Regulating the location of the metal promoters plays a vital role in catalyst structure and its catalytic behavior during CO_(2)hydrogenation to higher alcohols.Herein,we selected the metal promoters with a precipitat...Regulating the location of the metal promoters plays a vital role in catalyst structure and its catalytic behavior during CO_(2)hydrogenation to higher alcohols.Herein,we selected the metal promoters with a precipitation pH similar to that of Cu^(2+)or Fe^(3+)to prepare a series of CuFe-based catalysts.Characterization results show that doping Al or Cr promoter,located with the Fe phase,suppressed the excessive carburization of the Fe phase and maintained an optimal proportion between Fe_(3)O_(4) and amorphous iron carbide(FeC_(x)),thus exhibiting superior catalytic activity and stability.In contrast,doping Zn or In promoter,located with the Cu phase,underwent a deeper carburization and formed more crys-talline FeC_(x),showing an inferior performance.The CuFeCr catalyst achieved the highest space-time yield of 330 mg g_(cat)^(-1)h^(-1)for higher alcohols among these catalysts.This study provides a novel strategy for opti-mizing the structure of the active phases for CO_(2)hydrogenation.展开更多
Excessive fossil fuel use has increased carbon dioxide(CO_(2)) emissions,driving climate change and ocean acidification.This review evaluates the potential of higher alcohols as fuels for carbon circularity,comparing ...Excessive fossil fuel use has increased carbon dioxide(CO_(2)) emissions,driving climate change and ocean acidification.This review evaluates the potential of higher alcohols as fuels for carbon circularity,comparing their properties,energy efficiency,and technology readiness with hydrogen,methane,and methanol.Higher alcohols,produced via CO_(2) hydrogenation,exhibit advantages such as liquid-phase storage,higher energy density,and safer handling.Additionally,their clean combustion produces fewer pollutants like CO and NO_(x).However,CO_(2) hydrogenation to higher alcohols faces challenges,including high energy demands,kinetic barriers,and immature production technologies,resulting in lower energy efficiency compared to H_(2),methane,and methanol.Higher alcohols,with their superior energy density and safety,hold promise as sustainable fuels,particularly when integrated with CO_(2) capture technologies.However,improvements in catalyst performance,process integration,and production scalability are critical for their widespread adoption.展开更多
A series of surfactant-modified CuCoMn-based catalysts were prepared for higher alco- hol synthesis from biomass-based syngas. Three typical surfactants, cetyltrimethylammonium bromide （CTAB）, sodium dodecyl sulfate...A series of surfactant-modified CuCoMn-based catalysts were prepared for higher alco- hol synthesis from biomass-based syngas. Three typical surfactants, cetyltrimethylammonium bromide （CTAB）, sodium dodecyl sulfate （SDS） and pluronic P123 triblock copolymer （EO20PO70EO20）, were employed. Compared to surfactant-free CuCoMn catalyst, CO conversion increased from 17.4% to 29.7% over SDS-modified CuCoMn catalyst, and the selectivity of higher alcohols increased from 22.0% to 41.2% over CTAB-modified catalyst. Besides, the proportions of higher alcohols in total alcohols increased over all surfactantmodified catalysts. The catalysts were characterized by N2 adsorption/desorption, XRD, XPS and IR analysis. The results showed that several more favorable features rendered the CTAB-modified CuCoMn catalyst to be suitable for higher alcohol production, such as the larger pore size, better crystallinity of CuCoMnO4 spinel. moderate surface atomic distribution and lower valence of metallic ions. In addition, it was verified that CTAB addition at the metal precipitation stage was beneficial to higher alcohol synthesis. Surfactant-induced modification provides a promising alternative method for catalyst improvement in synthesis of higher alcohols.展开更多
