Photoreforming is an emerging photocatalytic process that converts organic waste into hydrogen H2 using solar energy,offering a dual solution for waste valorization and sustainable fuel production.This review comprehe...Photoreforming is an emerging photocatalytic process that converts organic waste into hydrogen H2 using solar energy,offering a dual solution for waste valorization and sustainable fuel production.This review comprehensively examines the fundamental mechanisms of photoreforming,emphasizing the critical role of photocatalyst design in optimizing hydrogen evolution.Key criteria for effective photocatalysts including suitable band edge positions,broad spectrum solar absorption,and photostability are systematically analyzed alongside advances in heterojunction engineering and defect modulation.The review further explores diverse waste-derived feedstocks,such as biomass:alcohols,saccharides,lignin and plastics:PET,PLA,polyolefins,highlighting substrate,specific challenges and pretreatment strategies.Despite progress,challenges like catalyst deactivation,limited visible-light utilization,and scalability persist.Future directions advocate for robust photocatalyst engineering,mechanistic insights into charge dynamics,and scalable reactor designs to realize photoreforming’s potential as a sustainable hydrogen production technology.展开更多
The valorization of agricultural waste into high-value nanomaterials is crucial for advancing sustainable biorefineries.This study presents an efficient approach for extracting carboxylated cellulose nanocrystals(CNCs...The valorization of agricultural waste into high-value nanomaterials is crucial for advancing sustainable biorefineries.This study presents an efficient approach for extracting carboxylated cellulose nanocrystals(CNCs)from poplar leaf waste(PL),an abundant and underutilized biomass.The process involved alkaline treatment and hydrogen peroxide bleaching to purify cellulose(PL-CEL),followed by sequential periodate-chlorite oxidation to produce dicarboxylic cellulose nanocrystals(PL-CNCs).The resulting nanocrystals were comprehensively characterized using compositional analysis,XRD,FTIR,TEM,TGA,and zeta potential measurements.XRD analysis confirmed a high crystallinity index of 82%for PL-CEL,which decreased to 72.2%after oxidation due to the introduction of carboxyl groups.FTIR spectra revealed a prominent peak at 1720 cm-1,confirming successful carboxylation.TEM images showed rod-like nanocrystalswith an average length of 271.22 nmand width of 14.68 nm,while conductometric titration indicated a carboxyl content of 1.9 mmol/g.The PL-CNCs exhibited good colloidal stability with a zeta potential of-30.2mV at pH7.0.TGA demonstratedmoderate thermal stability with enhanced char formation.This work highlights a green and scalable route for converting poplar leaf waste into functional nanocellulose,suitable for applications in composites,adsorption,and sustainable materials.The novelty of this study lies in the pioneering use of poplar leaf waste combined with a sequential periodate-chlorite oxidation to sustainably produce carboxylated CNCs with enhanced functionality.展开更多
1.Introduction The non-renewable fossil fuels have triggered severe energy crisis and global climate change,necessitating the development of sustainable solutions for the growing population.It is estimated that the gl...1.Introduction The non-renewable fossil fuels have triggered severe energy crisis and global climate change,necessitating the development of sustainable solutions for the growing population.It is estimated that the global annual production of biomass exceeds 180 billion tons[1].Due to its broad availability,renewability,and tunable molecular functionality,biomass is considered as a versatile and sustainable substitute to fossil fuels for the production of fuels and chemicals[2,3].展开更多
