Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR pr...Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.展开更多
In recent years,studies focusing on the conversion of renewable lignin-derived oxygenates(LDOs)have emphasized their potential as alternatives to fossil-based products.However,LDOs,existing as complex aromatic mixture...In recent years,studies focusing on the conversion of renewable lignin-derived oxygenates(LDOs)have emphasized their potential as alternatives to fossil-based products.However,LDOs,existing as complex aromatic mixtures with diverse oxygen-containing functional groups,pose a challenge as they cannot be easily separated via distillation for direct utilization.A promising solution to this challenge lies in the efficient removal of oxygen-containing functional groups from LDOs through hydrodeoxygenation(HDO),aiming to yield biomass products with singular components.However,the high dissociation energy of the carbon-oxygen bond,coupled with its similarity to the hydrogenation energy of the benzene ring,creates a competition between deoxygenation and benzene ring hydrogenation.Considering hydrogen consumption and lignin properties,the preference is directed towards generating aromatic hydrocarbons rather than saturated components.Thus,the goal is to selectively remove oxygen-containing functional groups while preserving the benzene ring structure.Studies on LDOs conversion have indicated that the design of active components and optimization of reaction conditions play pivotal roles in achieving selective deoxygenation,but a summary of the correlation between these factors and the reaction mechanism is lacking.This review addresses this gap in knowledge by firstly summarizing the various reaction pathways for HDO of LDOs.It explores the impact of catalyst design strategies,including morphology modulation,elemental doping,and surface modification,on the adsorption-desorption dynamics between reactants and catalysts.Secondly,we delve into the application of advanced techniques such as spectroscopic techniques and computational modeling,aiding in uncovering the true active sites in HDO reactions and understanding the interaction of reactive reactants with catalyst surface-interfaces.Additionally,fundamental insights into selective deoxygenation obtained through these techniques are highlighted.Finally,we outline the challenges that lie ahead in the design of highly active and selective HDO catalysts.These challenges include the development of detection tools for reactive species with high activity at low concentrations,the study of reaction medium-catalyst interactions,and the development of theoretical models that more closely approximate real reaction situations.Addressing these challenges will pave the way for the development of efficient and selective HDO catalysts,thus advancing the field of renewable LDOs conversion.展开更多
Direct cost-effective conversion of abundant methane to high value-added oxygenates(methanol,formic acid,acetic acid,etc.)under mild conditions is prospective for optimizing the structure of energy resources.However,t...Direct cost-effective conversion of abundant methane to high value-added oxygenates(methanol,formic acid,acetic acid,etc.)under mild conditions is prospective for optimizing the structure of energy resources.However,the CAH bond of products is more reactive than that of high thermodynamic stable methane.Exploring an appropriate approach to eliminate the‘‘seesaw effect"between methane conversion and oxygenate selectivity is significant.In this review,we briefly summarize the research progress in the past decade on low-temperature direct conversion of methane to oxygenates in gas-solid-liquid phase over various transition metal(Fe,Cu,Rh,Pd,Au Pd,etc.)based nanoparticle or single-atom catalyst.Furthermore,the prospects of catalyst design and catalysis process are also discussed.展开更多
The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic ...The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.展开更多
Iron-containing zeolites play an important role in the selective oxidation of methane to oxygenates by nitrous oxide.A solid-state ion exchange method is adopted to prepare Fe-MOR zeolite catalysts with different amou...Iron-containing zeolites play an important role in the selective oxidation of methane to oxygenates by nitrous oxide.A solid-state ion exchange method is adopted to prepare Fe-MOR zeolite catalysts with different amounts of extra-framework Al.EPR spectra and UV-vis spectra show that the percentage of iron ions in tetrahedral or octahedral coordination increases while those of clustered Fe species decrease by the addition of extra-framework Al species.Nitrous oxide titration reveals that more active Fe centers are formed,which promote the nitrous oxide consumption.The number of active centers in the catalyst with the introduction of extra-framework Al is about four times that of the catalyst without the addition of extra-framework Al.Due to this,there is an increase in the methane conversion,total selectivity and yield of oxygenates.展开更多
Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-M...Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-MS experiments. The results indicated that metal Pd loaded on MoOa/SiO2 has a significant effect on the photo absorbing performance of MoOa/SiO2, and an obvious blue shift of the absorption edge is produced. Under UV irradiation, the chemisorption state of CO2 undergoes decomposing process to form CO at 481 K, and a two-site adsorption state of ethane can be formed at around 496 K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol and acetaldehyde in the temperature range of 353-423 K. The presence of metal Pd improves the catalytic activity remarkably.展开更多