Activated carbon supported Mo-based catalysts were prepared and reduced under different activation atmospheres, including pure H2, syngas （H2/CO=2/1）, and pure CO. The cat- alysts structures were characterized by X-...Activated carbon supported Mo-based catalysts were prepared and reduced under different activation atmospheres, including pure H2, syngas （H2/CO=2/1）, and pure CO. The cat- alysts structures were characterized by X-ray diffraction , X-ray absorption fine structure, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The catalytic per- formance for the higher alcohol synthesis from syngas was tested. The pure H2 treatment showed a high reduction capacity. The presence of a large amount of metallic CoO and low valence state Mo^φ＋ （0〈φ〈2） on the surface suggested a super activity for the CO dissoci- ation and hydrogenation, which promoted hydrocarbons formation and reduced the alcohol selectivity. In contrast, the pure CO-reduced catalyst had a low reduction degree. The Mo and Co species at the catalyst mainly existed in the form of Mo^4＋ and Co^2＋. The syngas- reduced catalyst showed the highest activity and selectivity for the higher alcohols synthesis. We suggest that the syngas treatment had an appropriate reduction capacity that is between those of pure H2 and pure CO and led to the coexistence of multivalent Co species as well as the enrichment of Mo~＋ on the catalyst＇s surface. The synergistic effects between these active species provided a better cooperativity and equilibrium between the CO dissociation, hydrogenation and CO insertion and thus contributed beneficially to the formation of higher alcohols.展开更多
Cu-Fe composite oxides were prepared by co-precipitation method and tested for higher alcohol synthesis from syngas. The selectivity to C2＋OH and C6＋OH in alcohol distribution was very high while the methane product...Cu-Fe composite oxides were prepared by co-precipitation method and tested for higher alcohol synthesis from syngas. The selectivity to C2＋OH and C6＋OH in alcohol distribution was very high while the methane product fraction in hydrocarbon distribution was rather low, demonstrating a promising potential in higher alcohols synthesis from syngas. The distribution of alcohols and hydrocarbons approximately obeyed Anderson-Schulz-Flory distribution with similar chain growth probability, indicating alcohols and hydrocarbons derived from the same intermediates. The effects of Cu/Fe molar ratio, reaction temperature and gas hourly space velocity （GHSV） on catalytic performance were studied in detail. The sample with a Cu/Fe molar ratio of 10/1 exhibited the best catalytic performance. Higher reaction temperature accelerated water-gas-shift reaction and led to lower total alcohols selectivity. GHSV showed great effect on catalytic performance and higher GHSV increased the total alcohol selectivity, indicating there existed visible dehydration reaction of alcohol into hydrocarbon.展开更多
A series of carbon nanotubes-supported K-Co-Mo catalysts were prepared by a sol-gel method combined with incipient wetness impregnation. The catalyst structures were characterized by X-ray diffraction, N2 adsorption-d...A series of carbon nanotubes-supported K-Co-Mo catalysts were prepared by a sol-gel method combined with incipient wetness impregnation. The catalyst structures were characterized by X-ray diffraction, N2 adsorption-desorption, transmission electron microscopy and H2-TPD, and its catalytic performance toward the synthesis of higher alcohols from syngas was investigated. The as-prepared catalyst particles had a low crystallization degree and high dispersion on the outer and inner surface of CNTs. The uniform mesoporous structure of CNTs increased the diffusion rate of reactants and products, thus promoting the reaction conversion. Furthermore, the incorporation of CNTs support led to a high capability of hydrogen absorption and spillover and promoted the formation of alkyl group, which served as the key intermediate for the alcohol formation and carbon chain growth. Benefiting from these characteristics, the CNTs supported Mo-based catalyst showed the excellent catalytic performance for the higher alcohols synthesis as compared to the unsupported catalyst and activated carbon supported catalyst.展开更多
Cu-Co bi-metal catalysts derived from CuO/LaCoO3 perovskite structure were prepared by one-step citrate complexing method, and the structure evolution reaction from CuO/LaCoO3 to Cu-Co2C/La202CO3 under 1-12 pretreatme...Cu-Co bi-metal catalysts derived from CuO/LaCoO3 perovskite structure were prepared by one-step citrate complexing method, and the structure evolution reaction from CuO/LaCoO3 to Cu-Co2C/La202CO3 under 1-12 pretreatment was investigated by techniques of XRD, TPR and TEM. The results suggest that a much higher dispersion of copper significantly enhanced the reduction of cobalt, and a stronger interaction between copper and cobalt ions in LaCoO3 particles led to the formation of bi-metallic Cu-Co particles in the reduced catalysts and the enrichment of Co on the surface of bimetallic particles. The prepared catalysts were highly active and selective for the alcohol synthesis from syngas due to the presence of copper-modified C02C species.展开更多