Directional catalytic transformation of volatile organic compounds(VOCs)into value-added chemicals represents a more sustainable strategy than complete mineralization,as it simultaneously mitigates environmental pollu...Directional catalytic transformation of volatile organic compounds(VOCs)into value-added chemicals represents a more sustainable strategy than complete mineralization,as it simultaneously mitigates environmental pollution and reduces carbon emissions.The primary challenge in achieving multifunctional olefin production from alcohol-type VOCs is the lack of mechanistic clarity,which hinders the targeted synthesis of selective catalysts.Herein,we developed W-Ti hybrid metal oxide catalysts(WTiO_(x))with active Ti-O-W interfaces via a one-step hydrothermal synthesis and demonstrated their effectiveness for isopropanol conversion processes.Remarkably,WTiO_(x)-500 achieved 99.8%isopropanol conversion and 99.3% propylene yield at 140℃,significantly outperforming TiO_(2)(98.4% yield at 180℃)and WO_(3)(90.5% yield at 240℃).WTiO_(x)-500 also displayed higher thermal stability,with isopropanol conversion and propylene yield decreasing by 1.0%and 1.6% after 35 h on-stream reaction.Although impurities(e.g.,CO_(2),HCl,SO_(2))caused partial deactivation of WTiO_(x)-500,oxygen treatment regenerated the catalyst.A series of characterization techniques indicated that the controlled calcination temperature promoted the formation of an optimal Ti-O-Winterface in WTiO_(x)-500 through W substitution into the TiO_(2)lattice and WO_(3)-TiO_(2)surface interaction,where W species effectively tuned the electronic structure.This configuration endowed WTiO_(x)-500 with moderate acidity of BrФnsted(-OH)and Lewis(Ti^(4+)/W^(6+))acid sites,which synergistically facilitated charge transfer between isopropanol and catalyst,accelerated C-O bond cleavage during dehydration.This work provides mechanistic insights into isopropanol dehydration and demonstrates a potential approach for VOC valorization.展开更多
Directed degradation of abundant renewable lignin into small aromatic compounds is crucial for lignin valorization but challenging.The degradation of lignin in natural environments typically involves multienzyme syner...Directed degradation of abundant renewable lignin into small aromatic compounds is crucial for lignin valorization but challenging.The degradation of lignin in natural environments typically involves multienzyme synergy.However,the proteinaceous characteristics of lignin-degrading enzymes restrict their accessibility to certain regions of intricate lignin,resulting in the multienzyme systems being unable to fully demonstrate their effectiveness.Herein,a de novo biomimetic enzyme-nanozyme hybrid system was constructed by combiningλ-MnO_(2) nanozyme with laccase CotA from Bacillus subtilis,aimed at facilitating lignin degradation under mild conditions.The lignin degradation rate of the CotA+λ-MnO_(2) hybrid system was determined to be 25.15%,which was much higher than those of the lignin degradation systems with only laccase CotA(15.32%)orλ-MnO_(2) nanozyme(14.90%).Notably,the proportion of aromatic chemicals in the products derived from the hybrid system reached as much as 48%,which was 41.2%and 118.2%higher than those of the CotA-andλ-MnO_(2)-catalyzed systems,respectively.Analysis of products mapping and lignin structure changes suggested that the higher proportion of aromatic compounds in the CotA+λ-MnO_(2)hybrid system was more likely to benefit from the laccase-mediated methoxylation.Moreover,electron paramagnetic resonance analysis indicated that the intensity and kind of free radicals such as·OH and·O_(2)^(-)are closely linked to the degradation rate and reaction type.This work is the inaugural application of an enzyme-nanozyme hybrid system for lignin degradation,demonstrating the potential of the synergistic interaction between enzyme and nanozyme in the directed degradation of lignin.展开更多
The increasing demand for sustainable energy solutions necessitates innovative approaches to biomass utilization.This study introduces a comprehensive biorefinery model that valorizes poplar biomass into high-value pr...The increasing demand for sustainable energy solutions necessitates innovative approaches to biomass utilization.This study introduces a comprehensive biorefinery model that valorizes poplar biomass into high-value products,including ethanol,furfural,phenol,and biochar.These products not only serve as promising sources for biofuel and renewable chemicals but also contribute to pollution mitigation.The approach employs a biphasic pretreatment system utilizing p-toluenesulfonic acid,pentanol,and AlCl_(3) under