Biomass has been widely accepted as a "zero-emission" energy carrier to take place fossil fuels, while its catalytic conversion is still limited by low efficiency of carbon atoms. Biomass conversion via 5- hydroxyme...Biomass has been widely accepted as a "zero-emission" energy carrier to take place fossil fuels, while its catalytic conversion is still limited by low efficiency of carbon atoms. Biomass conversion via 5- hydroxymethylfurfural (HMF) as a platform chemical is highly attractive because almost all carbon atoms could he retained in the downstream chemicals under mild reaction conditions. Here we summarize recent fundamental researches and industrial progresses on all involved processes including biomass degradation to hexoses, HMF formation, hydrogenation and oxidation of HMF.展开更多
Simultaneous conversion of CO_(2)and biomass into value-added chemicals through solar-driven catalysis holds tremendous importance for fostering a sustainable circular economy.Herein,plasmonic Bi quantum dots were imm...Simultaneous conversion of CO_(2)and biomass into value-added chemicals through solar-driven catalysis holds tremendous importance for fostering a sustainable circular economy.Herein,plasmonic Bi quantum dots were immobilized on phosphoric acid modified attapulgite(P-ATP)nanorod using an in-situ reduction-deposition method,and were employed for photocatalytic reduction of CO_(2)coupled with oxidation of biomass-derived benzyl alcohol.Results revealed that Bi atoms successfully integrated into the basal structure of P-ATP,forming chemically coordinated Bi-O-Si bonds that served as efficient transportation channels for electrons.The incorporation of high-density monodispersed Bi quantum dots induced a surface plasmon resonance(SPR)effect,expanding the light absorption range into the near-infrared region.As a consequence,the photo-thermal transformation was significantly accelerated,leading to enhanced reaction kinetics.Notably,50%Bi/P-ATP nanocomposite exhibited the highest plasmon-mediated photocatalytic CH4 generation(115.7μmol·g^(−1)·h^(−1))and CO generation(44.9μmol·g^(−1)·h^(−1)),along with remarkable benzaldehyde generation rate of 79.5μmol·g^(−1)·h^(−1)in the photo-redox coupling system under solar light irradiation.The hydrogen protons released from the oxidation of benzyl alcohol facilitated the incorporation of more hydrogen protons into CO_(2)to form key CH_(3)O−intermediates.This work demonstrates the synergistic solar-driven valorization of CO_(2)and biomass using natural mineral based catalyst.展开更多
Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(...Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.展开更多
Renewable electrocatalytic upgrading of biomass feedstocks into valuable chemicals is one of the promising strategies to relieve the pressure of traditional energy-based systems.Through electrocatalytic carbon–carbon...Renewable electrocatalytic upgrading of biomass feedstocks into valuable chemicals is one of the promising strategies to relieve the pressure of traditional energy-based systems.Through electrocatalytic carbon–carbon bond cleavage of high selectivity,various functionalized molecules,such as organic acids,amides,esters,and nitriles,have great potential to be accessed from biomass.However,it has merely received finite concerns and interests in the biorefinery.This review first showcases the research progress on the electrocatalytic conversion of lipid/sugar-and lignin-derived molecules(e.g.,glycerol,mesoerythritol,xylose,glucose,1-phenylethanol,and cyclohexanol)into organic acids via specific carbon–carbon bond scission processes,with focus on disclosing reaction mechanisms,recognizing actual active species,and collecting feasible modification strategies.For the guidance of further extensive studies on biomass valorization,organic transformations via a variety of reactions,including decarboxylation,ring-opening,rearrangement,reductive hydrogenation,and carboxylation,are also disclosed for the construction of similar carbon skeletons/scaffolds.The remaining challenges,prospective applications,and future objectives in terms of biomass conversion are also proposed.This review is expected to provide references to develop renewed electrocatalytic carbon–carbon bond cleavage transformation paths/strategies for biomass upgrading.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
Conversion of levulinic acid and its esters into versatile y-valerolactone(GVL)is a pivotal and challenging step in biorefineries,limited by high catalyst cost,the use of hydrogen atmosphere,or tedious catalyst prepar...Conversion of levulinic acid and its esters into versatile y-valerolactone(GVL)is a pivotal and challenging step in biorefineries,limited by high catalyst cost,the use of hydrogen atmosphere,or tedious catalyst preparation and recycling process.Here we have successfully synthesized a ternary magnetic nanoparticle catalyst(Al_(2)O_(3)-ZrO_(2)/Fe_(3)O_(4)(5)),over which biomass-derived methyl levulinate(ML)can be quantitively converted to GVL with an extremely high selectivity of>99%and yield of-98%in the absence of molecular hydrogen.Al_(2)O_(3)-ZrO_(2)/Fe_(3)O_(4)(5)incorporates simultaneously inexpensive alumina and zirconia onto magnetite support by a facile coprecipitation method,giving rise to a core-shell