Ethanol induced method was applied to prepare Cu-Fe-Zr catalysts for conversion of syngas to higher alcohols. The catalytic performance of the catalysts induced by ethanol was superior to that of the catalyst prepared...Ethanol induced method was applied to prepare Cu-Fe-Zr catalysts for conversion of syngas to higher alcohols. The catalytic performance of the catalysts induced by ethanol was superior to that of the catalyst prepared by the conventional precipitation method. Among various procedures for ethanol induced method, it was found that incorporation of ethanol in the precipitation process was the better. After incorporation of ethanol, the crystal size of CuO decreased and the reduction of copper species became easier. The better activity of Cu-Fe-Zr catalysts prepared by ethanol induced procedures was probably caused by the higher dispersion of Cu species.展开更多
Higher alcohols are key factors affecting sensory quality and post-drinking comfort of alcoholic beverages. A strategy combining solid-phase extraction and gas chromatography-mass spectrometry(SPE-GC-MS) was establish...Higher alcohols are key factors affecting sensory quality and post-drinking comfort of alcoholic beverages. A strategy combining solid-phase extraction and gas chromatography-mass spectrometry(SPE-GC-MS) was established to analyze the metabolism pattern of higher alcohols in rat plasma after gavage of 4 common alcoholic beverages including huangjiu, baijiu, wine and brandy. 7 mL of dichloromethane was determined as the optimal extraction condition, and 8 higher alcohols were precisely quantified with detection limits of 1.82-11.65 μg/L, recoveries of 89.07%-110.89% and fine repeatability. The fastest absorption and elimination rates of plasma total higher alcohols were observed in baijiu and huangjiu group, respectively, and the highest peak concentration was found in brandy group. Additionally, the metabolic rate of plasma isoamyl alcohol in huangjiu group was faster than that in wine group at the same intragastric administration dosage. This study may provide potential insight for evaluation of alcoholic beverage quality.展开更多
Direct conversion of syngas from those non-petroleum carbon resources to higher alcohols are very attractive due to the process simplicity with low energy consumption.However,the reaction always suffers from low yield...Direct conversion of syngas from those non-petroleum carbon resources to higher alcohols are very attractive due to the process simplicity with low energy consumption.However,the reaction always suffers from low yield as well as low selectivity.Herein,effective increase of higher alcohols proportion in the product is realized by direct conversion of syngas over electronically-modulated ZnO semiconductor via Cu doping.It is considered that the lower Fermi level and narrower band gap of catalysts by embedding Cu^(2+)into ZnO lattice could facilitate donor reaction by boosting the process for the reactants to obtain electrons on the catalyst surface for the formation of CH_(x) species and carbon chain growth,in which the Cu doping on ZnO lattice play important role in the promotion of CO adsorption.As a result,4 mol%Cu doped ZnO exhibits a highest C_(2+) OH/ROH fraction of 48.1%.Selectivity of catalysts from straight chain alcohol is better than from branch chain alcohol,which is different from promoted Cu/ZnO based catalyst.However,over-doping of Cu(7 mol%)on ZnO results in the aggregation Cu species on ZnO surface,leading to a sharp decrease of higher alcohols proportion to 3.2%.The results shed light on the nature that a direct correlation between semiconductor Fermi level and synthesis of higher alcohols,and the semiconductor-based catalysts mainly accelerate the hydrogenation reactions by enhancing thermally excited electron transfer.展开更多
Co-Cu-based catalysts are widely applied in higher alcohol synthesis (HAS) from synthesis gas. Although the nature of the active sites is still not fully understood, the formation of Co2C under HAS conditions seems to...Co-Cu-based catalysts are widely applied in higher alcohol synthesis (HAS) from synthesis gas. Although the nature of the active sites is still not fully understood, the formation of Co2C under HAS conditions seems to play a major role. A CO pretreatment procedure was developed allowing a systematic investigation of the influence of cobalt carbidization on the structural properties and catalytic performance of the catalysts. By exposing the catalyst to a CO-containing atmosphere prior to HAS, Co enrichment of the catalyst surface occurred followed by carbide formation. This surface modification decreased the formation of hydrocarbons and enhanced the formation of C2+OH. The catalyst pretreated with CO at 20 bar achieved the highest selectivity to ethanol and the lowest hydrocarbon selectivity.展开更多