optimized conditions(120℃ for 45 min),achieving remarkable efficiencies of 95.8%xylan removal,90.2%delignification,and 90.7%glucan recovery.The underlying mechanism,elucidated through density functional theory,demonstrates how the disruption of lignin-carbohydrate complexes via electrostatic and hydrogen-bonding interactions enhances product yields.The cellulose-rich substrate yielded 71.3 g/L ethanol,while solubilized xylan converted to 86.7%furfural without additional acid.Furthermore,lignin pyrolysis produced bio-oil containing over 45.2%phenolic compounds,while biochar demonstrated significant adsorptive capacity for perfluorooctanoic acid.Scaling this biorefinery model to process 140 million tons of poplar biomass annually reduces CO_(2)emissions by 75.3 million tons and provides socioeconomic savings of $17.3 billion,supporting sustainable industrial transformation.展开更多
With global carbon emissions continuing to rise,carbon dioxide(CO_(2))capture and resource utilization have become central challenges in achieving the“dual carbon”goals(carbon peak and carbon neutrality).Traditional...With global carbon emissions continuing to rise,carbon dioxide(CO_(2))capture and resource utilization have become central challenges in achieving the“dual carbon”goals(carbon peak and carbon neutrality).Traditional carbon capture and storage(CCS)technology can only temporarily sequester CO_(2),whereas emerging green catalytic technologies(photo/electro/thermal catalysis)enable the conversion of CO_(2) into high-value chemicals(e.g.,fuels,pharmaceutical intermediates),advancing the closure of the artificial carbon cycle[1,2].展开更多
Photocatalytic oxygen reduction for hydrogen peroxide(H_(2)O_(2))synthesis presents a green and costeffective production method.However,achieving highly selective H_(2)O_(2)synthesis remains challenging,necessitating ...Photocatalytic oxygen reduction for hydrogen peroxide(H_(2)O_(2))synthesis presents a green and costeffective production method.However,achieving highly selective H_(2)O_(2)synthesis remains challenging,necessitating precise control over free radical reaction pathways and minimizing undesirable oxidative by-products.Herein,we report for the visible light-driven simultaneous co-photocatalytic reduction of O2to H_(2)O_(2)and oxidation of biomass using the atomic rubidium-nitride modified carbon nitride(CNRb).The optimized CNRb catalyst demonstrates a record photoreduction rate of 8.01 mM h^(-1)for H_(2)O_(2)generation and photooxidation rate of 3.75 mM h^(-1)for furfuryl alcohol to furoic acid,achieving a remarkable solar-to-chemical conversion(SCC)efficiency of up to 2.27%.Experimental characterizations and DFT calculation disclosed that the introducing atomic Rb–N configurations allows for the high-selective generation of superoxide radicals while suppressing hydroxyl free radical formation.This is because the Rb–N serves as the new alternative site to perceive a stronger connection position for O2adsorption and reinforce the capability to extract protons,thereby triggering a high selective redox product formation.This study holds great potential in precisely regulating reactive radical processes at the atomic level,thereby paving the way for efficient synthesis of H_(2)O_(2)coupled with biomass valorization.展开更多
Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as pre...Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.展开更多
Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the in...Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.展开更多
The electrochemical oxidation of biomass-derived platform molecule 5-hydroxymethylfurfural(HMF)represents a crucial pathway for green transformation into high-value chemicals,yet its reaction pathway selectivity,effic...The electrochemical oxidation of biomass-derived platform molecule 5-hydroxymethylfurfural(HMF)represents a crucial pathway for green transformation into high-value chemicals,yet its reaction pathway selectivity,efficiency,and catalyst stability are strongly dependent on the electrolyte pH environment.Under alkaline conditions,high OH−concentration facilitates preferential aldehyde group oxidation and efficient deprotonation,enabling highly efficient synthesis of 2,5-furandicarboxylic acid,but simultaneously induces HMF