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
A cost-effective and sustainable noble-metal free catalyst system based on ubiquitously available Mn-Cu bimetallic oxides was served as efficient catalysts for furfural selective oxidation to furancarboxylic acid(FA)....A cost-effective and sustainable noble-metal free catalyst system based on ubiquitously available Mn-Cu bimetallic oxides was served as efficient catalysts for furfural selective oxidation to furancarboxylic acid(FA). Interestingly, Mn_(2)Cu_(1)O_(x)exhibited an excellent furfural conversion of 99% with quantitative selectivity toward FA. Especially, we demonstrate the significant weakening of the Mn-O bonds with the incorporation of CuO into the Mn-Cu oxides, resulting in an improved OLreactivity of Mn_(2)Cu_(1)O_(x), which brings about a higher catalytic activity for furfural oxidation. More importantly, Mn_(2)Cu_(1)O_(x)could exhibit YFA>90% over 5 cycles of reusability test. Through this study, the relationship between the morphology, surface chemistry, and catalytic activity of Mn-Cu bimetallic oxides are elucidated, providing a simple and environmentally friendly catalytic strategy and scientific basis for the development of Mn-Cu bimetallic oxides bioderived molecular aerobic oxidation materials.展开更多
Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture ...Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.展开更多
Developing an efficient and easily available catalyst for the selective conversion of biomass-derived 5-hydroxymethylfurfural(HMF)into furan-2,5-dimethylcarboxylate(FDMC),a valuable biomass-based monomer,remains a hig...Developing an efficient and easily available catalyst for the selective conversion of biomass-derived 5-hydroxymethylfurfural(HMF)into furan-2,5-dimethylcarboxylate(FDMC),a valuable biomass-based monomer,remains a high demand but formidable challenge.Herein,a facile strategy for the synthesis of N-doped carbon-supported Co/Fe bimetallic catalyst(CoFe-NC)was developed,which provided an outstanding FDMC yield of 93%in a batch reactor(base-free,80℃,2 bar O_(2),4 h).Interestingly,CoFe-NC also gave a high FDMC yield of 91%under continuous-flow conditions for 80 h(5 bar O_(2),80℃,GHSV 1320 h^(-1),LHSV 0.6 h^(-1),base-free).Notably,it is the first time that a non-noble catalyst gave such a high FDMC yield under continuous-flow conditions.The introduction of Fe could greatly improve both the electron intensity of Co-N_(x)species and basicity of the catalyst,which endowed CoFe-NC with improved O_(2)activation capacity and enhanced dehydrogenation activity for the oxidation-esterification of HMF.This work delineates the efficient strategy on the construction of N-doped carbon-supported non-noble catalyst,which might open a new avenue for developing highly efficient catalyst for FDMC production.展开更多
Wood-based hydrogel with a unique anisotropic structure is an attractive soft material,but the presence of rigid crystalline cellulose in natural wood makes the hydrogel less flexible.In this study,an all-wood hydroge...Wood-based hydrogel with a unique anisotropic structure is an attractive soft material,but the presence of rigid crystalline cellulose in natural wood makes the hydrogel less flexible.In this study,an all-wood hydrogel was constructed by cross-linking cellulose fibers,polyvinyl alcohol(PVA)chains,and lignin molecules through the Hofmeister effect.The all-wood hydrogel shows a high tensile strength of 36.5 MPa and a strain up to~438%in the longitudinal direction,which is much higher than its tensile strength(~2.6 MPa)and strain(~198%)in the radial direction,respectively.The high mechanical strength of all-wood hydrogels is mainly attributed to the strong hydrogen bonding,physical entanglement,and van der Waals forces between lignin molecules,cellulose nanofibers,and PVA chains.Thanks to its excellent flexibility,good conductivity,and sensitivity,the all-wood hydrogel can accurately distinguish diverse macroscale or subtle human movements,including finger flexion,pulse,and swallowing behavior.In particular,when“An Qi”was called four times within 15 s,two variations of the pronunciation could be identified.With recyclable,biodegradable,and adjustable mechanical properties,the all-wood hydrogel is a multifunctional soft material with promising applications,such as human motion monitoring,tissue engineering,and robotics materials.展开更多