The kinetics of CO hydrogenation for the synthesis of C_2 oxygenates overRh-Mn-Li-Fe/SiO_2 was investigated. Kinetic parameters for the formation of ethanol, acetaldehyde,C'2 oxygenates, methanol and methane were ...The kinetics of CO hydrogenation for the synthesis of C_2 oxygenates overRh-Mn-Li-Fe/SiO_2 was investigated. Kinetic parameters for the formation of ethanol, acetaldehyde,C'2 oxygenates, methanol and methane were obtained. The activation energy. H_2 and CO dependenceorders for ethanol and acetaldehyde formation differed greatly, the large difference seemed to implythat they were formed through different intermediates.展开更多
Effectively controlling the selectivity of C_(2) oxygenates is desirable for electrocatalytic CO_(2) reduction.Copper catalyst has been considered as the most potential for reducing CO_(2) to C_(2) products,but it sti...Effectively controlling the selectivity of C_(2) oxygenates is desirable for electrocatalytic CO_(2) reduction.Copper catalyst has been considered as the most potential for reducing CO_(2) to C_(2) products,but it still suffers from low C_(2) selectivity,high overpotential,and competitive hydrogen evolution reaction(HER).Here,we propose a design strategy to introduce a second metal that weakly binds to H and a functional ligand that provides hydrogen bonds and protons to achieve high selectivity of C_(2)oxygenates and effective suppression of HER on the Cu(100)surface simultaneously.Seven metals and eleven ligands are screened using first-principles calculations,which shows that Sn is the most efficient for inhibiting HER and cysteamine(CYS)ligand is the most significant in reducing the limiting potential of^(*)CO hydrogenation to^(*)CHO.In the post C-C coupling steps,a so-called“pulling effect”that transfers H in the CYS ligand as a viable proton donor to the C_(2)intermediate to form an H bond,can further stabilize the OH group and facilitate the selection of C_(2)products toward oxygenates.Therefore,this heterogeneous electrocatalyst can effectively reduce CO_(2)to ethanol and ethylene glycol with an ultra-low limiting potential of-0.43 V.This study provides a new strategy for effectively improving the selectivity of C_(2)oxygenates and inhibiting HER to achieve advanced electrocatalytic CO_(2)reduction.展开更多
In this investigation, a clean, atomic economic and direct synthesis of oxygenates (methanol, ethanol) form water and methane via dielectric-barrier discharge was developed at room temperature and under atmospheric pr...In this investigation, a clean, atomic economic and direct synthesis of oxygenates (methanol, ethanol) form water and methane via dielectric-barrier discharge was developed at room temperature and under atmospheric pressure. The effect of discharge voltage on this process was studied. The results showed that the conversion of water can be as high as 7%, the selectivity of methanol and ethanol can be as high as 100%.展开更多
Partial oxidation of methane to formaldehyde and methanol was studied at atmospheric pressure in the temperature range of 700-750 °C using heteropolycompound catalysts （NH4）6HSiMo11FeO40, （NH4）4PMo11FeO39, an...Partial oxidation of methane to formaldehyde and methanol was studied at atmospheric pressure in the temperature range of 700-750 °C using heteropolycompound catalysts （NH4）6HSiMo11FeO40, （NH4）4PMo11FeO39, and H4PMo11VO40, which were prepared and characterized by various analysis techniques such as infrared, visible UV, XRD and DTA. O2 or N2O was used as the oxidizing agent, and the principal products of the reaction were CH3OH, CH2O, CO, CO2, and water. The conversion and the selectivity of products depend strongly on the reaction temperature, the nature of oxidizing agent, and the composition of catalyst.展开更多
Photoinduced synthesis of CO2 and CH4 was investigated using a batch reaction system on several photoactive materials supported on silicon dioxide. Single semiconductor showed higher selectivity to C1 compounds. The p...Photoinduced synthesis of CO2 and CH4 was investigated using a batch reaction system on several photoactive materials supported on silicon dioxide. Single semiconductor showed higher selectivity to C1 compounds. The production of C2-C3 oxygenates took place preferentially on composite semiconductor photocatalysts. In particular, it was found that acetone was the primary product over Cu / CdS –TiO2 / SiO2.展开更多
This work reports the preparation of bulk and KIT-6-diluted W-Nb-O mixed oxide bronzes by a reflux method. The influence of the incorporation of Nb and a mesoporous silica on the physicochemical features of the cataly...This work reports the preparation of bulk and KIT-6-diluted W-Nb-O mixed oxide bronzes by a reflux method. The influence of the incorporation of Nb and a mesoporous silica on the physicochemical features of the catalysts is studied. The addition of Nb favors the formation of single-phase oxide bronze structure, with improved Lewis acidity;while the incorporation of KIT-6 gives rise to well-dispersed mixed metal oxide particles on the diluter. These diluted W-Nb-O catalysts present enhanced surface areas and mesopore volumes. The materials have been tested in the valorization of an aqueous model mixture (acetol/propanal/ethanol/acetic acid/water weight ratio of 5/25/10/30/30), through C-C bond formation reactions. The increase in the Lewis nature of surface acid sites stands as the key point to maximize the total organic yield during the reaction (C5-C10 products). The best catalysts maintain their catalytic behavior after five consecutive uses.展开更多
