameters optimization and versatility were investigated in detail,and excellent yield(99.9%)and selectivity(99%)were obtained under the optimized reaction conditions of70℃ and 1.0 MPa for 6.0 h.Noteworthily,the polypyrazole acts as homogeneous catalyst during reaction(higher than T_(g)).And under room temperature,polypyrazoles can be easily separated and recovered,which is a promising feature of a heterogeneous catalyst.Furthermore,the reaction mechanism was proposed.The DFT calculation suggested that the formation of hydrogen bond between pyrazole and epoxide greatly reduced the energy barrier,which play an important role in promoting CO_(2)cycloaddition.展开更多
In this work,a dual-size MOF-derived Co catalyst(0.2Co_(1-NPs)@NC)composed of single atoms(Co_(1))and highly dispersed nanoparticles(Co NPs)was prepared by in-situ Zn evaporation for the highperformance conversion of ...In this work,a dual-size MOF-derived Co catalyst(0.2Co_(1-NPs)@NC)composed of single atoms(Co_(1))and highly dispersed nanoparticles(Co NPs)was prepared by in-situ Zn evaporation for the highperformance conversion of lignin-derived o-methoxyphenols(lignin oil)to cyclohexanols(up to 97%yield)via cascade demethoxylation and dearomatization.Theoretical calculations elaborated that the dual-size Co catalyst exhibited a cooperative effect in the selective demethoxylation process,in which the Co NPs could initially dissociate hydrogen at lower energies while Co1remarkably facilitated the cleavage of the C_(Ar)-OCH_(3)bond.Moreover,the intramolecular hydrogen bonds formed in the omethoxy-containing phenols were found to result in a decrease in the bond energy of the C_(Ar)-OCH_(3)bond,which was more prone to be activated by the dual-size Co sites.Notably,the pre-hydrogenated intermediate(e.g.,2-methoxycyclohexanol from guaiacol)is difficult to undergo demethoxylation,indicating that the selective C_(Ar)-OCH_(3)bond cleavage is a prerequisite for the synthesis of cyclohexanols.The 0.2Co_(1-NPs)@NC catalyst was highly recyclable with a neglect decline in activity during five consecutive cycles.This cooperative catalytic strategy based on the metal size effect opens new avenues for biomass upgrading via enhanced C-O bond cleavage of high selectivity.展开更多
Selective conversion of fructose to 1,2-propanediol(1,2-PDO)is considered as a sustainable and cost-effective alternative to petroleum-based processes,however,this approach still faces challenges associated with low e...Selective conversion of fructose to 1,2-propanediol(1,2-PDO)is considered as a sustainable and cost-effective alternative to petroleum-based processes,however,this approach still faces challenges associated with low efficiency and harsh reaction conditions.Here,we have successfully synthesized a novel bifunctional Ru-WO_(x)-MgO_(y) catalyst through a facile'one-pot'solvothermal method.Remarkably,this catalyst exhibits exceptional catalytic performances in the conversion of fructose to 1,2-PDO under mild reaction conditions.The yield of 1,2-PDO is up to 56.2%at 140°C for 4 h under an ultra-low hydrogen pressure of only 0.2 MPa,surpassing the reported results in recent literature(below 51%).Comprehensive characterizations and density functional theory(DFT)calculations reveal that the presence of oxygen vacancies in the Ru-WO_(x)-MgO_(y) catalyst,serving as active acidic sites,facilitates the chemoselective cleavage of C-C bonds in fructose,which leads to the generation of active intermediates and ultimately resulted in the high yield of 1,2-PDO.展开更多
Selective cleavage of Csp^(2)-OCH_(3)bond in lignin without breaking other types of C-O bonds followed by N-functionalization is fascinating for on-purpose valorization of biomass.Here,a Co/Ni-based dual-atom catalyst...Selective cleavage of Csp^(2)-OCH_(3)bond in lignin without breaking other types of C-O bonds followed by N-functionalization is fascinating for on-purpose valorization of biomass.Here,a Co/Ni-based dual-atom catalyst CoNiDA@NC prepared by in-situ evaporation and acid-etching of metal species from tailor-made metal–organic frameworks was efficient for reductive upgrading of various lignin-derived phenols to cyclohexanols(88.5%–99.9%yields),which had ca.4 times higher reaction rate than the single-atom catalyst and was superior to state-of-the-art heterogeneous catalysts.The synergistic catalysis of Co/Ni dual atoms facilitated both hydrogen dissociation and hydrogenolysis steps,and could optimize adsorption configuration of lignin-derived methoxylated phenols to further favor the Csp^(2)-OCH_(3)cleavage,as elaborated by theoretical calculations.Notably,the CoNi_(DA)@NC catalyst was highly recyclable,and exhibited excellent demethoxylation performance(77.1%yield)in real lignin monomer mixtures.Via in-situ cascade conversion processes assisted by dual-atom catalysis,various high-value N-containing chemicals,including caprolactams and cyclohexylamines,could be produced from lignin.展开更多
Development of active and non-noble metal-based catalyst for H2 production via NH3 decomposition is crucial for the implementation of NH3 as a H2 carrier.Co-based catalysts have received increasing attention because o...Development of active and non-noble metal-based catalyst for H2 production via NH3 decomposition is crucial for the implementation of NH3 as a H2 carrier.Co-based catalysts have received increasing attention because of its high intrinsic activity and moderate cost.In this work,we examined the effect of BaNH,CaNH and Mg3 N2 on the catalytic activity of Co in the NH3 decomposition reaction.The H2 formation rate ranks the order as Co-BaNH>Co-CaNH>Co-Mg3 N2≈Co/CNTs within a reaction temperature range of 300-550℃.It is worth pointing out that the H2 formation rate of Co-BaNH at 500℃reaches20 mmolH2 gcat-1 min-1,which is comparable to those of the active Ru/Al2 O3(ca.17 mmolH2 gcat-1 min1)and Ru/AC(21 mmolH2 gcat-1 min-1)catalysts under the similar reaction conditions.In-depth research shows that Co-BaNH exhibits an obviously higher intrinsic activity and much lower Ea(46.2 kJ mol-1)than other Co-based catalysts,suggesting that BaNH may play a different role from CaNH,Mg3 N2 and CNTs during the catalytic process.Combined results of XRD,Ar-TPD and XAS show that a[Co-N-Ba]-like intermediate species is likely formed at the interface of Co metal and BaNH,which may lead to a more energy-efficient reaction pathway than that of neat Co metal for NH3 decomposition.展开更多