With the fast generation of electronic waste(e-waste)and the increasing depletion of metal resources,“urban mining”that can selectively recover gold from secondary resources has attracted great interest.Construction...With the fast generation of electronic waste(e-waste)and the increasing depletion of metal resources,“urban mining”that can selectively recover gold from secondary resources has attracted great interest.Construction of materials with high extraction capacity and satisfying selectivity in complex aqueous-based matrices still remains challenging.Here,a novel metal-organic framework/polymer composite(Fe-BTC/poly(thioctic acid),denoted as Fe-BTC/pTA)has been newly synthesized and applied for selective gold recovery in different matrices(river water,seawater,and leaching solution of e-waste).Benefiting from the high specific surface area and suitable pore sizes as well as the rational design of active sites,the composite exhibits high adsorption capacity(920 mg/g),high removal efficiency(>99%),fast kinetics(below 0.1 ppb within 10 min),and good applicability in complex matrices,which are better than those of most reported sulfur-containing adsorbents.Solid-state metallic gold with high purity can be effectively enriched due to the high recyclability and long-term stability of the composite.The material after adsorption can be further applied as a heterogeneous catalyst for water remediation due to the in situ generated gold nanoparticles by the redox reaction between Au(III)ions and the S-containing groups in the composites.展开更多
Higher alcohol synthesis(HAS)from syngas could efficiently alleviate the dependence on the traditional fossil resources.However,it is still challenging to construct high-performance HAS catalysts with satisfying selec...Higher alcohol synthesis(HAS)from syngas could efficiently alleviate the dependence on the traditional fossil resources.However,it is still challenging to construct high-performance HAS catalysts with satisfying selectivity,space–time yield(STY),and stability.Herein,we designed a diatomic catalyst by anchoring Co and Cu sites onto a hierarchical porous N-doped carbon matrix(Co/Cu–N–C).The Co/Cu–N–C is efficient for HAS and is among the best catalysts reported.With a COconversion of 81.7%,C2+OHselectivity could reach 58.5%with an outstanding C2+OH STY of 851.8 mg/g·h.We found that the N4–Co1 and Cu1–N4 showed an excellent synergistic effect.The adsorption of CO occurred on the Co site,and the surrounding nitrogen sites served as a hydrogen reservoir for the CO reduction reactions to form CHxCo.Meanwhile,the Cu sites stabilized a CHOCu species to interact with CHxCo,facilitating a barrier-free formation of C2 species,which is responsible for the high selectivity of higher alcohols.展开更多
Traditional matrix does not allow matrix-assisted laser desorption/ionization mass spectrometry(MALDI MS) to analyze volatile compounds,because volatile analytes may vaporize during the sample preparation process or i...Traditional matrix does not allow matrix-assisted laser desorption/ionization mass spectrometry(MALDI MS) to analyze volatile compounds,because volatile analytes may vaporize during the sample preparation process or in the high vacuum circumstance of ion source.Herein,we reported a Co and N doped porous carbon material(Co-NC) which were synthesized by pyrolysis of a Schiff base coordination compound.Co-NC could simultaneously act as adsorbent of volatile compounds and as matrix of MALDI MS,to provide the capability of MALDI MS to analyze volatile compounds.As adsorbent,Co-NC could stro ngly adsorb and enrich the volatile compounds in perfume and herbs,and hold them even in the high vacuum circumstance.On the other hand,Co-NC could absorb the energy of the laser,and then transfer the energy to the analyte for desorption and ionization of analyte in both negative and positive ionization modes.Additionally,the background interferences were avoided in the low-mass region(<500 Da) when using Co-NC as matrix,overcoming the challenges of MALDI MS analysis of small molecule compounds.In summary,Co-NC as matrix tremendously extended the application of MALDI MS.展开更多
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supported by the National Natural Science Fund of China (Nos. 21978246 and 21776234)。
文摘A cost-effective and sustainable noble-metal free catalyst system based on ubiquitously available Mn-Cu bimetallic oxides was served as efficient catalysts for furfural selective oxidation to furancarboxylic acid(FA). Interestingly, Mn_(2)Cu_(1)O_(x)exhibited an excellent furfural conversion of 99% with quantitative selectivity toward FA. Especially, we demonstrate the significant weakening of the Mn-O bonds with the incorporation of CuO into the Mn-Cu oxides, resulting in an improved OLreactivity of Mn_(2)Cu_(1)O_(x), which brings about a higher catalytic activity for furfural oxidation. More importantly, Mn_(2)Cu_(1)O_(x)could exhibit YFA>90% over 5 cycles of reusability test. Through this study, the relationship between the morphology, surface chemistry, and catalytic activity of Mn-Cu bimetallic oxides are elucidated, providing a simple and environmentally friendly catalytic strategy and scientific basis for the development of Mn-Cu bimetallic oxides bioderived molecular aerobic oxidation materials.