self-degradation and complicates product separation.As pH decreases,the reaction mechanism shifts toward enhanced hydroxymethyl oxidation,leading to intermediate accumulation(such as 5-hydroxymethyl-2-furancarboxylic acid,2,5-diformylfuran,and 5-formyl-2-furancarboxylic acid)with challenging selectivity control and significantly slowed reaction kinetics.This review comprehensively examines the systematic differences in HMF oxidation pathways and surface catalytic mechanisms across the full pH range from alkaline to acidic conditions.Addressing the distinct reaction characteristics and core challenges in alkaline,near-neutral,and acidic media,we systematically evaluate design strategies for high-efficiency electrocatalysts and explore reactor design aspects.Future research should focus on process integration(with tailored reactor design)for energy consumption reduction in alkaline systems,targeted synthesis of diverse oxidation products in near-neutral systems,and innovative catalyst development for acidic systems,thereby advancing the efficiency,selectivity,and practical application of HMF electrooxidation technologies across the entire pH spectrum through synergistic optimization of catalyst,reactor,and process.展开更多
This study explores the use of black soldier fly larvae protein as a bio-based adhesive to produce particleboards from sugarcane bagasse.A comprehensive evaluation was conducted,including rheological characterization ...This study explores the use of black soldier fly larvae protein as a bio-based adhesive to produce particleboards from sugarcane bagasse.A comprehensive evaluation was conducted,including rheological characterization of the adhesive and physical–mechanical testing of the panels according to European standards.The black soldier fly larvae-based adhesive exhibited gel-like viscoelastic behavior,rapid partial structural recovery after shear,and favorable application properties.Particleboards manufactured with this adhesive and sugarcane bagasse achieved promising mechanical performance,with modulus of rupture and modulus of elasticity values of 30.2 and 3500 MPa,respectively.Internal bond strength exceeded 0.4 MPa,complying with European standard 312-3 specifications.For comparative purposes,a panel made with Eucalyptus grandis particles was also produced under the same conditions to demonstrate the versatility of the adhesive system.Compared to other bio-based and synthetic adhesives,this bio-based system showed competitive performance and derives from the bioconversion of organic residues.Protein adhesives were synthesized fromHermetia illucens larvae grown commercially on agriculturalwaste frompotato chip production,emphasizing the renewable origin of both the biomass and the final adhesive.These results highlight the potential of insect proteins as sustainable and circular alternatives for the wood panel industry.展开更多
基金supported by Universiti Teknologi PETRONAS and the Institute of Technology PETRONAS Sdn.Bhd.(ITPSB)through the Graduate Assistantship Scheme。
文摘Photoreforming is an emerging photocatalytic process that converts organic waste into hydrogen H2 using solar energy,offering a dual solution for waste valorization and sustainable fuel production.This review comprehensively examines the fundamental mechanisms of photoreforming,emphasizing the critical role of photocatalyst design in optimizing hydrogen evolution.Key criteria for effective photocatalysts including suitable band edge positions,broad spectrum solar absorption,and photostability are systematically analyzed alongside advances in heterojunction engineering and defect modulation.The review further explores diverse waste-derived feedstocks,such as biomass:alcohols,saccharides,lignin and plastics:PET,PLA,polyolefins,highlighting substrate,specific challenges and pretreatment strategies.Despite progress,challenges like catalyst deactivation,limited visible-light utilization,and scalability persist.Future directions advocate for robust photocatalyst engineering,mechanistic insights into charge dynamics,and scalable reactor designs to realize photoreforming’s potential as a sustainable hydrogen production technology.
基金funded by the basic scientific research Funds project of Heilongjiang Universities,grant number 2023-KYYWF-0570.