Due to metal leaching and poor catalyst stability, the chemical industry's fine chemical and pharmaceutical sectors have been historically reluctant to use supported transition metal catalysts to manufacture fine ...Due to metal leaching and poor catalyst stability, the chemical industry's fine chemical and pharmaceutical sectors have been historically reluctant to use supported transition metal catalysts to manufacture fine chemicals and active pharmaceutical ingredients. With the advent of new generation supported metal catalysts and flow chemistry, we argue in this study, this situation is poised to quickly change. Alongside heterogenized metal nanoparticles, both single-site molecular and single-atom catalyst will become ubiquitous. This study offers a critical outlook taking into account both technical and economic aspects.展开更多
In recent years,an increasing amount of interest has been dedicated to the synthesis and application of ZIF-67-based materials due to their exceptionally high surface area,tunable porosity,and excellent thermal and ch...In recent years,an increasing amount of interest has been dedicated to the synthesis and application of ZIF-67-based materials due to their exceptionally high surface area,tunable porosity,and excellent thermal and chemical stabilities.This review summarizes the latest strategies of synthesizing ZIF-67-based materials by exploring the prominent examples.Then,the recent progress in the applications of ZIF-67-based materials in heterogeneous catalysis,including catalysis of the redox reactions,addition reactions,esterification reactions,Knoevenagel condensations,and hydrogenation-dehydrogenation reactions,has been elaborately discussed.Finally,we end this work by shedding some light on the large-scale industrial production of ZIF-67-based materials and their applications in the future.展开更多
C1 chemistrymainly involves the catalytic transformation of C1molecules(i.e.,CO,CO2,CH4 and CH3OH),which usually encounters thermodynamic and/or kinetic limitations.To address these limitations,non-thermal plasma(NTP)...C1 chemistrymainly involves the catalytic transformation of C1molecules(i.e.,CO,CO2,CH4 and CH3OH),which usually encounters thermodynamic and/or kinetic limitations.To address these limitations,non-thermal plasma(NTP)activated heterogeneous catalysis offers a number of advantages,such as relatively mild reaction conditions and energy efficiency,in comparison to the conventional thermal catalysis.This review presents the state-of-the-art for the application of NTP-catalysis towards C1 chemistry,including the CO2 hydrogenation,reforming of CH4 and CH3OH,and water-gas shift(WGS)reaction.In the hybrid NTP-catalyst system,the plasma-catalyst interactions aremultifaceted.Accordingly,this reviewalso includes a brief discussion on the fundamental research into themechanisms of NTP activated catalytic C1 chemistry,such as the advanced characterisation methods(e.g.,in situ diffuse reflectance infrared Fourier transform spectroscopy,DRIFTS),temperatureprogrammed plasma surface reaction(TPPSR),kinetic studies.Finally,prospects for the future research on the development of tailor-made catalysts for NTP-catalysis systems(which will enable the further understanding of its mechanism)and the translation of the hybrid technique to practical applications of catalytic C1 chemistry are discussed.展开更多
Sulfonic acid functionalized mesoporous SBA-15 was prepared using the grafting method.The structure and acid properties were comprehensively characterized using multi-nuclear and quantitative probe molecule solid-stat...Sulfonic acid functionalized mesoporous SBA-15 was prepared using the grafting method.The structure and acid properties were comprehensively characterized using multi-nuclear and quantitative probe molecule solid-state NMR(SSNMR),together with powder X-ray diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),N2 adsorption-desorption techniques.Its catalytic performance in the conversion of fructose to 5-hydroxymethylfurfural(HMF)in dimethyl sulfoxide(DMSO)was studied.Catalyst dosage,reaction time,reaction temperature and solvent effect have been investigated.A high yield of HMF up to 93%was obtained at a relatively low temperature of 373 K for 180 min.The Brønsted acid of SBA-15_SO3H together with the solvent DMSO was found to synergistically catalyze the reaction.The catalyst preserved most of its activity after five times reuse and the catalytic activity can be recovered by H2O2 process.展开更多
5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated...5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.展开更多