The purpose of this paper is to study the effect of oxygenate additives into gasoline for the improvement of physicochemical properties of blends.Methyl Tertiary Butyl Ether（MTBE）,Methanol,Tertiary butyl alcohol（TB...The purpose of this paper is to study the effect of oxygenate additives into gasoline for the improvement of physicochemical properties of blends.Methyl Tertiary Butyl Ether（MTBE）,Methanol,Tertiary butyl alcohol（TBA）,and Tertiary amyl alcohol（TAA） blend into unleaded gasoline with various blended rates of 2.5%,5%,7.5%,10%,15%,and 20%.Physicochemical properties of blends are analyzed by the standard American Society of Testing and Materials（ASTM） methods.Methanol,TBA,and TAA increase density of the mixtures,but MTBE decreases density.The addition of oxygenates lead to a distortion of the base gasoline＇s distillation curves.The Reid vapor pressure（RVP） of gasoline is found to increase with the addition of the oxygenated compounds.All oxygenates improve both motor and research octane numbers.Among these four additives,TBA shows the best fuel properties.展开更多
EHMO calculations and orbital analyses of fragment;;have been performed for the formation of oxygenates in Fischer-Tropsch synthesis on the butterfly model for four different metal (Ni,Ru,Rh,Pd) catalysts supported on...EHMO calculations and orbital analyses of fragment;;have been performed for the formation of oxygenates in Fischer-Tropsch synthesis on the butterfly model for four different metal (Ni,Ru,Rh,Pd) catalysts supported on SiO2.Calculations were made for the four processes,i.e.,CO-dissociation;Coupling of CO and H to produce CHO;Insertion of CO to M-CH3;insertion of CH2 to M-CH3 On the basis of comparing the degree of CO bonds activation and the energy barriers of the foregoing processes for these four catalysts,it is concluded that Ni/SiO2 can be used as the methanation catalyst.On Ru/SiO2 and Rh/SiO2 C2-oxygenated compound can be produced (acetaldehyde),especially Rh/SiO2 is the even better catalyst,and Pd/SiO2 is a methanol synthesis catalyst.展开更多
The oxygen-containing compounds in Fischer Tropsch synthetic oil greatly affect the downstream deep processing of hydrocarbons,and effective removal is required.Com-pared to traditional removal technologies such as hy...The oxygen-containing compounds in Fischer Tropsch synthetic oil greatly affect the downstream deep processing of hydrocarbons,and effective removal is required.Com-pared to traditional removal technologies such as hydrogenation deoxygenation,solvent extraction,and extraction distillation,adsorption deoxygenation technology has the advantages of low cost,mild operating conditions,easy removal and recovery,and mini-mal impact on oil quality.Therefore,adsorption deoxygenation technology has devel-oped rapidly in various removal processes and has become a research hotspot in the cur-rent Fischer Tropsch oil deoxygenation.Adsorbents are the core of adsorption deoxygen-ation technology.Therefore,this article briefly introduces the adsorption mechanism and summarizes the research progress of adsorbents widely used in recent years,such as silica gel,alumina,molecular sieves,and metal organic frameworks,in adsorbing oxygen-containing compounds in Fischer Tropsch synthetic oils.And provide reference sugges-tions for further adsorption and deoxygenation directions in the future.展开更多
Research results regarding selective catalytic reduction(SCR)of NOx with ethanol and other C1-4 oxygenates as reductants over silver-alumina catalysts are summarized.The aspects of the process mechanism,nature of acti...Research results regarding selective catalytic reduction(SCR)of NOx with ethanol and other C1-4 oxygenates as reductants over silver-alumina catalysts are summarized.The aspects of the process mechanism,nature of active sites,role of alumina and silver(especially in the formation of bifunctional active sites),effects of reductants and reaction conditions are discussed.It has been determined that key stages of the process include formation of reactive enolic species,their interaction with NOx and formation of nitroorganic compounds which transform to NCOads species and further to N2.The results obtained over various silver-alumina catalysts demonstrate the perspectives of their application for reducing the level of nitrogen oxides in engine emissions,including in the presence of water vapor and sulfur oxides.Ways to improve the catalysts for the SCR of NOx with C1-4 oxygenates are outined.展开更多
Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,...Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,and necroptosis.Oligomerization of mitochondrial voltage-dependent anion channel 1 is an important pathological event in regulating cell death in retinal ischemia–reperfusion injury.However,its role in PANoptosis remains largely unknown.In this study,we demonstrated that voltage-dependent anion channel 1 oligomerization-mediated mitochondrial dysfunction was associated with PANoptosis in retinal ischemia–reperfusion injury.Inhibition of voltage-dependent anion channel 1 oligomerization suppressed mitochondrial dysfunction and PANoptosis in retinal cells subjected to ischemia–reperfusion injury.Mechanistically,mitochondria-derived reactive oxygen species played a central role in the voltagedependent anion channel 1-mediated regulation of PANoptosis by promoting PANoptosome assembly.Moreover,inhibiting voltage-dependent anion channel 1 oligomerization protected against PANoptosis in the retinas of rats subjected to ischemia–reperfusion injury.Overall,our findings reveal the critical role of voltage-dependent anion channel 1 oligomerization in regulating PANoptosis in retinal ischemia–reperfusion injury,highlighting voltage-dependent anion channel 1 as a promising therapeutic target.展开更多