structure,welldistributed acid-base sites,and strong magnetism,as evidenced by the X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM),transmission electron microscopy(TEM),high-angle annular dark-field scanning-TEM(HAADF-STEM),SEM-energy dispersive Xray spectroscopy(SEM-EDX),temperature-programmed desorption of ammonia(NH3-TPD),temperature-programmed desorption of carbon dioxide(CO_(2)-TPD),pyridine-adsorption infrared spectra(Py-IR),and vibrating sample magnetometry(VSM).Such characteristics enable it to be highly active and easily recycled by a magnet for at least five cycles with a slight loss of its catalytic activity,avoiding a time-consuming and energy-intensive reactivation process.It is found that there was a synergistic effect among the metal oxides,and the high efficiency and selectivity originating from such synergism are evidenced by kinetic studies.Furthermore,a reaction mechanism regarding the hydrogenation of ML to GVL is proposed by these findings,coupled with gas chromatography-mass spectrometry(GC-MS)analysis.Accordingly,this readily synthesized and recovered magnetic nanocatalyst for conversion of biomassderived ML into GVL can provide an eco-friendly and safe way for biomass valorization.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
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
Estimating individual tree biomass is critical to forest carbon accounting and ecosystem service modeling.In this study,we developed one-(tree diameter only) and two-variable(tree diameter and height) biomass equa...Estimating individual tree biomass is critical to forest carbon accounting and ecosystem service modeling.In this study,we developed one-(tree diameter only) and two-variable(tree diameter and height) biomass equations,biomass conversion factor(BCF) models,and an integrated simultaneous equation system(ISES) to estimate the aboveground biomass for five conifer species in China,i.e.,Cunninghamia lanceolata(Lamb.) Hook.,Pinus massoniana Lamb.,P.yunnanensis Faranch,P.tabulaeformis Carr.and P.elliottii Engelm.,based on the field measurement data of aboveground biomass and stem volumes from 1055 destructive sample trees across the country.We found that all three methods,including the one-and two-variable equations,could adequately estimate aboveground biomass with a mean prediction error less than 5%,except for Pinus yunnanensis which yielded an error of about 6%.The BCF method was slightly poorer than the biomass equation and the ISES methods.The average coefficients of determination(R^2) were 0.944,0.938 and 0.943 and the mean prediction errors were 4.26,4.49 and 4.29% for the biomass equation method,the BCF method and the ISES method,respectively.The ISES method was the best approach for estimating aboveground biomass,which not only had high accuracy but also could estimate stocking volumes simultaneously that was compatible with aboveground biomass.In addition,we found that it is possible to develop a species-invariant one-variable allometric model for estimating aboveground biomass of all the five coniferous species.The model had an exponent parameter of 7/3 and the intercept parameter a_0 could be estimated indirectly from stem basic density(a_0= 0.294 q).展开更多
Addressing climate change has become a common issue around the world in the 21st century and equally an important mission in Chinese forestry.Understanding the development of monitoring and assessment of forest biomas...Addressing climate change has become a common issue around the world in the 21st century and equally an important mission in Chinese forestry.Understanding the development of monitoring and assessment of forest biomass and carbon storage in China is important for promoting the evaluation of forest carbon sequestration capacity of China.The author conducts a systematic analysis of domestic publications addressing"monitoring and assessment of forest biomass and carbon storage"in order to understand the development trends,describes the brief history through three stages,and gives the situation of new development.Towards the end of the 20th century,a large number of papers on biomass and productivity of the major forest types in China had been published,covering the exploration and efforts of more than 20 years,while investigations into assessment of forest carbon storage had barely begun.Based on the data of the 7th and 8th National Forest Inventories,forest biomass and carbon storage of the entire country were assessed using individual tree biomass models and carbon conversion factors of major tree species,both previously published and newly developed.Accompanying the implementation of the 8th National Forest Inventory,a program of individual tree biomass modeling for major tree species in China was carried out simultaneously.By means of thematic research on classification of modeling populations,as well as procedures for collecting samples and methodology for biomass modeling,two technical regulations on sample collection and model construction were published as ministerial standards for application.Requests for approval of individual tree biomass models and carbon accounting parameters of major tree species have been issued for approval as ministerial standards.With the improvement of biomass models and carbon accounting parameters,thematic assessment of forest biomass and carbon storage will be gradually changed into a general monitoring of forest biomass and carbon storage,in order to realize their dynamic monitoring in national forest inventories.Strengthening the analysis and assessment of spatial distribution patterns of forest biomass and carbon storage through application of remote sensing techniques and geostatistical approaches will also be one of the major directions of development in the near future.展开更多