文摘The valorization of agricultural waste into high-value nanomaterials is crucial for advancing sustainable biorefineries.This study presents an efficient approach for extracting carboxylated cellulose nanocrystals(CNCs)from poplar leaf waste(PL),an abundant and underutilized biomass.The process involved alkaline treatment and hydrogen peroxide bleaching to purify cellulose(PL-CEL),followed by sequential periodate-chlorite oxidation to produce dicarboxylic cellulose nanocrystals(PL-CNCs).The resulting nanocrystals were comprehensively characterized using compositional analysis,XRD,FTIR,TEM,TGA,and zeta potential measurements.XRD analysis confirmed a high crystallinity index of 82%for PL-CEL,which decreased to 72.2%after oxidation due to the introduction of carboxyl groups.FTIR spectra revealed a prominent peak at 1720 cm-1,confirming successful carboxylation.TEM images showed rod-like nanocrystalswith an average length of 271.22 nmand width of 14.68 nm,while conductometric titration indicated a carboxyl content of 1.9 mmol/g.The PL-CNCs exhibited good colloidal stability with a zeta potential of-30.2mV at pH7.0.TGA demonstratedmoderate thermal stability with enhanced char formation.This work highlights a green and scalable route for converting poplar leaf waste into functional nanocellulose,suitable for applications in composites,adsorption,and sustainable materials.The novelty of this study lies in the pioneering use of poplar leaf waste combined with a sequential periodate-chlorite oxidation to sustainably produce carboxylated CNCs with enhanced functionality.
基金supported by the Shanghai Pilot Program for Basic Research-Shanghai Jiao Tong University(21TQ1400211)the National Key Research and Development Program(YFB20234004900)+2 种基金the Shanghai Municipal Science and Technology Major Projectthe State Key Laboratory of Photoelectric Conversion and Utilization of Solar Energy(Innovation Fund Project SKLPCU24OP009)the National Science Foundation of China(No.22579110)。
文摘1.Introduction The non-renewable fossil fuels have triggered severe energy crisis and global climate change,necessitating the development of sustainable solutions for the growing population.It is estimated that the global annual production of biomass exceeds 180 billion tons[1].Due to its broad availability,renewability,and tunable molecular functionality,biomass is considered as a versatile and sustainable substitute to fossil fuels for the production of fuels and chemicals[2,3].
基金supported by the National Natural Science Foundation of China(U23A20120 and 22425601)National Key R&D Program of China(2023YFB3810801)+2 种基金Natural Science Foundation of Hebei Province(B2021208033)Beijing Nova Program(20240484659)R&D Program of Beijing Municipal Education Commission(KZ202210005011).
文摘Directional catalytic transformation of volatile organic compounds(VOCs)into value-added chemicals represents a more sustainable strategy than complete mineralization,as it simultaneously mitigates environmental pollution and reduces carbon emissions.The primary challenge in achieving multifunctional olefin production from alcohol-type VOCs is the lack of mechanistic clarity,which hinders the targeted synthesis of selective catalysts.Herein,we developed W-Ti hybrid metal oxide catalysts(WTiO_(x))with active Ti-O-W interfaces via a one-step hydrothermal synthesis and demonstrated their effectiveness for isopropanol conversion processes.Remarkably,WTiO_(x)-500 achieved 99.8%isopropanol conversion and 99.3% propylene yield at 140℃,significantly outperforming TiO_(2)(98.4% yield at 180℃)and WO_(3)(90.5% yield at 240℃).WTiO_(x)-500 also displayed higher thermal stability,with isopropanol conversion and propylene yield decreasing by 1.0%and 1.6% after 35 h on-stream reaction.Although impurities(e.g.,CO_(2),HCl,SO_(2))caused partial deactivation of WTiO_(x)-500,oxygen treatment regenerated the catalyst.A series of characterization techniques indicated that the controlled calcination temperature promoted the formation of an optimal Ti-O-Winterface in WTiO_(x)-500 through W substitution into the TiO_(2)lattice and WO_(3)-TiO_(2)surface interaction,where W species effectively tuned the electronic structure.This configuration endowed WTiO_(x)-500 with moderate acidity of BrФnsted(-OH)and Lewis(Ti^(4+)/W^(6+))acid sites,which synergistically facilitated charge transfer between isopropanol and catalyst,accelerated C-O bond cleavage during dehydration.This work provides mechanistic insights into isopropanol dehydration and demonstrates a potential approach for VOC valorization.