In this paper, the molybdenum phosphide(MoP) catalysts(TPR-MoP and TPR-MoP-Pla) were prepared by the traditional method and the RF(radio frequency) thermal plasma technique respectively and characterized by x-ray diff...In this paper, the molybdenum phosphide(MoP) catalysts(TPR-MoP and TPR-MoP-Pla) were prepared by the traditional method and the RF(radio frequency) thermal plasma technique respectively and characterized by x-ray diffraction(XRD), x-ray photoelectron spectroscopy(XPS), transmission electron microscope(TEM), hydrogen temperature-programmed desorption(H_2-TPD) and carbon monoxide temperature-programmed desorption(CO-TPD) measurements,and their catalytic performance for HAS was evaluated. The results showed that the total and C_(2+) alcohols selectivity of the catalyst after plasma treatment(TPR-MoP-Pla) were enhanced.The enhanced catalytic performance could be related to more dislocation defects and the synergistic effect between Mo^(0–2+) and Mo^(4+) valence species in the TPR-MoP-Pla catalyst. In addition, this work suggests that thermal plasma treatment can be used as a new preparation technique for the synthesis of materials with rich species.展开更多
The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no ...The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no Co_9S_8 is found. The pure H_2 activated catalyst shows a higher intrinsic activity, especially the C_(2+) OH selectivity for the higher alcohol synthesis compared to the one activated by 5% H_2/N_2 atmosphere. The reason is attributed to that the pure H_2 activation more effectively suppresses the formation of Co_9S_8 and stabilizes the Co–Mo–S active phase during the reaction due to the formation of SH species.展开更多
Surface chemical properties of supports have an important influence on active sites and their catalytic behavio r.Here,we fabricated a series of cobalt-based catalysts supported by carbon layer-coated ordered mesoporo...Surface chemical properties of supports have an important influence on active sites and their catalytic behavio r.Here,we fabricated a series of cobalt-based catalysts supported by carbon layer-coated ordered mesoporous silica(OMS) composites for higher alcohol synthesis(HAS).The carbon layers were derived from different sources and uniformly coated on the porous surface of OMS.Combined with the characterization results of carbonized catalysts,it is demonstrated that the carbon layer-coated supports significantly enhanced the metal dispersion and increased the ratio of Co2+ to Co0 sites,which further increased the CO conversion and alcohols selectivity.Moreover,it is found that the catalytic activity changed in line with the amount of defects and surface oxygenic groups of carbon layers,which re sulted from the different carbon sources.The highest space time yield of C2+OH was 27.5 mmol gcat-1h-1)obtained by the catalyst coated with glucose-derived carbon layer.But the carbon source is not the key factor influencing the distribution of Co-Co2+ dual sites and shows little effect on selectivity in HAS.These results may guide for further design of carbon supported catalysts.展开更多
Excessive levels of higher alcohols have negative impacts on the quality of Baijiu.Understanding the key mi-croorganisms responsible for producing higher alcohols and their assembly processes is crucial for controllin...Excessive levels of higher alcohols have negative impacts on the quality of Baijiu.Understanding the key mi-croorganisms responsible for producing higher alcohols and their assembly processes is crucial for controlling higher alcohols in multi-species Baijiu fermentation.This study investigated the changes in volatile compounds,including higher alcohols,and microbial communities in the four fermentation cycles of Jiang-flavor Baijiu.Higher alcohols were the most abundant in the first cycle.Through metatranscriptomic and culture-dependent analysis,Saccharomyces cerevisiae and four non-Saccharomyces yeasts(Pichia kudriavzevii,Zygosaccharomyces bailii,Schizosaccharomyces pombe,and Torulaspora delbrueckii)were demonstrated to be the main contributors to higher alcohol(isobutanol,isoamylol,and 1-propanol)production,with S.cerevisiae producing the highest levels.A higher abundance of Saccharomyces resulted in the highest levels of higher alcohols in the first cycle.Moreover,our results revealed that yeast community was assembled from stochastic to deterministic processes with the increase of fermentation cycles,driven by lactic acid.These findings provide valuable insights into controlling higher alcohol production in Baijiu fermentation.展开更多