The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide poten...The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide potential window with promising Faradic efficiency(FE) towards BHMF,Cu-based electrode has been in the center of investigation.However,its structure-activity relationship remains ambiguous and its intrinsic catalytic activity is still unsatisfactory.In this work,we develop a two-step oxidation-reduction strategy to reconstruct the surface atom arrangement of the Cu foam(CF).By combination of multiple quasi-situ/in-situ techniques and density functional theory(DFT) calculation,the critical factor that governs the reaction is demonstrated to be facet effect of the metallic Cu crystal:Cu(110) facet accounts for the most favorable surface with enhanced chemisorption with reactants and selective production of BHMF,while Cu(100) facet might trigger the accumulation of the by-product 5,5'-bis(hydroxy methy)hydrofurion(BHH).With the optimized composition of the facets on the reconstructed Cu(OH)_(2)-ER/CF,the performance could be noticeably enhanced with a BHMF FE of 92.3% and HMF conversion of 98.5% at a potential of -0.15 V versus reversible hydrogen electrode(vs.RHE) in 0.1 M KOH solution.This work sheds light on the incomplete mechanistic puzzle for Cu-catalyzed electrochemical hydrogenation of HMF to BHMF,and provides a theoretical foundation for further precise design of highly efficient catalytic electrodes.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
Aloe vera plant is known worldwide for its medicinal properties and application in gel-based products such as shampoo,soap,and sunscreen.However,the demand for these gel-based products has led to a surplus production ...Aloe vera plant is known worldwide for its medicinal properties and application in gel-based products such as shampoo,soap,and sunscreen.However,the demand for these gel-based products has led to a surplus production of Aloe vera processing waste.An Aloe vera gel processing facility could generate up to 4000 kg of Aloe vera waste per month.Currently the Aloe vera waste is being disposed to the landfill or used as fertilizer.A sustainable management system for the Aloe vera processing waste should be considered,due to the negative societal and environmental impacts of the currents waste disposal methods.Therefore,this review focuses on various approaches that can be used to valorize Aloe vera waste into value-added products,such as animal and aquaculture feeds,biosorbents,biofuel and natural polymers.Researchers have reported Aloe vera waste for environmental applications biosorbents used for wastewater treatment of various pollutants.Several studies have also reported on the valorization of Aloe vera waste for production of biofuels such as bioethanol,mixed alcohol fuels,biogas and syngas.Aloe vera waste could also be valorized through isolation and synthesis of natural polymers for application in wound dressing,tissue engineering and drug delivery systems.Aloe vera waste valorization was also reviewed through extraction of value-added bioactive compounds such as aloe-emodin,aloin and aloeresin.These value-added bioactive compounds have various applications in the cosmetics(non-steroidal anti-inflammatory,tyrosinase inhibitors)and pharmaceutical(anticancer agent and COVID 19 inhibitors)industry.展开更多
Lignocellulosic biomass is a critical renewable carbon resource,but most of its utilization is inefficient,and elec-trocatalytic oxidation is a promising method of upgrading lignocellulose into value-added fuels and c...Lignocellulosic biomass is a critical renewable carbon resource,but most of its utilization is inefficient,and elec-trocatalytic oxidation is a promising method of upgrading lignocellulose into value-added fuels and chemicals under mild operating conditions.Recently,efforts to enable conversion with a high efficiency and low energy con-sumption have been reported,but understanding the reaction mechanisms and realizing scaled-up applications of the electrooxidation of lignocellulosic biomass are still in their early stages.A timely overview of recently reported general reaction mechanisms,particularly the strategies developed for use in improving the reaction efficiencies,is necessary to inspire research regarding the highly efficient utilization of lignocellulose.Herein,we summa-rize the strategies developed to improve electrocatalytic performance in oxidative lignocellulose conversion.The organized summary includes strategies ranging from designing efficient electrocatalysts and adding functional co-catalysts or electrolytes to employing advanced electrolyzers.A comprehensive overview of representative examples should provide universal principles to yield insight into the reaction processes and guide the design of efficient electrocatalytic systems.Finally,the challenges and opportunities in developing the electrocatalytic oxidative upgrading of lignocellulosic biomass in the near future are proposed.展开更多