Blood-brain barrier disruption and the neuroinflammatory response are significant pathological features that critically influence disease progression and treatment outcomes.This review systematically analyzes the curr...Blood-brain barrier disruption and the neuroinflammatory response are significant pathological features that critically influence disease progression and treatment outcomes.This review systematically analyzes the current understanding of the bidirectional relationship between blood-brain barrier disruption and neuroinflammation in traumatic brain injury,along with emerging combination therapeutic strategies.Literature review indicates that blood-brain barrier disruption and neuroinflammatory responses are key pathological features following traumatic brain injury.In the acute phase after traumatic brain injury,the pathological characteristics include primary blood-brain barrier disruption and the activation of inflammatory cascades.In the subacute phase,the pathological features are characterized by repair mechanisms and inflammatory modulation.In the chronic phase,the pathological features show persistent low-grade inflammation and incomplete recovery of the blood-brain barrier.Various physiological changes,such as structural alterations of the blood-brain barrier,inflammatory cascades,and extracellular matrix remodeling,interact with each other and are influenced by genetic,age,sex,and environmental factors.The dynamic balance between blood-brain barrier permeability and neuroinflammation is regulated by hormones,particularly sex hormones and stress-related hormones.Additionally,the role of gastrointestinal hormones is receiving increasing attention.Current treatment strategies for traumatic brain injury include various methods such as conventional drug combinations,multimodality neuromonitoring,hyperbaric oxygen therapy,and non-invasive brain stimulation.Artificial intelligence also shows potential in treatment decision-making and personalized therapy.Emerging sequential combination strategies and precision medicine approaches can help improve treatment outcomes;however,challenges remain,such as inadequate research on the mechanisms of the chronic phase traumatic brain injury and difficulties with technology integration.Future research on traumatic brain injury should focus on personalized treatment strategies,the standardization of techniques,costeffectiveness evaluations,and addressing the needs of patients with comorbidities.A multidisciplinary approach should be used to enhance treatment and improve patient outcomes.展开更多
The selective oxidation of methane under mild conditions remains the“Holy Grail of Catalysis”.The key to activating methane and inhibiting over-oxidation of target oxygenates lies in designing active centers.Copper ...The selective oxidation of methane under mild conditions remains the“Holy Grail of Catalysis”.The key to activating methane and inhibiting over-oxidation of target oxygenates lies in designing active centers.Copper nanoparticles were loaded onto TiO_(2)nanofibers using the photo-deposition method.The resulting catalysts were found to effectively convert methane into C1 oxygenated products under mild conditions.Compared with previously reported catalysts,it delivers a superior performance of up to 2510.7 mmol·g_(Cu)^(-1)·h^(-1)productivity with a selectivity of around 100%at 80℃for 5 min.Microstructure characterizations and density functional theory(DFT)calculations indicate that TiO_(2)in the mixed phase of anatase and rutile significantly increases the Cu^(+)/CuO ratio of the supported Cu species,and this ratio is linearly related to the formation rate of oxygen-containing species.The CuI site promotes the generation of active O species from H_(2)O_(2)dissociation on Cu_(2)O(111).These active O species reduce the energy barrier for breaking the C-H bond of CH_(4),thus boosting the catalytic activity.The methane conversion mechanism was proposed as a methyl radical pathway to form CH_(3)OH and CH_(3)OOH,and then the generated CH_(3)OH is further oxidized to HOCH_(2)OOH.展开更多
Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and of...Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.展开更多
基金financial supports from the National Natural Science Foundation of China(52201237)the Talent Introduction Project of Chinese Academy of Sciences(E344011)+4 种基金the Shenzhen High Level Talent Team Project(KQTD2022110109364705)the Joint Research Project of China Merchants Group and SIAT(E2Z1521)the Cross Institute Joint Research Youth Team Project of SIAT(E25427)National Natural Science Foundation of China(52402136)the China Postdoctoral Science Foundation(E325281005)。
文摘Electrocatalytic CO_(2)reduction(ECR)to produce value-added fuels and chemicals using renewable electricity is an emerging strategy to mitigate global warming and decrease reliance on fossil fuels.Among various ECR products,liquid oxygenates(Oxys)are especially attractive due to their high energy density,high safety and transportability that could be adapted to the existing infrastructure and transportation system.However,efficiently generating these highly reduced oxygen-containing products by ECR remains challenging due to the complexity of coupled proton and electron transfer processes.In recent years,in-depth studies of reaction mechanisms have advanced the design of catalysts and the regulation of reaction systems for ECR to produce Oxys,Here,by focusing on the production of typical Oxys,such as methanol,acetic acid,ethanol,acetone,n-propanol,and isopropanol,we outline various reaction paths and key intermediates for the electrochemical conversion of CO_(2)into these target products.We also summarize the current research status and recent advances in catalysts based on their elemental composition,and consider recent studies on the change of catalyst geometry and electronic structure,as well as the optimization of reaction systems to increase ECR performance.Finally,we analyze the challenges in the field of ECR to Oxys and provide an outlook on future directions for high-efficiency catalyst prediction and design,as well as the development of advanced reaction systems.