The sluggish kinetics of multiphase sulfur conversion with homogeneous and heterogeneous electrochemical processes,causing the“shuttle effect”of soluble polysulfide species(PSs),is the challenges in terms of lithium...The sluggish kinetics of multiphase sulfur conversion with homogeneous and heterogeneous electrochemical processes,causing the“shuttle effect”of soluble polysulfide species(PSs),is the challenges in terms of lithium-sulfur batteries(LSBs).In this paper,a Mn_(3)O_(4-x) catalyst,which has much higher activity for heterogeneous reactions than for homogeneous reactions(namely,preferentialactivity catalysts),is designed by surface engineering with rational oxygen vacancies.Due to the rational design of the electronic structure,the Mn_(3)O_(4-x) catalyst prefers to accelerate the conversion of Li2S4 into Li_(2)S_(2)/Li_(2)S and optimize Li_(2)S deposition,reducing the accumulation of PSs and thus suppressing the“shuttle effect.”Both density functional theory calculations and in situ X-ray diffraction measurements are used to probe the catalytic mechanism and identify the reaction intermediates of MnS and Li_(y)Mn_(z)O_(4-x) for fundamental understanding.The cell with Mn_(3)O_(4-x) delivers an ultralow attenuation rate of 0.028% per cycle over 2000 cycles at 2.5 C.Even with sulfur loadings of 4.93 and 7.10mg cm^(-2) in a lean electrolyte(8.4μL mg s^(-1)),the cell still shows an initial areal capacity of 7.3mAh cm^(-2).This study may provide a new way to develop preferential-activity heterogeneous-reaction catalysts to suppress the“shuttle effect”of the soluble PSs generated during the redox process of LSBs.展开更多
The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an e...The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.展开更多
The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to amm...The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.展开更多
Since the discovery of mesoporous silica in 1990s,there have been numerous mesoporous silica-based nanomaterials developed for catalytic applications,aiming at enhanced catalytic activity and stability.Recently,there ...Since the discovery of mesoporous silica in 1990s,there have been numerous mesoporous silica-based nanomaterials developed for catalytic applications,aiming at enhanced catalytic activity and stability.Recently,there have also been considerable interests in endowing them with hierarchical porosities to overcome the diffusional limitation for those with long unimodal channels.Present processes of making mesoporous silica largely rely on chemical sources which are relatively expensive and impose environmental concerns on their processes.In this regard,it is desirable to develop hierarchical silica supports from natural minerals.Herein,we present a series of work on surface reconstruction,modification,and functionalization to produce diatomite-based catalysts with original morphology and macro-meso-micro porosities and to test their suitability as catalyst supports for both liquid-and gas-phase reactions.Two wet-chemical routes were developed to introduce mesoporosity to both amorphous and crystalline diatomites.Importantly,we have used computational modeling to affirm that the diatomite morphology can improve catalytic performance based on fluid dynamics simulations.Thus,one could obtain this type of catalysts from numerous natural diatoms that have inherently intricate morphologies and shapes in micrometer scale.In principle,such catalytic nanocomposites acting as miniaturized industrial catalysts could be employed in microfluidic reactors for process intensification.展开更多
In this study,high-gravity intensified heterogeneous catalytic ozonation is utilized for treatment of phenol-containing wastewater,and the kinetics of the direct reaction between ozone and phenol in the presence of ex...In this study,high-gravity intensified heterogeneous catalytic ozonation is utilized for treatment of phenol-containing wastewater,and the kinetics of the direct reaction between ozone and phenol in the presence of excess tertiary butanol(TBA)is investigated.It is revealed that the direct reaction between ozone and phenol in the rotating packed bed(RPB)follows the pseudo-first-order kinetics with a reaction rate constant higher than that in the conventional bubbling reactor(BR).Under different conditions of temperature,initial pH,high-gravity factor,and gaseous ozone concentration,the apparent reaction rate constant varies in the range of 0.0160–0.115 min-1.An empirical power-exponential model is established to characterize the effects of these parameters on the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation.展开更多
This work aims to solve the problems of low reaction activity of Cu-based catalysts and agglomeration of active centers in acetylene hydrochlorination.Cu-based catalysts supported by NAP co-doped activated carbon(AC)w...This work aims to solve the problems of low reaction activity of Cu-based catalysts and agglomeration of active centers in acetylene hydrochlorination.Cu-based catalysts supported by NAP co-doped activated carbon(AC)with different content(mCu-xNP/AC)were manufactured and applied in the acetylene hydrochlorination reaction.It was found that the doping of carriers N and P induced the transformation of Cu^(2+)to Cu^(+),and the catalytic activity was markedly improved.Under the optimal reaction temperature of 220℃,the gas hourly space velocity(GHSV)of C_(2)H_(2)was 90 h^(-1)and V_(HCl):V_(C_(2)H_(2))was 1.15.The initial activity of the 5%Cu-30 NP/AC catalyst reached 95.59%.Through some characterization methods showed the addition of N and P improved the dispersion of Cu in carbon,which increased the ratio of Cu^+/Cu^(2+).The measurement results confirmed that the chemisorption capacity of mCu-xNP/AC for C_(2)H_(2)decreased slightly,and the chemisorption capacity for HCl increased significantly,which was the reason for the increased activity of the catalyst.The conclusion provides a reference for the development of acetylene hydrochlorination Cu catalyst.展开更多
Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture ...Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.展开更多