Photocatalytic upgrading of renewable biomass is a promising way to relieve energy crisis and environmental pollution.However,low photocatalytic efficiency and uncontrollable selectivity still limit its development.He...Photocatalytic upgrading of renewable biomass is a promising way to relieve energy crisis and environmental pollution.However,low photocatalytic efficiency and uncontrollable selectivity still limit its development.Herein,ultrathin SnNb_(2)O_(6)nanosheets with high dispersed Pt nanoparticles(Pt/SN)were successfully developed as an efficient photocatalyst for the precise hydrogenation of furfural(FUR)to furfuryl alcohol(FOL)under visible light irradiation and exhibited the high conversion of FUR(99.9%)with the high selectivity for FOL(99.9%).It was revealed that SN with only 4.1 nm thickness possess good separation ability of photo-generated carriers and abundant surface Lewis acid sites(Nb^(5+))which would selectively chemisorb and activate FUR molecules via the Nb···O=C coordination.Meanwhile,Pt nanoparticles would gather photo-generated electrons for greatly promoting the generation of active H species to support the hydrogenation of FUR to FOL.The synergistic effects between SnNb_(2)O_(6)nanosheets and Pt nanoparticles remarkably facilitate the photocatalytic performance for hydrogenation.This work not only confirms the great potential of ultrathin nanosheet photocatalyst with functional metal sites for precise upgrading of biomass but also provides an in-depth view to understand the surface/interface interaction between reactant molecules and surface sites of a photocatalyst.展开更多
Hierarchical porous carbon co-doped with heterogeneous atoms has attracted much attention thanks to sizable internal void space accommodating electrolyte,high-density microporous structure physically con-fining polysu...Hierarchical porous carbon co-doped with heterogeneous atoms has attracted much attention thanks to sizable internal void space accommodating electrolyte,high-density microporous structure physically con-fining polysulfides(LPS),and heterogeneous atoms serving as active sites to capture LPS.However,solely relying on carbon material defects to capture LPS proves ineffective.Hence,metal compounds must be introduced to chemisorb LPS.Herein,cobalt ions are in-situ grown on the polydopamine layer coated on the surface of biomass-derived S,N,P co-doped hierarchical porous carbon(SNP-PC).Then a layer of nitrogen-doped porous carbon(MPC)dotted with CoSe nanoparticles is acquired by selenizing.Thus,a strong-polar/weak-polar composite material of SNP-PC studded with CoSe nanoparticles is obtained(SNP-PC@MPC@CoSe).Button cells assembled with SNP-PC@MPC@CoSe-modified separator enable superb long-cycle stability and satisfactory rate performance.An excellent rate capacity of 796 mAh g^(−1)at a high current rate of 4 C with an ultra-low capacity fading of 0.06%over 700 cycles can be acquired.More impressively,even in a harsh test condition of 5.65 mg cm^(−2)sulfur loading and 4μL mg^(−1)ratio of electrolyte to active materials,the battery can still display a specific capacity of 980 mAh g^(−1)(area capacity of∼5.54 mAh cm^(−2))at 0.1 C.This work provides a promising route toward high-performance Li-S batteries.展开更多
Glucose isomerase(GI)is an enzyme with high potential applications.Characterization of GI producing bacteria with interesting properties from an industrial point of view is essential.Bacillus sp.,Paenarthrobacter sp.,...Glucose isomerase(GI)is an enzyme with high potential applications.Characterization of GI producing bacteria with interesting properties from an industrial point of view is essential.Bacillus sp.,Paenarthrobacter sp.,Chryseobacterium sp.,Hymenobacter sp.,Mycobacterium sp.,and Stenotrophomonas sp.were isolated from soil samples.Optimization of enzyme production yield was investigated in various fermentation conditions using response surface methodology.All isolates exhibited maximum GI activity at 40℃,pH 6–8 after 4 days of incubation.A mixture of peptone/yeast extract or tryptone/peptone enhanced higher enzyme production.The same trend was observed in fermentation medium containing 1%xylose or 2%–2.5%wheat straw.This study advanced the knowledge of these bacterial isolates in promoting wheat straw as feedstock for the bio-based industry.展开更多
基金supported by the National Natural Science Foundation of China (20576025, 21133010, 21473223)Ningbo Agricultural Key Science and Technology Program (2013C11035)the Laboratory of Science and Technology on Surface Physics and Chemistry (ZDXKFZ201304, ZDXKFZ201306)
文摘Biomass has been widely accepted as a "zero-emission" energy carrier to take place fossil fuels, while its catalytic conversion is still limited by low efficiency of carbon atoms. Biomass conversion via 5- hydroxymethylfurfural (HMF) as a platform chemical is highly attractive because almost all carbon atoms could he retained in the downstream chemicals under mild reaction conditions. Here we summarize recent fundamental researches and industrial progresses on all involved processes including biomass degradation to hexoses, HMF formation, hydrogenation and oxidation of HMF.