文摘Directed degradation of abundant renewable lignin into small aromatic compounds is crucial for lignin valorization but challenging.The degradation of lignin in natural environments typically involves multienzyme synergy.However,the proteinaceous characteristics of lignin-degrading enzymes restrict their accessibility to certain regions of intricate lignin,resulting in the multienzyme systems being unable to fully demonstrate their effectiveness.Herein,a de novo biomimetic enzyme-nanozyme hybrid system was constructed by combiningλ-MnO_(2) nanozyme with laccase CotA from Bacillus subtilis,aimed at facilitating lignin degradation under mild conditions.The lignin degradation rate of the CotA+λ-MnO_(2) hybrid system was determined to be 25.15%,which was much higher than those of the lignin degradation systems with only laccase CotA(15.32%)orλ-MnO_(2) nanozyme(14.90%).Notably,the proportion of aromatic chemicals in the products derived from the hybrid system reached as much as 48%,which was 41.2%and 118.2%higher than those of the CotA-andλ-MnO_(2)-catalyzed systems,respectively.Analysis of products mapping and lignin structure changes suggested that the higher proportion of aromatic compounds in the CotA+λ-MnO_(2)hybrid system was more likely to benefit from the laccase-mediated methoxylation.Moreover,electron paramagnetic resonance analysis indicated that the intensity and kind of free radicals such as·OH and·O_(2)^(-)are closely linked to the degradation rate and reaction type.This work is the inaugural application of an enzyme-nanozyme hybrid system for lignin degradation,demonstrating the potential of the synergistic interaction between enzyme and nanozyme in the directed degradation of lignin.
基金funded by the National Natural Science Foundation of China(22278189,22478154)the Fundamental Research Funds for the Central Universities(Jiangnan University,JUSRP202501024)the Priority Academic Program Development of Jiangsu Higher Education Institutions,the 111 Project(No.111-2-06)。
文摘The increasing demand for sustainable energy solutions necessitates innovative approaches to biomass utilization.This study introduces a comprehensive biorefinery model that valorizes poplar biomass into high-value products,including ethanol,furfural,phenol,and biochar.These products not only serve as promising sources for biofuel and renewable chemicals but also contribute to pollution mitigation.The approach employs a biphasic pretreatment system utilizing p-toluenesulfonic acid,pentanol,and AlCl_(3) under optimized conditions(120℃ for 45 min),achieving remarkable efficiencies of 95.8%xylan removal,90.2%delignification,and 90.7%glucan recovery.The underlying mechanism,elucidated through density functional theory,demonstrates how the disruption of lignin-carbohydrate complexes via electrostatic and hydrogen-bonding interactions enhances product yields.The cellulose-rich substrate yielded 71.3 g/L ethanol,while solubilized xylan converted to 86.7%furfural without additional acid.Furthermore,lignin pyrolysis produced bio-oil containing over 45.2%phenolic compounds,while biochar demonstrated significant adsorptive capacity for perfluorooctanoic acid.Scaling this biorefinery model to process 140 million tons of poplar biomass annually reduces CO_(2)emissions by 75.3 million tons and provides socioeconomic savings of $17.3 billion,supporting sustainable industrial transformation.
基金supported by the National Natural Science Foundation of China(22472069,22102064,and 22302080)China Postdoctoral Science Foundation(2024M760028).