基金supported by the National Natural Science Foundation of China,Pilot Group Program of the Research Fund for International Senior Scientists(22250710676)National Natural Science Foundation of China(22078064,22378062,22304028)+1 种基金Natural Science Foundation of Fujian Province(2021J02009)Tianjin University-Fuzhou University Independent Innovation Fund Cooperation Project(TF2023-1,TF2023-8).
文摘In recent years,studies focusing on the conversion of renewable lignin-derived oxygenates(LDOs)have emphasized their potential as alternatives to fossil-based products.However,LDOs,existing as complex aromatic mixtures with diverse oxygen-containing functional groups,pose a challenge as they cannot be easily separated via distillation for direct utilization.A promising solution to this challenge lies in the efficient removal of oxygen-containing functional groups from LDOs through hydrodeoxygenation(HDO),aiming to yield biomass products with singular components.However,the high dissociation energy of the carbon-oxygen bond,coupled with its similarity to the hydrogenation energy of the benzene ring,creates a competition between deoxygenation and benzene ring hydrogenation.Considering hydrogen consumption and lignin properties,the preference is directed towards generating aromatic hydrocarbons rather than saturated components.Thus,the goal is to selectively remove oxygen-containing functional groups while preserving the benzene ring structure.Studies on LDOs conversion have indicated that the design of active components and optimization of reaction conditions play pivotal roles in achieving selective deoxygenation,but a summary of the correlation between these factors and the reaction mechanism is lacking.This review addresses this gap in knowledge by firstly summarizing the various reaction pathways for HDO of LDOs.It explores the impact of catalyst design strategies,including morphology modulation,elemental doping,and surface modification,on the adsorption-desorption dynamics between reactants and catalysts.Secondly,we delve into the application of advanced techniques such as spectroscopic techniques and computational modeling,aiding in uncovering the true active sites in HDO reactions and understanding the interaction of reactive reactants with catalyst surface-interfaces.Additionally,fundamental insights into selective deoxygenation obtained through these techniques are highlighted.Finally,we outline the challenges that lie ahead in the design of highly active and selective HDO catalysts.These challenges include the development of detection tools for reactive species with high activity at low concentrations,the study of reaction medium-catalyst interactions,and the development of theoretical models that more closely approximate real reaction situations.Addressing these challenges will pave the way for the development of efficient and selective HDO catalysts,thus advancing the field of renewable LDOs conversion.
基金funded by National Natural Science Foundation of China(22022814,21878283)Youth Innovation Promotion Association CAS(2017223)+1 种基金"Strategic Priority Research Program"of the Chinese academy of Sciences(XDB17020100)the National Key projects for Fundamental Research and Development of China(2016YFA0202801)。
文摘Direct cost-effective conversion of abundant methane to high value-added oxygenates(methanol,formic acid,acetic acid,etc.)under mild conditions is prospective for optimizing the structure of energy resources.However,the CAH bond of products is more reactive than that of high thermodynamic stable methane.Exploring an appropriate approach to eliminate the‘‘seesaw effect"between methane conversion and oxygenate selectivity is significant.In this review,we briefly summarize the research progress in the past decade on low-temperature direct conversion of methane to oxygenates in gas-solid-liquid phase over various transition metal(Fe,Cu,Rh,Pd,Au Pd,etc.)based nanoparticle or single-atom catalyst.Furthermore,the prospects of catalyst design and catalysis process are also discussed.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(NRF,2021R1C1C1013953,2022K1A4A7A04094394,2022K1A4A7A04095890)。
文摘The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.
基金This research was supported by the Zhejiang Provincial Natural Science Foundation of China(LR18B060001)Basic Research Project of Sinopec Group(415025)the Fundamental Research Funds for the Central Universities.
文摘Iron-containing zeolites play an important role in the selective oxidation of methane to oxygenates by nitrous oxide.A solid-state ion exchange method is adopted to prepare Fe-MOR zeolite catalysts with different amounts of extra-framework Al.EPR spectra and UV-vis spectra show that the percentage of iron ions in tetrahedral or octahedral coordination increases while those of clustered Fe species decrease by the addition of extra-framework Al species.Nitrous oxide titration reveals that more active Fe centers are formed,which promote the nitrous oxide consumption.The number of active centers in the catalyst with the introduction of extra-framework Al is about four times that of the catalyst without the addition of extra-framework Al.Due to this,there is an increase in the methane conversion,total selectivity and yield of oxygenates.
基金This work was supported by the National Key Basic Research Project of China (No. 2001CCA03600).