Spontaneous fermentation(SF)is a fermentation strategy used to enhance the aromatic complexity of wine.However,studies on the application of SF to enhance icewine aroma remain limited.In this study,headspace solid-pha...Spontaneous fermentation(SF)is a fermentation strategy used to enhance the aromatic complexity of wine.However,studies on the application of SF to enhance icewine aroma remain limited.In this study,headspace solid-phase microextraction and gas chromatography-mass spectrometry(HS-SPME-GC-MS),combined with an electronic nose(E-nose),were used to investigate the effect of SF on the aromatic profile of icewine.The results indicated that SF completed fermentation successfully and produced lower acetic acid levels compared to fermentation with commercial yeast(BV818).GC-MS analysis revealed that SF increased the total volatile compound content by 23.75%.SF increased the alcohol and ester contents by 43%and 35%,respectively.The key aroma compounds identified through odor activity value analysis included phenylethyl alcohol,ethyl decenoate,ethyl caprylate,ethyl laurate,2,4-di-tert-butylphenol,and octanoic acid.E-nose analysis showed that the differences between SF and BV818 were mainly in response to the sensors W1S and W2S.SF was strongly associated with key aromatic compounds,predominantly contributing to the honey,fruity,and floral notes.Consequently,SF more effectively transforms the raw green flavor of must into the characteristic aroma of icewine.These findings provide insights into the use of SF for developing icewines with unique regional characteristics.展开更多
Non-Saccharomyces yeasts have attracted great oenological interest due to their contribution to wine aroma,while the underlying mechanisms remain complex and insufficiently understood.To elucidate the potential mechan...Non-Saccharomyces yeasts have attracted great oenological interest due to their contribution to wine aroma,while the underlying mechanisms remain complex and insufficiently understood.To elucidate the potential mechanisms responsible for the high fruity esters production by P.kluyveri PK-19,a non-Saccharomyces yeast strain known for its aroma production,the nitrogen assimilation profile,fermentation capacity,and volatile production were compared with those of three other yeast strains,namely Saccharomyces cerevisiae SC-19,Pichia fermentans Z9Y-3,and Hanseniaspora uvarum Yun268.Despite the intermediate fermentation capacity,P.kluyveri PK-19 showed strong nitrogen consumption and rapid uptake of Ehrlich pathway-related amino acids during the early stages of alcoholic fermentation.Moreover,P.kluyveri demonstrated a high efficiency in converting Ehrlich pathway-related amino acids into their corresponding higher alcohol acetates(HAAs),indicating an enhanced ability to synthesize HAAs from Ehrlich pathway precursors.The rapid assimilation of Ehrlich pathway-related amino acids and efficient transformation to HAAs potentially contributed to the high production of HAAs in P.kluyveri PK-19.These results suggest that supplementing P.kluyveri-involved fermentation with Ehrlich pathway-related amino acids can increase HAA production and modify wine aroma profiles.展开更多
CO_(2)hydrogenation to higher alcohols(C^(2+)OH) is an effective way to realize carbon recycling, which can not only reduce the CO_(2)amounts in atmosphere and mitigate the greenhouse effect, but also provides a new r...CO_(2)hydrogenation to higher alcohols(C^(2+)OH) is an effective way to realize carbon recycling, which can not only reduce the CO_(2)amounts in atmosphere and mitigate the greenhouse effect, but also provides a new route to synthesize important chemicals.However, this process is a challenge because the inert CO_(2)molecule is difficult to be activated and undergo C–C coupling. The key to achieve selective conversion of CO_(2)to C^(2+)OH is to design high-performance catalytic systems and unravel the reaction mechanism. In this review, we report several typical CO_(2)hydrogenation-to-C^(2+)OH catalyst materials, including noble-metal catalysts, Cu-based catalysts, Co-based catalysts and Mo-based catalysts, and evaluate the effects of various promoters on the catalytic performance and reaction mechanism. It will provide not only fundamental insights into the CO_(2)hydrogenation-to-C^(2+)OH reaction mechanism, but also guidance for the development of related high-performance catalysts.展开更多