基金the National Natural Science Foundation of China(No.51674043)Jiangsu High Institutions Key Basic Research Projects of Natural Science(No.21KJA430002)+1 种基金Changzhou International Cooperation Project(No.CZ20230018)International Joint Laboratory of the Jiangsu Education Department.
文摘Simultaneous conversion of CO_(2)and biomass into value-added chemicals through solar-driven catalysis holds tremendous importance for fostering a sustainable circular economy.Herein,plasmonic Bi quantum dots were immobilized on phosphoric acid modified attapulgite(P-ATP)nanorod using an in-situ reduction-deposition method,and were employed for photocatalytic reduction of CO_(2)coupled with oxidation of biomass-derived benzyl alcohol.Results revealed that Bi atoms successfully integrated into the basal structure of P-ATP,forming chemically coordinated Bi-O-Si bonds that served as efficient transportation channels for electrons.The incorporation of high-density monodispersed Bi quantum dots induced a surface plasmon resonance(SPR)effect,expanding the light absorption range into the near-infrared region.As a consequence,the photo-thermal transformation was significantly accelerated,leading to enhanced reaction kinetics.Notably,50%Bi/P-ATP nanocomposite exhibited the highest plasmon-mediated photocatalytic CH4 generation(115.7μmol·g^(−1)·h^(−1))and CO generation(44.9μmol·g^(−1)·h^(−1)),along with remarkable benzaldehyde generation rate of 79.5μmol·g^(−1)·h^(−1)in the photo-redox coupling system under solar light irradiation.The hydrogen protons released from the oxidation of benzyl alcohol facilitated the incorporation of more hydrogen protons into CO_(2)to form key CH_(3)O−intermediates.This work demonstrates the synergistic solar-driven valorization of CO_(2)and biomass using natural mineral based catalyst.
基金supported by the National Key R&D Program of China(2022YFA2105900)the National Natural Science Foundation of China(No.22178197)。
文摘Electrochemical reduction of CO_(2)(CO_(2)RR)has become a research hot spot in recent years in the context of carbon neutrality.HCOOH is one of the most promising products obtained by electrochemical reduction of CO_(2) due to its high energy value as estimated by market price per energy unit and wide application in chemical industry.Biomass is the most abundant renewable resource in the natural world.Coupling biomass oxidative conversion with CO_(2)RR driven by renewable electricity would well achieve carbon negativity.In this work,we comprehensively reviewed the current research progress on CO_(2)RR to produce HCOOH and coupled system for conversion of biomass and its derivatives to produce value-added products.Sn-and Bi-based electrocatalysts are discussed for CO_(2)RR with regards to the structure of the catalyst and reaction mechanisms.Electro-oxidation reactions of biomass derived sugars,alcohols,furan aldehydes and even polymeric components of lignocellulose were reviewed as alternatives to replace oxygen evolution reaction(OER)in the conventional electrolysis process.It was recommended that to further improve the efficiency of the coupled system,future work should be focused on the development of more efficient and stable catalysts,careful design of the electrolytic cells for improving the mass transfer and development of environment-friendly processes for recovering the formed formate and biomass oxidation products.
基金financially supported by the National Natural Science Foundation of China(22368014)the Guizhou Provincial S&T Project(ZK[2022]011,GCC[2023]011)+1 种基金the Guizhou Provincial Higher Education Institution Program(Qianjiaoji[2023]082)supported by RUDN University Strategic Academic Leadership Program。
文摘Renewable electrocatalytic upgrading of biomass feedstocks into valuable chemicals is one of the promising strategies to relieve the pressure of traditional energy-based systems.Through electrocatalytic carbon–carbon bond cleavage of high selectivity,various functionalized molecules,such as organic acids,amides,esters,and nitriles,have great potential to be accessed from biomass.However,it has merely received finite concerns and interests in the biorefinery.This review first showcases the research progress on the electrocatalytic conversion of lipid/sugar-and lignin-derived molecules(e.g.,glycerol,mesoerythritol,xylose,glucose,1-phenylethanol,and cyclohexanol)into organic acids via specific carbon–carbon bond scission processes,with focus on disclosing reaction mechanisms,recognizing actual active species,and collecting feasible modification strategies.For the guidance of further extensive studies on biomass valorization,organic transformations via a variety of reactions,including decarboxylation,ring-opening,rearrangement,reductive hydrogenation,and carboxylation,are also disclosed for the construction of similar carbon skeletons/scaffolds.The remaining challenges,prospective applications,and future objectives in terms of biomass conversion are also proposed.This review is expected to provide references to develop renewed electrocatalytic carbon–carbon bond cleavage transformation paths/strategies for biomass upgrading.