文摘Pd-MoO3/SiO2 catalyst has been prepared using the method of incipient wetness impregnation. The photo absorbing behaviors and chemisorbing properties of the catalyst have been characterized by UV-vis spectra and TPD-MS experiments. The results indicated that metal Pd loaded on MoOa/SiO2 has a significant effect on the photo absorbing performance of MoOa/SiO2, and an obvious blue shift of the absorption edge is produced. Under UV irradiation, the chemisorption state of CO2 undergoes decomposing process to form CO at 481 K, and a two-site adsorption state of ethane can be formed at around 496 K. Photo-oxidation of ethane using carbon dioxide can mainly produce propanal, ethanol and acetaldehyde in the temperature range of 353-423 K. The presence of metal Pd improves the catalytic activity remarkably.
基金This work was financially by the Chinese Science and Technology Ministry (Grant No.G1999022404)
文摘The kinetics of CO hydrogenation for the synthesis of C_2 oxygenates overRh-Mn-Li-Fe/SiO_2 was investigated. Kinetic parameters for the formation of ethanol, acetaldehyde,C'2 oxygenates, methanol and methane were obtained. The activation energy. H_2 and CO dependenceorders for ethanol and acetaldehyde formation differed greatly, the large difference seemed to implythat they were formed through different intermediates.
基金supported by the National Natural Science Foundation of China(Grant No.22033002,21525311,21773027)the Scientific Research Foundation of Graduate School of Southeast University(YBPY1920)+1 种基金the China Postdoctoral Science Foundation(Grant No.2020M681450)the China Scholarship Council(CSC,201906090150)。
文摘Effectively controlling the selectivity of C_(2) oxygenates is desirable for electrocatalytic CO_(2) reduction.Copper catalyst has been considered as the most potential for reducing CO_(2) to C_(2) products,but it still suffers from low C_(2) selectivity,high overpotential,and competitive hydrogen evolution reaction(HER).Here,we propose a design strategy to introduce a second metal that weakly binds to H and a functional ligand that provides hydrogen bonds and protons to achieve high selectivity of C_(2)oxygenates and effective suppression of HER on the Cu(100)surface simultaneously.Seven metals and eleven ligands are screened using first-principles calculations,which shows that Sn is the most efficient for inhibiting HER and cysteamine(CYS)ligand is the most significant in reducing the limiting potential of^(*)CO hydrogenation to^(*)CHO.In the post C-C coupling steps,a so-called“pulling effect”that transfers H in the CYS ligand as a viable proton donor to the C_(2)intermediate to form an H bond,can further stabilize the OH group and facilitate the selection of C_(2)products toward oxygenates.Therefore,this heterogeneous electrocatalyst can effectively reduce CO_(2)to ethanol and ethylene glycol with an ultra-low limiting potential of-0.43 V.This study provides a new strategy for effectively improving the selectivity of C_(2)oxygenates and inhibiting HER to achieve advanced electrocatalytic CO_(2)reduction.
文摘In this investigation, a clean, atomic economic and direct synthesis of oxygenates (methanol, ethanol) form water and methane via dielectric-barrier discharge was developed at room temperature and under atmospheric pressure. The effect of discharge voltage on this process was studied. The results showed that the conversion of water can be as high as 7%, the selectivity of methanol and ethanol can be as high as 100%.
文摘Partial oxidation of methane to formaldehyde and methanol was studied at atmospheric pressure in the temperature range of 700-750 °C using heteropolycompound catalysts （NH4）6HSiMo11FeO40, （NH4）4PMo11FeO39, and H4PMo11VO40, which were prepared and characterized by various analysis techniques such as infrared, visible UV, XRD and DTA. O2 or N2O was used as the oxidizing agent, and the principal products of the reaction were CH3OH, CH2O, CO, CO2, and water. The conversion and the selectivity of products depend strongly on the reaction temperature, the nature of oxidizing agent, and the composition of catalyst.
文摘Photoinduced synthesis of CO2 and CH4 was investigated using a batch reaction system on several photoactive materials supported on silicon dioxide. Single semiconductor showed higher selectivity to C1 compounds. The production of C2-C3 oxygenates took place preferentially on composite semiconductor photocatalysts. In particular, it was found that acetone was the primary product over Cu / CdS –TiO2 / SiO2.
基金Financial support by the Spanish Government(RTI2018-099668-B-C21,PGC2018-097277-B-100,and SEV-2016-0683)the Severo Ochoa Excellence Program(SVP-2014-068669)the “La Caixa-Severo Ochoa” Foundation,respectively,for their fellowships~~
文摘This work reports the preparation of bulk and KIT-6-diluted W-Nb-O mixed oxide bronzes by a reflux method. The influence of the incorporation of Nb and a mesoporous silica on the physicochemical features of the catalysts is studied. The addition of Nb favors the formation of single-phase oxide bronze structure, with improved Lewis acidity;while the incorporation of KIT-6 gives rise to well-dispersed mixed metal oxide particles on the diluter. These diluted W-Nb-O catalysts present enhanced surface areas and mesopore volumes. The materials have been tested in the valorization of an aqueous model mixture (acetol/propanal/ethanol/acetic acid/water weight ratio of 5/25/10/30/30), through C-C bond formation reactions. The increase in the Lewis nature of surface acid sites stands as the key point to maximize the total organic yield during the reaction (C5-C10 products). The best catalysts maintain their catalytic behavior after five consecutive uses.