文摘With global carbon emissions continuing to rise,carbon dioxide(CO_(2))capture and resource utilization have become central challenges in achieving the“dual carbon”goals(carbon peak and carbon neutrality).Traditional carbon capture and storage(CCS)technology can only temporarily sequester CO_(2),whereas emerging green catalytic technologies(photo/electro/thermal catalysis)enable the conversion of CO_(2) into high-value chemicals(e.g.,fuels,pharmaceutical intermediates),advancing the closure of the artificial carbon cycle[1,2].
基金National Natural Science Foundation of China(22309032,22109120,and 62104170)Guangdong Basic and Applied Basic Research Foundation(2022A1515011737)+2 种基金Science and Technology Program of Guangzhou(2023A04J1395)GDAS’Project of Science and Technology Development(2021GDASYL-20210102010)Zhejiang Provincial Natural Science Foundation of China(LY23F040001)。
文摘Photocatalytic oxygen reduction for hydrogen peroxide(H_(2)O_(2))synthesis presents a green and costeffective production method.However,achieving highly selective H_(2)O_(2)synthesis remains challenging,necessitating precise control over free radical reaction pathways and minimizing undesirable oxidative by-products.Herein,we report for the visible light-driven simultaneous co-photocatalytic reduction of O2to H_(2)O_(2)and oxidation of biomass using the atomic rubidium-nitride modified carbon nitride(CNRb).The optimized CNRb catalyst demonstrates a record photoreduction rate of 8.01 mM h^(-1)for H_(2)O_(2)generation and photooxidation rate of 3.75 mM h^(-1)for furfuryl alcohol to furoic acid,achieving a remarkable solar-to-chemical conversion(SCC)efficiency of up to 2.27%.Experimental characterizations and DFT calculation disclosed that the introducing atomic Rb–N configurations allows for the high-selective generation of superoxide radicals while suppressing hydroxyl free radical formation.This is because the Rb–N serves as the new alternative site to perceive a stronger connection position for O2adsorption and reinforce the capability to extract protons,thereby triggering a high selective redox product formation.This study holds great potential in precisely regulating reactive radical processes at the atomic level,thereby paving the way for efficient synthesis of H_(2)O_(2)coupled with biomass valorization.
基金supported by the National Natural Sci-ence Foundation of China(Nos.22478263,22308230)Natural Science Foundation of Sichuan(No.2024NSF-SC1134)+2 种基金China Postdoctoral Science Foundation(No.2024T170612)111 center(B17030)the Fun-damental Research Funds for the Central Universities.
文摘Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.
基金financially supported by the National Natural Science Foundation of China (22472199)Chinese Universities Scientific Fund (15055009)Central University Guided Funds for Building World-Class Universities (Disciplines) and Advancing Characteristic Development
文摘Electrocatalytic glucose oxidation to high-value chemicals provides a sustainable route for biomass valorization.NiCo-based catalysts have emerged as promising candidates for glucose oxidation reaction owing to the intrinsic activity of Ni and Co catalytic centers.However,the dynamic evolution and atomic-scale synergy between these centers remain elusive.Herein,we fabricated NiCo_(2)O_(4)nanosheets supported on nickel foam,where Ni preferentially occupies tetrahedral sites to regulate the electronic configuration of octahedral Co.Experimental and theoretical results demonstrate that the incorporation of tetrahedral Ni induces low-to-intermediate spin transition in octahedral Co,thereby optimizing eg orbital occupancy and stabilizing active sites.This spin-state engineering establishes Ni-Co synergistic catalytic centers for the selective oxidation of glucose to formate(FA).At higher potential(≥1.4 V vs.RHE),octahedral Co undergoes reconstruction into excessive active CoOOH and CoO_(2)species,resulting in glucose overoxidation to CO_(2)and intensified competitive oxygen evolution.In contrast,at lower potentials(<1.4 V vs.RHE),tetrahedral Ni facilitates electron delocalization across the Ni–O–Co lattice,thereby stabilizing octahedral Co for glucose adsorption and oxidation.Subsequently,a coupled electrocatalytic system was constructed,achieving 80.7%FA yield with 91.3%Faradaic efficiency(FE)at NiCo_(2)O_(4)anode and H2 evolution rate of 696μmol h^(−1)with 99.9%FE at Pt cathode for 2 h under 1.35 V vs.RHE.This work provides a deep insight into spin-state regulation of the catalytic center,offering valuable guidance for rational catalyst design.