High alcohols are important flavor compounds in alcoholic beverages,but high concentration of high alcohols is harmful to human health.Higher alcohol synthesis pathways in brewing microorganisms have been investigated...High alcohols are important flavor compounds in alcoholic beverages,but high concentration of high alcohols is harmful to human health.Higher alcohol synthesis pathways in brewing microorganisms have been investigated,but the interactions between key genes remain to be explored,especially in industrial strains of Saccharomyces cerevisiae.The PDC1 gene was considered to be the main encoding gene ofα-keto acid decarboxylase,and its deletion resulted in a 92.23%increase in isobutanol production and a 14.89%decrease in isoamyl alcohol production.Transcriptome sequencing was used to explore the effects of PDC1 gene deletion on global gene transcription levels,and deletion strategies were utilized to verify the effects of differential genes on higher alcohol production.Deletion of differential gene HMLALPHA2 increased isobutanol production by 26.23%,and decreased isoamyl alcohol and 2-phenylethanol production by 30.31%and 22.35%,respectively.The THI2,THI4,THI20 genes were proved to be related to n-propanol synthesis.In addition,HMRA2 and SIR3 genes were found to influence isoamyl alcohol synthesis pathways,and their deletion increased isoamyl alcohol production by 25.18%and 21.76%.Our discovery of new target genes is useful for elucidating the molecular mechanisms of higher alcohols and the construction of novel low-producing higher alcohol strains.展开更多
基金financially supported by the National Key R&D Program of China (2023YFB4104501)the National Natural Science Foundation of China (22372165)+2 种基金the Liaoning Binhai Laboratory (LBLA-2024-01)the Grant. YLU-DNL Fund (2023001)DICP (Grant: DICP I202457)
文摘Regulating the location of the metal promoters plays a vital role in catalyst structure and its catalytic behavior during CO_(2)hydrogenation to higher alcohols.Herein,we selected the metal promoters with a precipitation pH similar to that of Cu^(2+)or Fe^(3+)to prepare a series of CuFe-based catalysts.Characterization results show that doping Al or Cr promoter,located with the Fe phase,suppressed the excessive carburization of the Fe phase and maintained an optimal proportion between Fe_(3)O_(4) and amorphous iron carbide(FeC_(x)),thus exhibiting superior catalytic activity and stability.In contrast,doping Zn or In promoter,located with the Cu phase,underwent a deeper carburization and formed more crys-talline FeC_(x),showing an inferior performance.The CuFeCr catalyst achieved the highest space-time yield of 330 mg g_(cat)^(-1)h^(-1)for higher alcohols among these catalysts.This study provides a novel strategy for opti-mizing the structure of the active phases for CO_(2)hydrogenation.
基金the financial support from the National Natural Science Foundation of China (U22B20148,22208143,and 22278204)the International Science and Technology Cooperation Project of the Innovative Supporting Plan from the Jiangsu Provincial Department of Science and Technology (BZ2022040)+1 种基金the State Key Laboratory of Materials-Oriented Chemical Engineering (ZK202101,SKL-MCE-24A09,and the Open Project SKL-MCE-23B)support from the China National Petroleum Corporation。
文摘Excessive fossil fuel use has increased carbon dioxide(CO_(2)) emissions,driving climate change and ocean acidification.This review evaluates the potential of higher alcohols as fuels for carbon circularity,comparing their properties,energy efficiency,and technology readiness with hydrogen,methane,and methanol.Higher alcohols,produced via CO_(2) hydrogenation,exhibit advantages such as liquid-phase storage,higher energy density,and safer handling.Additionally,their clean combustion produces fewer pollutants like CO and NO_(x).However,CO_(2) hydrogenation to higher alcohols faces challenges,including high energy demands,kinetic barriers,and immature production technologies,resulting in lower energy efficiency compared to H_(2),methane,and methanol.Higher alcohols,with their superior energy density and safety,hold promise as sustainable fuels,particularly when integrated with CO_(2) capture technologies.However,improvements in catalyst performance,process integration,and production scalability are critical for their widespread adoption.