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financed by the National Natural Science Foundation of China(31671572)the National Key R&D Program of China(2016YFE0112800)the Program for Changjiang Scholars and Innovative Research Team in University of Ministry of Education of China(IRT-17R105)。
文摘Conversion of levulinic acid and its esters into versatile y-valerolactone(GVL)is a pivotal and challenging step in biorefineries,limited by high catalyst cost,the use of hydrogen atmosphere,or tedious catalyst preparation and recycling process.Here we have successfully synthesized a ternary magnetic nanoparticle catalyst(Al_(2)O_(3)-ZrO_(2)/Fe_(3)O_(4)(5)),over which biomass-derived methyl levulinate(ML)can be quantitively converted to GVL with an extremely high selectivity of>99%and yield of-98%in the absence of molecular hydrogen.Al_(2)O_(3)-ZrO_(2)/Fe_(3)O_(4)(5)incorporates simultaneously inexpensive alumina and zirconia onto magnetite support by a facile coprecipitation method,giving rise to a core-shell structure,welldistributed acid-base sites,and strong magnetism,as evidenced by the X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),scanning electron microscopy(SEM),transmission electron microscopy(TEM),high-angle annular dark-field scanning-TEM(HAADF-STEM),SEM-energy dispersive Xray spectroscopy(SEM-EDX),temperature-programmed desorption of ammonia(NH3-TPD),temperature-programmed desorption of carbon dioxide(CO_(2)-TPD),pyridine-adsorption infrared spectra(Py-IR),and vibrating sample magnetometry(VSM).Such characteristics enable it to be highly active and easily recycled by a magnet for at least five cycles with a slight loss of its catalytic activity,avoiding a time-consuming and energy-intensive reactivation process.It is found that there was a synergistic effect among the metal oxides,and the high efficiency and selectivity originating from such synergism are evidenced by kinetic studies.Furthermore,a reaction mechanism regarding the hydrogenation of ML to GVL is proposed by these findings,coupled with gas chromatography-mass spectrometry(GC-MS)analysis.Accordingly,this readily synthesized and recovered magnetic nanocatalyst for conversion of biomassderived ML into GVL can provide an eco-friendly and safe way for biomass valorization.
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(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funded by National Natural Science Foundation of China(Grant Nos.31270697,31370634,31570628)supported by State Forestry Administration of China(Grant No.2030208)
文摘Estimating individual tree biomass is critical to forest carbon accounting and ecosystem service modeling.In this study,we developed one-(tree diameter only) and two-variable(tree diameter and height) biomass equations,biomass conversion factor(BCF) models,and an integrated simultaneous equation system(ISES) to estimate the aboveground biomass for five conifer species in China,i.e.,Cunninghamia lanceolata(Lamb.) Hook.,Pinus massoniana Lamb.,P.yunnanensis Faranch,P.tabulaeformis Carr.and P.elliottii Engelm.,based on the field measurement data of aboveground biomass and stem volumes from 1055 destructive sample trees across the country.We found that all three methods,including the one-and two-variable equations,could adequately estimate aboveground biomass with a mean prediction error less than 5%,except for Pinus yunnanensis which yielded an error of about 6%.The BCF method was slightly poorer than the biomass equation and the ISES methods.The average coefficients of determination(R^2) were 0.944,0.938 and 0.943 and the mean prediction errors were 4.26,4.49 and 4.29% for the biomass equation method,the BCF method and the ISES method,respectively.The ISES method was the best approach for estimating aboveground biomass,which not only had high accuracy but also could estimate stocking volumes simultaneously that was compatible with aboveground biomass.In addition,we found that it is possible to develop a species-invariant one-variable allometric model for estimating aboveground biomass of all the five coniferous species.The model had an exponent parameter of 7/3 and the intercept parameter a_0 could be estimated indirectly from stem basic density(a_0= 0.294 q).
基金funded by the State Forestry Administration of China
文摘Addressing climate change has become a common issue around the world in the 21st century and equally an important mission in Chinese forestry.Understanding the development of monitoring and assessment of forest biomass and carbon storage in China is important for promoting the evaluation of forest carbon sequestration capacity of China.The author conducts a systematic analysis of domestic publications addressing"monitoring and assessment of forest biomass and carbon storage"in order to understand the development trends,describes the brief history through three stages,and gives the situation of new development.Towards the end of the 20th century,a large number of papers on biomass and productivity of the major forest types in China had been published,covering the exploration and efforts of more than 20 years,while investigations into assessment of forest carbon storage had barely begun.Based on the data of the 7th and 8th National Forest Inventories,forest biomass and carbon storage of the entire country were assessed using individual tree biomass models and carbon conversion factors of major tree species,both previously published and newly developed.Accompanying the implementation of the 8th National Forest Inventory,a program of individual tree biomass modeling for major tree species in China was carried out simultaneously.By means of thematic research on classification of modeling populations,as well as procedures for collecting samples and methodology for biomass modeling,two technical regulations on sample collection and model construction were published as ministerial standards for application.Requests for approval of individual tree biomass models and carbon accounting parameters of major tree species have been issued for approval as ministerial standards.With the improvement of biomass models and carbon accounting parameters,thematic assessment of forest biomass and carbon storage will be gradually changed into a general monitoring of forest biomass and carbon storage,in order to realize their dynamic monitoring in national forest inventories.Strengthening the analysis and assessment of spatial distribution patterns of forest biomass and carbon storage through application of remote sensing techniques and geostatistical approaches will also be one of the major directions of development in the near future.