Sustainable acquisition of bioactive compounds from biomass-based platform molecules is a green alternative for existing CO_(2)-emitting fossil-fuel technologies.Herein,a core–shell magnetic biocarbon catalyst functi...Sustainable acquisition of bioactive compounds from biomass-based platform molecules is a green alternative for existing CO_(2)-emitting fossil-fuel technologies.Herein,a core–shell magnetic biocarbon catalyst functionalized with sulfonic acid(Fe3O4@SiO_(2)@chitosan-SO_(3)H,MBC-SO_(3)H)was prepared to be efficient for the synthesis of various N-substituted pyrroles(up to 99% yield)from bio-based hexanedione and amines under mild conditions.The abundance of Bronsted acid sites in the MBC-SO_(3)H ensured smooth condensation of 2,5-hexanedione with a variety of amines to produce N-substituted pyrroles.The reaction was illustrated to follow the conventional Pall-Knorr coupling pathway,which includes three cascade reaction steps:amination,loop closure and dehydration.The prepared MBC-SO_(3)H catalyst could effectively activate 2,5-hexanedione,thus weakening the dependence of the overall conversion process on the amine nucleophilicity.The influence of different factors(e.g.,reaction temperature,time,amount of catalyst,molar ratio of substrates,and solvent type)on the reaction activity and selectivity were investigated comprehensively.Moreover,the MBC-SO_(3)H possessed excellent thermochemical stability,reusability,and easy separation due to the presence of magnetic core-shell structures.Notably,there was no activity attenuation after 5 consecutive catalytic experiments.This work demonstrates a wide range of potential applications of developing functionalized core-shell magnetic materials to construct bioactive backbones from biomass-based platform molecules.展开更多
Metal hydrides (MeH) on solid surfaces, i.e., surface MeH, are ubiquitous but criticalspecies in heterogeneous catalysis, and their intermediate roles have been proposed innumerous reactions such as (de)hydrogenation ...Metal hydrides (MeH) on solid surfaces, i.e., surface MeH, are ubiquitous but criticalspecies in heterogeneous catalysis, and their intermediate roles have been proposed innumerous reactions such as (de)hydrogenation and alkanes activation, etc., however, thedetailed spectroscopic characterizations remain challenging. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy has become a powerful tool in surface studies, asit provides access to local structural characterizations at atomic level from multipleviews, with comprehensive information on chemical bonding and spatial structures. Inthis review, we summarized and discussed the latest research developments on thesuccessful application of ssNMR to characterize surface MeH species on solid catalystsincluding supported single-site heterogeneous catalysts, bulk metal oxides and metalmodified zeolites. We also discussed the opportunities and challenges in this field, aswell as the potential application/development of state-of-the-art ssNMR technologies toenable further exploration of metal hydrides in heterogeneous catalysis.展开更多
基金Fundacao de Amparo a Pes- quisa do Estado de Sao Paulo
文摘Vinasse is the main residue generated during alcohol, sugar and blue rum production by fermentation process. This residue is effluent that could cause serious environmental pollution due to high organic load when is not treated adequately. The aim of this work consists of evaluating the efficiency and application of heterogeneous photocatalysis with TiO2, followed by a biological treatment (activated sludge system) to reduce organic load in the referred effluent. Complete factorial designs indicated the best experimental conditions subsequent to photacatalytic and biological treatments providing a reduction of non-purgeable organic carbon (NPOC) as a variable response. After the photocatalytic process, the sample from the best experiment condition was treated by a biological process in order to verify the degradation efficiency of the effluent organic matter studied according to the hybrid system (Advanced Oxidation Process—Acti- vated Sludge System). This system, which presented more efficiency, had a photochemical treatment of 180 minutes carried out in aerated solutions, pH 9 and effluent in natura, while the biological treatment was performed at pH 8 and sludge concentration of 5 gL–1. The reduction of biochemical oxygen demand (BOD) was >80%.
基金financially supported by the National Natural Science Foundation of China(21504025)the Natural Science Foundation of Fujian Province(2019J05040)+4 种基金Fujian Provincial Department of Education(JT180038)Key Program of Qingyuan Innovation Laboratory(00221003)Fuzhou University Testing Fund of precious apparatus(2021T022)Talent Program(GXRC18041)Higher Education Disciplinary Innovation Program(‘111’Program)of Fuzhou University。
文摘The cycloaddition between CO_(2)and epoxides to produce cyclic carbonate is an attractive and efficiency pathway for the utilization of CO_(2)as C1 source.The development of catalyst to mediate cycloaddition between CO_(2)and epoxides at low temperature and pressure is still a challenge.Herein,a series of polypyrazoles with glass transition temperature(T_(g))in the range of 42.3-52.5℃ were synthesized and served as catalyst to mediate the cycloaddition of CO_(2)and epoxides by the assistant of tetrabutylammonium bromide.The catalytic behaviors of polypyrazole on the model cycloaddition of CO_(2)to epichlorohydrin,including the reaction parameters optimization and versatility were investigated in detail,and excellent yield(99.9%)and selectivity(99%)were obtained under the optimized reaction conditions of70℃ and 1.0 MPa for 6.0 h.Noteworthily,the polypyrazole acts as homogeneous catalyst during reaction(higher than T_(g)).And under room temperature,polypyrazoles can be easily separated and recovered,which is a promising feature of a heterogeneous catalyst.Furthermore,the reaction mechanism was proposed.The DFT calculation suggested that the formation of hydrogen bond between pyrazole and epoxide greatly reduced the energy barrier,which play an important role in promoting CO_(2)cycloaddition.