文摘The purpose of this paper is to study the effect of oxygenate additives into gasoline for the improvement of physicochemical properties of blends.Methyl Tertiary Butyl Ether（MTBE）,Methanol,Tertiary butyl alcohol（TBA）,and Tertiary amyl alcohol（TAA） blend into unleaded gasoline with various blended rates of 2.5%,5%,7.5%,10%,15%,and 20%.Physicochemical properties of blends are analyzed by the standard American Society of Testing and Materials（ASTM） methods.Methanol,TBA,and TAA increase density of the mixtures,but MTBE decreases density.The addition of oxygenates lead to a distortion of the base gasoline＇s distillation curves.The Reid vapor pressure（RVP） of gasoline is found to increase with the addition of the oxygenated compounds.All oxygenates improve both motor and research octane numbers.Among these four additives,TBA shows the best fuel properties.
文摘EHMO calculations and orbital analyses of fragment;;have been performed for the formation of oxygenates in Fischer-Tropsch synthesis on the butterfly model for four different metal (Ni,Ru,Rh,Pd) catalysts supported on SiO2.Calculations were made for the four processes,i.e.,CO-dissociation;Coupling of CO and H to produce CHO;Insertion of CO to M-CH3;insertion of CH2 to M-CH3 On the basis of comparing the degree of CO bonds activation and the energy barriers of the foregoing processes for these four catalysts,it is concluded that Ni/SiO2 can be used as the methanation catalyst.On Ru/SiO2 and Rh/SiO2 C2-oxygenated compound can be produced (acetaldehyde),especially Rh/SiO2 is the even better catalyst,and Pd/SiO2 is a methanol synthesis catalyst.
文摘The oxygen-containing compounds in Fischer Tropsch synthetic oil greatly affect the downstream deep processing of hydrocarbons,and effective removal is required.Com-pared to traditional removal technologies such as hydrogenation deoxygenation,solvent extraction,and extraction distillation,adsorption deoxygenation technology has the advantages of low cost,mild operating conditions,easy removal and recovery,and mini-mal impact on oil quality.Therefore,adsorption deoxygenation technology has devel-oped rapidly in various removal processes and has become a research hotspot in the cur-rent Fischer Tropsch oil deoxygenation.Adsorbents are the core of adsorption deoxygen-ation technology.Therefore,this article briefly introduces the adsorption mechanism and summarizes the research progress of adsorbents widely used in recent years,such as silica gel,alumina,molecular sieves,and metal organic frameworks,in adsorbing oxygen-containing compounds in Fischer Tropsch synthetic oils.And provide reference sugges-tions for further adsorption and deoxygenation directions in the future.
文摘Research results regarding selective catalytic reduction(SCR)of NOx with ethanol and other C1-4 oxygenates as reductants over silver-alumina catalysts are summarized.The aspects of the process mechanism,nature of active sites,role of alumina and silver(especially in the formation of bifunctional active sites),effects of reductants and reaction conditions are discussed.It has been determined that key stages of the process include formation of reactive enolic species,their interaction with NOx and formation of nitroorganic compounds which transform to NCOads species and further to N2.The results obtained over various silver-alumina catalysts demonstrate the perspectives of their application for reducing the level of nitrogen oxides in engine emissions,including in the presence of water vapor and sulfur oxides.Ways to improve the catalysts for the SCR of NOx with C1-4 oxygenates are outined.
基金supported by the National Natural Science Foundation of China,Nos.82172196(to KX),82372507(to KX)the Natural Science Foundation of Hunan Province,China,No.2023JJ40804(to QZ)the Key Laboratory of Emergency and Trauma(Hainan Medical University)of the Ministry of Education,China,No.KLET-202210(to QZ)。
文摘Ischemia–reperfusion injury is a common pathophysiological mechanism in retinal degeneration.PANoptosis is a newly defined integral form of regulated cell death that combines the key features of pyroptosis,apoptosis,and necroptosis.Oligomerization of mitochondrial voltage-dependent anion channel 1 is an important pathological event in regulating cell death in retinal ischemia–reperfusion injury.However,its role in PANoptosis remains largely unknown.In this study,we demonstrated that voltage-dependent anion channel 1 oligomerization-mediated mitochondrial dysfunction was associated with PANoptosis in retinal ischemia–reperfusion injury.Inhibition of voltage-dependent anion channel 1 oligomerization suppressed mitochondrial dysfunction and PANoptosis in retinal cells subjected to ischemia–reperfusion injury.Mechanistically,mitochondria-derived reactive oxygen species played a central role in the voltagedependent anion channel 1-mediated regulation of PANoptosis by promoting PANoptosome assembly.Moreover,inhibiting voltage-dependent anion channel 1 oligomerization protected against PANoptosis in the retinas of rats subjected to ischemia–reperfusion injury.Overall,our findings reveal the critical role of voltage-dependent anion channel 1 oligomerization in regulating PANoptosis in retinal ischemia–reperfusion injury,highlighting voltage-dependent anion channel 1 as a promising therapeutic target.