基金supported by the National Key R&D Program of China(2023YFA1507400)the National Natural Science Foundation of China(Grant No.22325805,22441010,22408203)+2 种基金Beijing Natural Science Foundation(Grant No.JQ22003)the Haihe Laboratory of Sustainable Chemical Transformations(24HHWCSS00007)Tsinghua University Dushi Program,and Sinopec Group(PR20232572).
文摘The electrochemical oxidation of biomass-derived platform molecule 5-hydroxymethylfurfural(HMF)represents a crucial pathway for green transformation into high-value chemicals,yet its reaction pathway selectivity,efficiency,and catalyst stability are strongly dependent on the electrolyte pH environment.Under alkaline conditions,high OH−concentration facilitates preferential aldehyde group oxidation and efficient deprotonation,enabling highly efficient synthesis of 2,5-furandicarboxylic acid,but simultaneously induces HMF self-degradation and complicates product separation.As pH decreases,the reaction mechanism shifts toward enhanced hydroxymethyl oxidation,leading to intermediate accumulation(such as 5-hydroxymethyl-2-furancarboxylic acid,2,5-diformylfuran,and 5-formyl-2-furancarboxylic acid)with challenging selectivity control and significantly slowed reaction kinetics.This review comprehensively examines the systematic differences in HMF oxidation pathways and surface catalytic mechanisms across the full pH range from alkaline to acidic conditions.Addressing the distinct reaction characteristics and core challenges in alkaline,near-neutral,and acidic media,we systematically evaluate design strategies for high-efficiency electrocatalysts and explore reactor design aspects.Future research should focus on process integration(with tailored reactor design)for energy consumption reduction in alkaline systems,targeted synthesis of diverse oxidation products in near-neutral systems,and innovative catalyst development for acidic systems,thereby advancing the efficiency,selectivity,and practical application of HMF electrooxidation technologies across the entire pH spectrum through synergistic optimization of catalyst,reactor,and process.
基金supported by the Consejo Nacional de Investigaciones Cientificas y Tecnicas(CONICET)via grant Proyectos de Investigacion Plurianuales(PIP 2021:2894)Agencia I+D+i via grant Proyectos de Investigacion Cientifica y Tecnologica(PICT-2021-I-A-00294).
文摘This study explores the use of black soldier fly larvae protein as a bio-based adhesive to produce particleboards from sugarcane bagasse.A comprehensive evaluation was conducted,including rheological characterization of the adhesive and physical–mechanical testing of the panels according to European standards.The black soldier fly larvae-based adhesive exhibited gel-like viscoelastic behavior,rapid partial structural recovery after shear,and favorable application properties.Particleboards manufactured with this adhesive and sugarcane bagasse achieved promising mechanical performance,with modulus of rupture and modulus of elasticity values of 30.2 and 3500 MPa,respectively.Internal bond strength exceeded 0.4 MPa,complying with European standard 312-3 specifications.For comparative purposes,a panel made with Eucalyptus grandis particles was also produced under the same conditions to demonstrate the versatility of the adhesive system.Compared to other bio-based and synthetic adhesives,this bio-based system showed competitive performance and derives from the bioconversion of organic residues.Protein adhesives were synthesized fromHermetia illucens larvae grown commercially on agriculturalwaste frompotato chip production,emphasizing the renewable origin of both the biomass and the final adhesive.These results highlight the potential of insect proteins as sustainable and circular alternatives for the wood panel industry.