基金the Guizhou Provincial S&T Project(ZK[2022]011)the National Natural Science Foundation of China(21908033,21922513)+1 种基金the Natural Science Foundation of Guangxi Zhuang Autonomous Region(2020GXNSFAA297072)the Fok Ying-Tong Education Foundation(161030)。
文摘In this work,a dual-size MOF-derived Co catalyst(0.2Co_(1-NPs)@NC)composed of single atoms(Co_(1))and highly dispersed nanoparticles(Co NPs)was prepared by in-situ Zn evaporation for the highperformance conversion of lignin-derived o-methoxyphenols(lignin oil)to cyclohexanols(up to 97%yield)via cascade demethoxylation and dearomatization.Theoretical calculations elaborated that the dual-size Co catalyst exhibited a cooperative effect in the selective demethoxylation process,in which the Co NPs could initially dissociate hydrogen at lower energies while Co1remarkably facilitated the cleavage of the C_(Ar)-OCH_(3)bond.Moreover,the intramolecular hydrogen bonds formed in the omethoxy-containing phenols were found to result in a decrease in the bond energy of the C_(Ar)-OCH_(3)bond,which was more prone to be activated by the dual-size Co sites.Notably,the pre-hydrogenated intermediate(e.g.,2-methoxycyclohexanol from guaiacol)is difficult to undergo demethoxylation,indicating that the selective C_(Ar)-OCH_(3)bond cleavage is a prerequisite for the synthesis of cyclohexanols.The 0.2Co_(1-NPs)@NC catalyst was highly recyclable with a neglect decline in activity during five consecutive cycles.This cooperative catalytic strategy based on the metal size effect opens new avenues for biomass upgrading via enhanced C-O bond cleavage of high selectivity.
基金the financial support from the Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX0458)the State Key Laboratory of Coal Mine Disaster Dynamics and Control(2011DA105287-MS202203)+4 种基金the Joint Fund for Innovation and Development of Chongqing(CSTB2022NSCQ-LZX0030)the financial support from the National Natural Science Foundation of China(22168027 and 22308169)the financial support from the Natural Science Foundation of Chongqing(cstc2021jcyj-msxmX0741)the financial support from the National Natural Science Foundation of China(22105028)the Natural Science Foundation of Chongqing(cstc2021jcyj-msxmX0572)。
文摘Selective conversion of fructose to 1,2-propanediol(1,2-PDO)is considered as a sustainable and cost-effective alternative to petroleum-based processes,however,this approach still faces challenges associated with low efficiency and harsh reaction conditions.Here,we have successfully synthesized a novel bifunctional Ru-WO_(x)-MgO_(y) catalyst through a facile'one-pot'solvothermal method.Remarkably,this catalyst exhibits exceptional catalytic performances in the conversion of fructose to 1,2-PDO under mild reaction conditions.The yield of 1,2-PDO is up to 56.2%at 140°C for 4 h under an ultra-low hydrogen pressure of only 0.2 MPa,surpassing the reported results in recent literature(below 51%).Comprehensive characterizations and density functional theory(DFT)calculations reveal that the presence of oxygen vacancies in the Ru-WO_(x)-MgO_(y) catalyst,serving as active acidic sites,facilitates the chemoselective cleavage of C-C bonds in fructose,which leads to the generation of active intermediates and ultimately resulted in the high yield of 1,2-PDO.
基金the National Natural Science Foundation of China(22368014)the Guizhou Provincial S&T Project(ZK[2022]011,GCC[2023]011)+2 种基金the Natural Science Foundation of Guangxi Zhuang Autonomous Region(2023JJA120098)the Guangxi Key Laboratory of Green Chemical Materials and Safety Technology,the Beibu Gulf University(2022SYSZZ02,2022ZZKT04)the Guizhou Provincial Higher Education Institution Program(Qianjiaoji[2023]082)。
文摘Selective cleavage of Csp^(2)-OCH_(3)bond in lignin without breaking other types of C-O bonds followed by N-functionalization is fascinating for on-purpose valorization of biomass.Here,a Co/Ni-based dual-atom catalyst CoNiDA@NC prepared by in-situ evaporation and acid-etching of metal species from tailor-made metal–organic frameworks was efficient for reductive upgrading of various lignin-derived phenols to cyclohexanols(88.5%–99.9%yields),which had ca.4 times higher reaction rate than the single-atom catalyst and was superior to state-of-the-art heterogeneous catalysts.The synergistic catalysis of Co/Ni dual atoms facilitated both hydrogen dissociation and hydrogenolysis steps,and could optimize adsorption configuration of lignin-derived methoxylated phenols to further favor the Csp^(2)-OCH_(3)cleavage,as elaborated by theoretical calculations.Notably,the CoNi_(DA)@NC catalyst was highly recyclable,and exhibited excellent demethoxylation performance(77.1%yield)in real lignin monomer mixtures.Via in-situ cascade conversion processes assisted by dual-atom catalysis,various high-value N-containing chemicals,including caprolactams and cyclohexylamines,could be produced from lignin.
基金financial supports from the Project of the National Natural Science Foundation of China(Grant Nos.21633011and 21872137)“Transformational Technologies for Clean Energy and Demonstration”+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA21000000)Youth Innovation Promotion Association CAS(No.2018213)the Shanghai Synchrotron Radiation Facility(SSRF)for providing the beam time。
文摘Development of active and non-noble metal-based catalyst for H2 production via NH3 decomposition is crucial for the implementation of NH3 as a H2 carrier.Co-based catalysts have received increasing attention because of its high intrinsic activity and moderate cost.In this work,we examined the effect of BaNH,CaNH and Mg3 N2 on the catalytic activity of Co in the NH3 decomposition reaction.The H2 formation rate ranks the order as Co-BaNH>Co-CaNH>Co-Mg3 N2≈Co/CNTs within a reaction temperature range of 300-550℃.It is worth pointing out that the H2 formation rate of Co-BaNH at 500℃reaches20 mmolH2 gcat-1 min-1,which is comparable to those of the active Ru/Al2 O3(ca.17 mmolH2 gcat-1 min1)and Ru/AC(21 mmolH2 gcat-1 min-1)catalysts under the similar reaction conditions.In-depth research shows that Co-BaNH exhibits an obviously higher intrinsic activity and much lower Ea(46.2 kJ mol-1)than other Co-based catalysts,suggesting that BaNH may play a different role from CaNH,Mg3 N2 and CNTs during the catalytic process.Combined results of XRD,Ar-TPD and XAS show that a[Co-N-Ba]-like intermediate species is likely formed at the interface of Co metal and BaNH,which may lead to a more energy-efficient reaction pathway than that of neat Co metal for NH3 decomposition.