基金supported by the National Natural Science Foundation of China (21808035, 21901040)the Natural Science Foundation of Fujian Province (2019J05058, 2021J05216, 2022J01922)+3 种基金the Fujian Provincial Department of Finance (GY-Z220231)the fund of the State Key Laboratory of Catalysis in DICP (N-22-08)the Fujian Fishery Disaster Reduction Center (GY-H-22146)College Student Innovation and Entrepreneurship Training Program (x202110388068)。
文摘The electrochemical hydrogenation of HMF to BHMF is an elegant alternative to the conventio nal thermocatalytic route for the production of high-value-added chemicals from biomass resources.In virtue of the wide potential window with promising Faradic efficiency(FE) towards BHMF,Cu-based electrode has been in the center of investigation.However,its structure-activity relationship remains ambiguous and its intrinsic catalytic activity is still unsatisfactory.In this work,we develop a two-step oxidation-reduction strategy to reconstruct the surface atom arrangement of the Cu foam(CF).By combination of multiple quasi-situ/in-situ techniques and density functional theory(DFT) calculation,the critical factor that governs the reaction is demonstrated to be facet effect of the metallic Cu crystal:Cu(110) facet accounts for the most favorable surface with enhanced chemisorption with reactants and selective production of BHMF,while Cu(100) facet might trigger the accumulation of the by-product 5,5'-bis(hydroxy methy)hydrofurion(BHH).With the optimized composition of the facets on the reconstructed Cu(OH)_(2)-ER/CF,the performance could be noticeably enhanced with a BHMF FE of 92.3% and HMF conversion of 98.5% at a potential of -0.15 V versus reversible hydrogen electrode(vs.RHE) in 0.1 M KOH solution.This work sheds light on the incomplete mechanistic puzzle for Cu-catalyzed electrochemical hydrogenation of HMF to BHMF,and provides a theoretical foundation for further precise design of highly efficient catalytic electrodes.
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.
文摘Aloe vera plant is known worldwide for its medicinal properties and application in gel-based products such as shampoo,soap,and sunscreen.However,the demand for these gel-based products has led to a surplus production of Aloe vera processing waste.An Aloe vera gel processing facility could generate up to 4000 kg of Aloe vera waste per month.Currently the Aloe vera waste is being disposed to the landfill or used as fertilizer.A sustainable management system for the Aloe vera processing waste should be considered,due to the negative societal and environmental impacts of the currents waste disposal methods.Therefore,this review focuses on various approaches that can be used to valorize Aloe vera waste into value-added products,such as animal and aquaculture feeds,biosorbents,biofuel and natural polymers.Researchers have reported Aloe vera waste for environmental applications biosorbents used for wastewater treatment of various pollutants.Several studies have also reported on the valorization of Aloe vera waste for production of biofuels such as bioethanol,mixed alcohol fuels,biogas and syngas.Aloe vera waste could also be valorized through isolation and synthesis of natural polymers for application in wound dressing,tissue engineering and drug delivery systems.Aloe vera waste valorization was also reviewed through extraction of value-added bioactive compounds such as aloe-emodin,aloin and aloeresin.These value-added bioactive compounds have various applications in the cosmetics(non-steroidal anti-inflammatory,tyrosinase inhibitors)and pharmaceutical(anticancer agent and COVID 19 inhibitors)industry.
基金supported by the National Natural Science Foundation of China(grant numbers 22275138,22271219,22071172,22375142).