基金supported by Open Scientific Research Program of Military Logistics,No.BLB20J009(to YZhao).
文摘Blood-brain barrier disruption and the neuroinflammatory response are significant pathological features that critically influence disease progression and treatment outcomes.This review systematically analyzes the current understanding of the bidirectional relationship between blood-brain barrier disruption and neuroinflammation in traumatic brain injury,along with emerging combination therapeutic strategies.Literature review indicates that blood-brain barrier disruption and neuroinflammatory responses are key pathological features following traumatic brain injury.In the acute phase after traumatic brain injury,the pathological characteristics include primary blood-brain barrier disruption and the activation of inflammatory cascades.In the subacute phase,the pathological features are characterized by repair mechanisms and inflammatory modulation.In the chronic phase,the pathological features show persistent low-grade inflammation and incomplete recovery of the blood-brain barrier.Various physiological changes,such as structural alterations of the blood-brain barrier,inflammatory cascades,and extracellular matrix remodeling,interact with each other and are influenced by genetic,age,sex,and environmental factors.The dynamic balance between blood-brain barrier permeability and neuroinflammation is regulated by hormones,particularly sex hormones and stress-related hormones.Additionally,the role of gastrointestinal hormones is receiving increasing attention.Current treatment strategies for traumatic brain injury include various methods such as conventional drug combinations,multimodality neuromonitoring,hyperbaric oxygen therapy,and non-invasive brain stimulation.Artificial intelligence also shows potential in treatment decision-making and personalized therapy.Emerging sequential combination strategies and precision medicine approaches can help improve treatment outcomes;however,challenges remain,such as inadequate research on the mechanisms of the chronic phase traumatic brain injury and difficulties with technology integration.Future research on traumatic brain injury should focus on personalized treatment strategies,the standardization of techniques,costeffectiveness evaluations,and addressing the needs of patients with comorbidities.A multidisciplinary approach should be used to enhance treatment and improve patient outcomes.
基金supported by the National Natural Science Foundation of China(Nos.92145301,91845201,22002094,22102106,22309061)the Natural Science Foundation of Jilin Province(No.YDZJ202201ZYTS360).
文摘The selective oxidation of methane under mild conditions remains the“Holy Grail of Catalysis”.The key to activating methane and inhibiting over-oxidation of target oxygenates lies in designing active centers.Copper nanoparticles were loaded onto TiO_(2)nanofibers using the photo-deposition method.The resulting catalysts were found to effectively convert methane into C1 oxygenated products under mild conditions.Compared with previously reported catalysts,it delivers a superior performance of up to 2510.7 mmol·g_(Cu)^(-1)·h^(-1)productivity with a selectivity of around 100%at 80℃for 5 min.Microstructure characterizations and density functional theory(DFT)calculations indicate that TiO_(2)in the mixed phase of anatase and rutile significantly increases the Cu^(+)/CuO ratio of the supported Cu species,and this ratio is linearly related to the formation rate of oxygen-containing species.The CuI site promotes the generation of active O species from H_(2)O_(2)dissociation on Cu_(2)O(111).These active O species reduce the energy barrier for breaking the C-H bond of CH_(4),thus boosting the catalytic activity.The methane conversion mechanism was proposed as a methyl radical pathway to form CH_(3)OH and CH_(3)OOH,and then the generated CH_(3)OH is further oxidized to HOCH_(2)OOH.
基金supported by Basic Science Research Program(Priority Research Institute)through the NRF of Korea funded by the Ministry of Education(2021R1A6A1A10039823)by the Korea Basic Science Institute(National Research Facilities and Equipment Center)grant funded by the Ministry of Education(2020R1A6C101B194)。
文摘Lithium-oxygen(Li-O2)batteries are perceived as a promising breakthrough in sustainable electrochemical energy storage,utilizing ambient air as an energy source,eliminating the need for costly cathode materials,and offering the highest theoretical energy density(~3.5 k Wh kg^(-1))among discussed candidates.Contributing to the poor cycle life of currently reported Li-O_(2)cells is singlet oxygen(1O_(2))formation,inducing parasitic reactions,degrading key components,and severely deteriorating cell performance.Here,we harness the chirality-induced spin selectivity effect of chiral cobalt oxide nanosheets(Co_(3)O_(4)NSs)as cathode materials to suppress 1O_(2)in Li-O_(2)batteries for the first time.Operando photoluminescence spectroscopy reveals a 3.7-fold and 3.23-fold reduction in 1O_(2)during discharge and charge,respectively,compared to conventional carbon paperbased cells,consistent with differential electrochemical mass spectrometry results,which indicate a near-theoretical charge-to-O_(2)ratio(2.04 e-/O_(2)).Density functional theory calculations demonstrate that chirality induces a peak shift near the Fermi level,enhancing Co 3d-O 2p hybridization,stabilizing reaction intermediates,and lowering activation barriers for Li_(2)O_(2)formation and decomposition.These findings establish a new strategy for improving the stability and energy efficiency of sustainable Li-O_(2)batteries,abridging the current gap to commercialization.