文摘Due to metal leaching and poor catalyst stability, the chemical industry's fine chemical and pharmaceutical sectors have been historically reluctant to use supported transition metal catalysts to manufacture fine chemicals and active pharmaceutical ingredients. With the advent of new generation supported metal catalysts and flow chemistry, we argue in this study, this situation is poised to quickly change. Alongside heterogenized metal nanoparticles, both single-site molecular and single-atom catalyst will become ubiquitous. This study offers a critical outlook taking into account both technical and economic aspects.
基金financial support from the National Natural Science Foundation of China(22008032)the Guangdong Basic and Applied Basic Research Foundation(2019A1515110706)+1 种基金the Shandong Provincial Natural Science Foundation(ZR2020ZD08)the Guangdong Provincial Key Lab of Green Chemical Product Technology(GC202111)
文摘In recent years,an increasing amount of interest has been dedicated to the synthesis and application of ZIF-67-based materials due to their exceptionally high surface area,tunable porosity,and excellent thermal and chemical stabilities.This review summarizes the latest strategies of synthesizing ZIF-67-based materials by exploring the prominent examples.Then,the recent progress in the applications of ZIF-67-based materials in heterogeneous catalysis,including catalysis of the redox reactions,addition reactions,esterification reactions,Knoevenagel condensations,and hydrogenation-dehydrogenation reactions,has been elaborately discussed.Finally,we end this work by shedding some light on the large-scale industrial production of ZIF-67-based materials and their applications in the future.
基金the financial support from the Jiangsu Specially-Appointed Professors Program and the European Commission under the Marie Skłodowska-Curie Individual Fellowship(H2020-MSCA-IFNTPleasure-748196).
文摘C1 chemistrymainly involves the catalytic transformation of C1molecules(i.e.,CO,CO2,CH4 and CH3OH),which usually encounters thermodynamic and/or kinetic limitations.To address these limitations,non-thermal plasma(NTP)activated heterogeneous catalysis offers a number of advantages,such as relatively mild reaction conditions and energy efficiency,in comparison to the conventional thermal catalysis.This review presents the state-of-the-art for the application of NTP-catalysis towards C1 chemistry,including the CO2 hydrogenation,reforming of CH4 and CH3OH,and water-gas shift(WGS)reaction.In the hybrid NTP-catalyst system,the plasma-catalyst interactions aremultifaceted.Accordingly,this reviewalso includes a brief discussion on the fundamental research into themechanisms of NTP activated catalytic C1 chemistry,such as the advanced characterisation methods(e.g.,in situ diffuse reflectance infrared Fourier transform spectroscopy,DRIFTS),temperatureprogrammed plasma surface reaction(TPPSR),kinetic studies.Finally,prospects for the future research on the development of tailor-made catalysts for NTP-catalysis systems(which will enable the further understanding of its mechanism)and the translation of the hybrid technique to practical applications of catalytic C1 chemistry are discussed.
基金the National Natural Science Foundation of China(21773056 and 21703056)the Key Science and Technology Program of Henan Province(212102210608 and 202102110289)the Young Backbone Teacher Program of Young Backbone Teacher Program of Henan University of Technology(0503/21420046 and 0503/21420110)。
文摘Sulfonic acid functionalized mesoporous SBA-15 was prepared using the grafting method.The structure and acid properties were comprehensively characterized using multi-nuclear and quantitative probe molecule solid-state NMR(SSNMR),together with powder X-ray diffraction(XRD),scanning electron microscope(SEM),transmission electron microscopy(TEM),N2 adsorption-desorption techniques.Its catalytic performance in the conversion of fructose to 5-hydroxymethylfurfural(HMF)in dimethyl sulfoxide(DMSO)was studied.Catalyst dosage,reaction time,reaction temperature and solvent effect have been investigated.A high yield of HMF up to 93%was obtained at a relatively low temperature of 373 K for 180 min.The Brønsted acid of SBA-15_SO3H together with the solvent DMSO was found to synergistically catalyze the reaction.The catalyst preserved most of its activity after five times reuse and the catalytic activity can be recovered by H2O2 process.
基金financially supported by the National Key R&D Program of China 2021YFC2101604)the National Natural Science Foundation of China(22278339,21978248)+1 种基金the Guangdong Provincial Key Research and Development Program(2020B0101070001)the Natural Science Foundation of Fujian Province of China(2019J06005)。
文摘5-(Chloromethyl)furfural(CMF),as a new platform molecular,has become a hot topic in the field of biorefinery.Herein,the one-pot conversion of CMF to 2,5-bis(hydroxymethyl)furan(BHMF)in the water phase was demonstrated for the first time.A 91%BHMF yield was obtained over Ru/Cu Oxcatalyst,and BHMF was mainly produced by the consecutive hydrolysis and hydrogenation of CMF with 5-hydroxymethylfurfural(HMF)as an intermediate.Kinetic studies revealed that the conversion of HMF to BHMF was the rate-determining step.Remarkably,the characterizations and density functional theory(DFT)calculations further revealed the lower electron density of Ru NPs in Ru/Cu Oxcatalyst,resulting in a larger adsorption energy and a smaller free energy difference for the formation of alcohols.The present findings offered a new pathway for biomass-derived diol production through CMF as a potential source.