基金financial support from the National Natural Science Foundation of China(22078274,21903066)。
文摘Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.
基金funding supported by the National Natural Science Foundation of China(22078275)the Key-Area Research and Development Program of Guangdong Province(2020B0101070001)+1 种基金the Natural Science Foundation of Fujian Province of China(2021H0009)the Petro China Innovation Foundation(2019D-5007-0413)。
文摘Developing an efficient and easily available catalyst for the selective conversion of biomass-derived 5-hydroxymethylfurfural(HMF)into furan-2,5-dimethylcarboxylate(FDMC),a valuable biomass-based monomer,remains a high demand but formidable challenge.Herein,a facile strategy for the synthesis of N-doped carbon-supported Co/Fe bimetallic catalyst(CoFe-NC)was developed,which provided an outstanding FDMC yield of 93%in a batch reactor(base-free,80℃,2 bar O_(2),4 h).Interestingly,CoFe-NC also gave a high FDMC yield of 91%under continuous-flow conditions for 80 h(5 bar O_(2),80℃,GHSV 1320 h^(-1),LHSV 0.6 h^(-1),base-free).Notably,it is the first time that a non-noble catalyst gave such a high FDMC yield under continuous-flow conditions.The introduction of Fe could greatly improve both the electron intensity of Co-N_(x)species and basicity of the catalyst,which endowed CoFe-NC with improved O_(2)activation capacity and enhanced dehydrogenation activity for the oxidation-esterification of HMF.This work delineates the efficient strategy on the construction of N-doped carbon-supported non-noble catalyst,which might open a new avenue for developing highly efficient catalyst for FDMC production.
基金The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China,China(Nos.21978248,21676223)the Natural Science Foundation of Fujian Province of China(No.2019J06005)+1 种基金Guangdong Provincial Key Research and Development Program(No.2020B0101070001)Open access funding provided by Shanghai Jiao Tong University
文摘Wood-based hydrogel with a unique anisotropic structure is an attractive soft material,but the presence of rigid crystalline cellulose in natural wood makes the hydrogel less flexible.In this study,an all-wood hydrogel was constructed by cross-linking cellulose fibers,polyvinyl alcohol(PVA)chains,and lignin molecules through the Hofmeister effect.The all-wood hydrogel shows a high tensile strength of 36.5 MPa and a strain up to~438%in the longitudinal direction,which is much higher than its tensile strength(~2.6 MPa)and strain(~198%)in the radial direction,respectively.The high mechanical strength of all-wood hydrogels is mainly attributed to the strong hydrogen bonding,physical entanglement,and van der Waals forces between lignin molecules,cellulose nanofibers,and PVA chains.Thanks to its excellent flexibility,good conductivity,and sensitivity,the all-wood hydrogel can accurately distinguish diverse macroscale or subtle human movements,including finger flexion,pulse,and swallowing behavior.In particular,when“An Qi”was called four times within 15 s,two variations of the pronunciation could be identified.With recyclable,biodegradable,and adjustable mechanical properties,the all-wood hydrogel is a multifunctional soft material with promising applications,such as human motion monitoring,tissue engineering,and robotics materials.