文摘Lignocellulosic biomass is a critical renewable carbon resource,but most of its utilization is inefficient,and elec-trocatalytic oxidation is a promising method of upgrading lignocellulose into value-added fuels and chemicals under mild operating conditions.Recently,efforts to enable conversion with a high efficiency and low energy con-sumption have been reported,but understanding the reaction mechanisms and realizing scaled-up applications of the electrooxidation of lignocellulosic biomass are still in their early stages.A timely overview of recently reported general reaction mechanisms,particularly the strategies developed for use in improving the reaction efficiencies,is necessary to inspire research regarding the highly efficient utilization of lignocellulose.Herein,we summa-rize the strategies developed to improve electrocatalytic performance in oxidative lignocellulose conversion.The organized summary includes strategies ranging from designing efficient electrocatalysts and adding functional co-catalysts or electrolytes to employing advanced electrolyzers.A comprehensive overview of representative examples should provide universal principles to yield insight into the reaction processes and guide the design of efficient electrocatalytic systems.Finally,the challenges and opportunities in developing the electrocatalytic oxidative upgrading of lignocellulosic biomass in the near future are proposed.
基金supported by the National Natural Science Foundation of China(21872032)。
文摘Photocatalytic upgrading of renewable biomass is a promising way to relieve energy crisis and environmental pollution.However,low photocatalytic efficiency and uncontrollable selectivity still limit its development.Herein,ultrathin SnNb_(2)O_(6)nanosheets with high dispersed Pt nanoparticles(Pt/SN)were successfully developed as an efficient photocatalyst for the precise hydrogenation of furfural(FUR)to furfuryl alcohol(FOL)under visible light irradiation and exhibited the high conversion of FUR(99.9%)with the high selectivity for FOL(99.9%).It was revealed that SN with only 4.1 nm thickness possess good separation ability of photo-generated carriers and abundant surface Lewis acid sites(Nb^(5+))which would selectively chemisorb and activate FUR molecules via the Nb···O=C coordination.Meanwhile,Pt nanoparticles would gather photo-generated electrons for greatly promoting the generation of active H species to support the hydrogenation of FUR to FOL.The synergistic effects between SnNb_(2)O_(6)nanosheets and Pt nanoparticles remarkably facilitate the photocatalytic performance for hydrogenation.This work not only confirms the great potential of ultrathin nanosheet photocatalyst with functional metal sites for precise upgrading of biomass but also provides an in-depth view to understand the surface/interface interaction between reactant molecules and surface sites of a photocatalyst.
基金supported by the National Natural Science Foundation of China(No.52003110)the Natural Science Foundation of Jiangxi Province(Nos.20202ACB202002,20202ACB214002).
文摘Hierarchical porous carbon co-doped with heterogeneous atoms has attracted much attention thanks to sizable internal void space accommodating electrolyte,high-density microporous structure physically con-fining polysulfides(LPS),and heterogeneous atoms serving as active sites to capture LPS.However,solely relying on carbon material defects to capture LPS proves ineffective.Hence,metal compounds must be introduced to chemisorb LPS.Herein,cobalt ions are in-situ grown on the polydopamine layer coated on the surface of biomass-derived S,N,P co-doped hierarchical porous carbon(SNP-PC).Then a layer of nitrogen-doped porous carbon(MPC)dotted with CoSe nanoparticles is acquired by selenizing.Thus,a strong-polar/weak-polar composite material of SNP-PC studded with CoSe nanoparticles is obtained(SNP-PC@MPC@CoSe).Button cells assembled with SNP-PC@MPC@CoSe-modified separator enable superb long-cycle stability and satisfactory rate performance.An excellent rate capacity of 796 mAh g^(−1)at a high current rate of 4 C with an ultra-low capacity fading of 0.06%over 700 cycles can be acquired.More impressively,even in a harsh test condition of 5.65 mg cm^(−2)sulfur loading and 4μL mg^(−1)ratio of electrolyte to active materials,the battery can still display a specific capacity of 980 mAh g^(−1)(area capacity of∼5.54 mAh cm^(−2))at 0.1 C.This work provides a promising route toward high-performance Li-S batteries.
基金supported by the Natural Science and Engineering Research Council of Canada(NSERC)Discovery Grant(RGPIN-2017-05366)to WQ.
文摘Glucose isomerase(GI)is an enzyme with high potential applications.Characterization of GI producing bacteria with interesting properties from an industrial point of view is essential.Bacillus sp.,Paenarthrobacter sp.,Chryseobacterium sp.,Hymenobacter sp.,Mycobacterium sp.,and Stenotrophomonas sp.were isolated from soil samples.Optimization of enzyme production yield was investigated in various fermentation conditions using response surface methodology.All isolates exhibited maximum GI activity at 40℃,pH 6–8 after 4 days of incubation.A mixture of peptone/yeast extract or tryptone/peptone enhanced higher enzyme production.The same trend was observed in fermentation medium containing 1%xylose or 2%–2.5%wheat straw.This study advanced the knowledge of these bacterial isolates in promoting wheat straw as feedstock for the bio-based industry.