基金National Nature Science Foundation of China,Grant/Award Number:21908124。
文摘The sluggish kinetics of multiphase sulfur conversion with homogeneous and heterogeneous electrochemical processes,causing the“shuttle effect”of soluble polysulfide species(PSs),is the challenges in terms of lithium-sulfur batteries(LSBs).In this paper,a Mn_(3)O_(4-x) catalyst,which has much higher activity for heterogeneous reactions than for homogeneous reactions(namely,preferentialactivity catalysts),is designed by surface engineering with rational oxygen vacancies.Due to the rational design of the electronic structure,the Mn_(3)O_(4-x) catalyst prefers to accelerate the conversion of Li2S4 into Li_(2)S_(2)/Li_(2)S and optimize Li_(2)S deposition,reducing the accumulation of PSs and thus suppressing the“shuttle effect.”Both density functional theory calculations and in situ X-ray diffraction measurements are used to probe the catalytic mechanism and identify the reaction intermediates of MnS and Li_(y)Mn_(z)O_(4-x) for fundamental understanding.The cell with Mn_(3)O_(4-x) delivers an ultralow attenuation rate of 0.028% per cycle over 2000 cycles at 2.5 C.Even with sulfur loadings of 4.93 and 7.10mg cm^(-2) in a lean electrolyte(8.4μL mg s^(-1)),the cell still shows an initial areal capacity of 7.3mAh cm^(-2).This study may provide a new way to develop preferential-activity heterogeneous-reaction catalysts to suppress the“shuttle effect”of the soluble PSs generated during the redox process of LSBs.
基金the National Natural Science Foundation of China, China (Grant 21920102005, 22288101, and 21835002)the 111 Project, China (B17020)+2 种基金the European Union through the European Research Council, European Union (grant ERC-AdG-2014-671093, SynCatMatch)the Spanish Government through “Severo Ochoa”, Spain (SEV2016-0683, MINECO) for supporting this workthe financial support from China Scholarship Council, China
文摘The exploration of highly efficient catalysts based on nano-sized Ti-rich titanosilicate zeolites with controllable active titanium species is of great importance in zeolite catalytic reactions.Herein,we reported an efficient and facile synthesis of nano-sized Ti-rich TS-1(MFI)zeolites by replacing tetrabutyl orthotitanate(TBOT)with tetrabutyl orthotitanate tetramer(TBOT-tetramer)as the titanium source.The introduced TBOT-tetramer slowed down the zeolite crystallization process,and accordingly balanced the rate of incorporating Ti and the crystal growth and inhibited the massive formation of anatase species.Notably,the prepared Ti-rich TS-1 zeolite sample had a Si/Ti as low as 27.6 in contrast to conventional one with a molar ratio of 40.The TBOT-tetramer endowed the titanosilicate zeolites with enriched active titanium species and enlarged external surface area.It also impeded the formation of anatase species,resulting in superior catalytic behavior toward the oxidative desulfurization of dibenzothiophene compared with the conventional TS-1 zeolite counterpart prepared with TBOT.
基金financially supported by the National Natural Science Foundation of China (22279118, 22279117, 22075254,31901272)the Top-Notch Talent Program of Henan Agricultural University (30501034)。
文摘The water gas shift(WGS) reaction is a standard reaction that is widely used in industrial hydrogen production and removal of carbon monoxide. The improved catalytic performance of WGS reaction also contributes to ammonia synthesis and other reactions. Advanced catalysts have been developed for both high and low-temperature reactions and are widely used in industry. In recent years, supported metal nanoparticle catalysts have been researched due to their high metal utilization. Low-temperature catalysts have shown promising results, including high selectivity, high shift rates, and higher activity potential. Additionally, significant progress has been made in removing trace CO through the redox reaction in electrolytic cell. This paper reviews the development of WGS reaction catalysts, including the reaction mechanism, catalyst design, and innovative research methods. The catalyst plays a crucial role in the WGS reaction, and this paper provides an instant of catalyst design under different conditions. The progress of catalysts is closely related to the development of advanced characterization techniques.Furthermore, modifying the catalyst surface to enhance activity and significantly increase reaction kinetics is a current research direction. This review goals to stimulate a better understanding of catalyst design, performance optimization, and driving mechanisms, leading to further progress in this field.
基金the financial support provided by the National Research Foundation (NRF), Prime Minister’s Office, Singapore, under its Campus for Research Excellence and Technological Enterprise (CREATE) programpartially funded by the National University of Singapore under its Flagship Green Energy Program (GEP), Agency for Science, Technology and Research (A*STAR) under its Low Carbon Energy Research Funding Initiative (LCER-FI)Chongqing Science and Technology Research and Development Base Construction Project (cstc2013gjhz0029)
文摘Since the discovery of mesoporous silica in 1990s,there have been numerous mesoporous silica-based nanomaterials developed for catalytic applications,aiming at enhanced catalytic activity and stability.Recently,there have also been considerable interests in endowing them with hierarchical porosities to overcome the diffusional limitation for those with long unimodal channels.Present processes of making mesoporous silica largely rely on chemical sources which are relatively expensive and impose environmental concerns on their processes.In this regard,it is desirable to develop hierarchical silica supports from natural minerals.Herein,we present a series of work on surface reconstruction,modification,and functionalization to produce diatomite-based catalysts with original morphology and macro-meso-micro porosities and to test their suitability as catalyst supports for both liquid-and gas-phase reactions.Two wet-chemical routes were developed to introduce mesoporosity to both amorphous and crystalline diatomites.Importantly,we have used computational modeling to affirm that the diatomite morphology can improve catalytic performance based on fluid dynamics simulations.Thus,one could obtain this type of catalysts from numerous natural diatoms that have inherently intricate morphologies and shapes in micrometer scale.In principle,such catalytic nanocomposites acting as miniaturized industrial catalysts could be employed in microfluidic reactors for process intensification.