基金support from the National Natural Science Foundation of China(Nos.22078274,22373080,and 21903066)the President Fund of Xiamen University(No.20720210046).
文摘With the fast generation of electronic waste(e-waste)and the increasing depletion of metal resources,“urban mining”that can selectively recover gold from secondary resources has attracted great interest.Construction of materials with high extraction capacity and satisfying selectivity in complex aqueous-based matrices still remains challenging.Here,a novel metal-organic framework/polymer composite(Fe-BTC/poly(thioctic acid),denoted as Fe-BTC/pTA)has been newly synthesized and applied for selective gold recovery in different matrices(river water,seawater,and leaching solution of e-waste).Benefiting from the high specific surface area and suitable pore sizes as well as the rational design of active sites,the composite exhibits high adsorption capacity(920 mg/g),high removal efficiency(>99%),fast kinetics(below 0.1 ppb within 10 min),and good applicability in complex matrices,which are better than those of most reported sulfur-containing adsorbents.Solid-state metallic gold with high purity can be effectively enriched due to the high recyclability and long-term stability of the composite.The material after adsorption can be further applied as a heterogeneous catalyst for water remediation due to the in situ generated gold nanoparticles by the redox reaction between Au(III)ions and the S-containing groups in the composites.
基金the National Key Research and Development Program of China(grant nos.2019YFB1503903,2019YFB1503904,and 2018YFB1501403)The Natural Science Foundation of Fujian Province of China(grant no.2019J06005).
文摘Higher alcohol synthesis(HAS)from syngas could efficiently alleviate the dependence on the traditional fossil resources.However,it is still challenging to construct high-performance HAS catalysts with satisfying selectivity,space–time yield(STY),and stability.Herein,we designed a diatomic catalyst by anchoring Co and Cu sites onto a hierarchical porous N-doped carbon matrix(Co/Cu–N–C).The Co/Cu–N–C is efficient for HAS and is among the best catalysts reported.With a COconversion of 81.7%,C2+OHselectivity could reach 58.5%with an outstanding C2+OH STY of 851.8 mg/g·h.We found that the N4–Co1 and Cu1–N4 showed an excellent synergistic effect.The adsorption of CO occurred on the Co site,and the surrounding nitrogen sites served as a hydrogen reservoir for the CO reduction reactions to form CHxCo.Meanwhile,the Cu sites stabilized a CHOCu species to interact with CHxCo,facilitating a barrier-free formation of C2 species,which is responsible for the high selectivity of higher alcohols.
基金supported by the National Key R&D Program of China(No.2018YFA0506900)National Natural Science Foundation of China(Nos.21635008 and 21621062)the Military Medicine and Healthy Major Project,China(No.AWS16J016)。
文摘Traditional matrix does not allow matrix-assisted laser desorption/ionization mass spectrometry(MALDI MS) to analyze volatile compounds,because volatile analytes may vaporize during the sample preparation process or in the high vacuum circumstance of ion source.Herein,we reported a Co and N doped porous carbon material(Co-NC) which were synthesized by pyrolysis of a Schiff base coordination compound.Co-NC could simultaneously act as adsorbent of volatile compounds and as matrix of MALDI MS,to provide the capability of MALDI MS to analyze volatile compounds.As adsorbent,Co-NC could stro ngly adsorb and enrich the volatile compounds in perfume and herbs,and hold them even in the high vacuum circumstance.On the other hand,Co-NC could absorb the energy of the laser,and then transfer the energy to the analyte for desorption and ionization of analyte in both negative and positive ionization modes.Additionally,the background interferences were avoided in the low-mass region(<500 Da) when using Co-NC as matrix,overcoming the challenges of MALDI MS analysis of small molecule compounds.In summary,Co-NC as matrix tremendously extended the application of MALDI MS.