基金supported by the Fund for Shanxi Province Higher Education“1331 Project”for Improving Quality and Efficiency Construction(nuc2021-006)Key Research&Development Plan of Shanxi Province(201903D321059)+1 种基金Scientific Activities of Selected Returned Overseas Professionals in Shanxi Province(20200004)Transformation and Cultivation Projects of Scientific and Technological Achievements in Universities of Shanxi Province Institutions(2020CG040).
文摘In this study,high-gravity intensified heterogeneous catalytic ozonation is utilized for treatment of phenol-containing wastewater,and the kinetics of the direct reaction between ozone and phenol in the presence of excess tertiary butanol(TBA)is investigated.It is revealed that the direct reaction between ozone and phenol in the rotating packed bed(RPB)follows the pseudo-first-order kinetics with a reaction rate constant higher than that in the conventional bubbling reactor(BR).Under different conditions of temperature,initial pH,high-gravity factor,and gaseous ozone concentration,the apparent reaction rate constant varies in the range of 0.0160–0.115 min-1.An empirical power-exponential model is established to characterize the effects of these parameters on the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation.
基金supported by the Taishan Scholars Program of Shandong Province(tsqn202103051)the Project of Scientific Research in Shihezi University(CXFZ202205)。
文摘This work aims to solve the problems of low reaction activity of Cu-based catalysts and agglomeration of active centers in acetylene hydrochlorination.Cu-based catalysts supported by NAP co-doped activated carbon(AC)with different content(mCu-xNP/AC)were manufactured and applied in the acetylene hydrochlorination reaction.It was found that the doping of carriers N and P induced the transformation of Cu^(2+)to Cu^(+),and the catalytic activity was markedly improved.Under the optimal reaction temperature of 220℃,the gas hourly space velocity(GHSV)of C_(2)H_(2)was 90 h^(-1)and V_(HCl):V_(C_(2)H_(2))was 1.15.The initial activity of the 5%Cu-30 NP/AC catalyst reached 95.59%.Through some characterization methods showed the addition of N and P improved the dispersion of Cu in carbon,which increased the ratio of Cu^+/Cu^(2+).The measurement results confirmed that the chemisorption capacity of mCu-xNP/AC for C_(2)H_(2)decreased slightly,and the chemisorption capacity for HCl increased significantly,which was the reason for the increased activity of the catalyst.The conclusion provides a reference for the development of acetylene hydrochlorination Cu catalyst.
基金financial support from the National Natural Science Foundation of China(22078274,21903066)。
文摘Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.
基金funded by the Guizhou Provincial S&T Project(ZK[2022]011)Guizhou Natural Science Foundation(20201Y182)College Students’Innovation and Entrepreneurship Training Program(S202110657036).
文摘Sustainable acquisition of bioactive compounds from biomass-based platform molecules is a green alternative for existing CO_(2)-emitting fossil-fuel technologies.Herein,a core–shell magnetic biocarbon catalyst functionalized with sulfonic acid(Fe3O4@SiO_(2)@chitosan-SO_(3)H,MBC-SO_(3)H)was prepared to be efficient for the synthesis of various N-substituted pyrroles(up to 99% yield)from bio-based hexanedione and amines under mild conditions.The abundance of Bronsted acid sites in the MBC-SO_(3)H ensured smooth condensation of 2,5-hexanedione with a variety of amines to produce N-substituted pyrroles.The reaction was illustrated to follow the conventional Pall-Knorr coupling pathway,which includes three cascade reaction steps:amination,loop closure and dehydration.The prepared MBC-SO_(3)H catalyst could effectively activate 2,5-hexanedione,thus weakening the dependence of the overall conversion process on the amine nucleophilicity.The influence of different factors(e.g.,reaction temperature,time,amount of catalyst,molar ratio of substrates,and solvent type)on the reaction activity and selectivity were investigated comprehensively.Moreover,the MBC-SO_(3)H possessed excellent thermochemical stability,reusability,and easy separation due to the presence of magnetic core-shell structures.Notably,there was no activity attenuation after 5 consecutive catalytic experiments.This work demonstrates a wide range of potential applications of developing functionalized core-shell magnetic materials to construct bioactive backbones from biomass-based platform molecules.
基金the National Natural Science Foundation of China(Grant Nos.21902158,21773230,91945302)the National Key R&D Program of China(No.2021YFA1502803)LiaoNing Revitalization Talents Program(XLYC1807207),DICP I202104.
文摘Metal hydrides (MeH) on solid surfaces, i.e., surface MeH, are ubiquitous but criticalspecies in heterogeneous catalysis, and their intermediate roles have been proposed innumerous reactions such as (de)hydrogenation and alkanes activation, etc., however, thedetailed spectroscopic characterizations remain challenging. Solid-state nuclear magnetic resonance (ssNMR) spectroscopy has become a powerful tool in surface studies, asit provides access to local structural characterizations at atomic level from multipleviews, with comprehensive information on chemical bonding and spatial structures. Inthis review, we summarized and discussed the latest research developments on thesuccessful application of ssNMR to characterize surface MeH species on solid catalystsincluding supported single-site heterogeneous catalysts, bulk metal oxides and metalmodified zeolites. We also discussed the opportunities and challenges in this field, aswell as the potential application/development of state-of-the-art ssNMR technologies toenable further exploration of metal hydrides in heterogeneous catalysis.