基金V. ACKNOWLEDGMENTS This work was supported by the National Key Basic Program of China （No.2013CB228105）, and the National Natural Science Foundation of China （No.51161140331）. The assistance of Song-bai Qiu and Tong-qi Ye from University of Science and Technology of China is gratefully acknowledged.
文摘A series of surfactant-modified CuCoMn-based catalysts were prepared for higher alco- hol synthesis from biomass-based syngas. Three typical surfactants, cetyltrimethylammonium bromide （CTAB）, sodium dodecyl sulfate （SDS） and pluronic P123 triblock copolymer （EO20PO70EO20）, were employed. Compared to surfactant-free CuCoMn catalyst, CO conversion increased from 17.4% to 29.7% over SDS-modified CuCoMn catalyst, and the selectivity of higher alcohols increased from 22.0% to 41.2% over CTAB-modified catalyst. Besides, the proportions of higher alcohols in total alcohols increased over all surfactantmodified catalysts. The catalysts were characterized by N2 adsorption/desorption, XRD, XPS and IR analysis. The results showed that several more favorable features rendered the CTAB-modified CuCoMn catalyst to be suitable for higher alcohol production, such as the larger pore size, better crystallinity of CuCoMnO4 spinel. moderate surface atomic distribution and lower valence of metallic ions. In addition, it was verified that CTAB addition at the metal precipitation stage was beneficial to higher alcohol synthesis. Surfactant-induced modification provides a promising alternative method for catalyst improvement in synthesis of higher alcohols.
文摘Activated carbon supported Mo-based catalysts were prepared and reduced under different activation atmospheres, including pure H2, syngas （H2/CO=2/1）, and pure CO. The cat- alysts structures were characterized by X-ray diffraction , X-ray absorption fine structure, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The catalytic per- formance for the higher alcohol synthesis from syngas was tested. The pure H2 treatment showed a high reduction capacity. The presence of a large amount of metallic CoO and low valence state Mo^φ＋ （0〈φ〈2） on the surface suggested a super activity for the CO dissoci- ation and hydrogenation, which promoted hydrocarbons formation and reduced the alcohol selectivity. In contrast, the pure CO-reduced catalyst had a low reduction degree. The Mo and Co species at the catalyst mainly existed in the form of Mo^4＋ and Co^2＋. The syngas- reduced catalyst showed the highest activity and selectivity for the higher alcohols synthesis. We suggest that the syngas treatment had an appropriate reduction capacity that is between those of pure H2 and pure CO and led to the coexistence of multivalent Co species as well as the enrichment of Mo~＋ on the catalyst＇s surface. The synergistic effects between these active species provided a better cooperativity and equilibrium between the CO dissociation, hydrogenation and CO insertion and thus contributed beneficially to the formation of higher alcohols.
基金the State Key Fundamental Research Program(Ministry of Science and Technology of China,No.2011CBA00501)Shanghai Municipal Science and Technology Commission,China(Grant No:11DZ1200300)the Foundation of State Key Laboratory of Coal Conversion(Grant No:1112610)
文摘Cu-Fe composite oxides were prepared by co-precipitation method and tested for higher alcohol synthesis from syngas. The selectivity to C2＋OH and C6＋OH in alcohol distribution was very high while the methane product fraction in hydrocarbon distribution was rather low, demonstrating a promising potential in higher alcohols synthesis from syngas. The distribution of alcohols and hydrocarbons approximately obeyed Anderson-Schulz-Flory distribution with similar chain growth probability, indicating alcohols and hydrocarbons derived from the same intermediates. The effects of Cu/Fe molar ratio, reaction temperature and gas hourly space velocity （GHSV） on catalytic performance were studied in detail. The sample with a Cu/Fe molar ratio of 10/1 exhibited the best catalytic performance. Higher reaction temperature accelerated water-gas-shift reaction and led to lower total alcohols selectivity. GHSV showed great effect on catalytic performance and higher GHSV increased the total alcohol selectivity, indicating there existed visible dehydration reaction of alcohol into hydrocarbon.
基金This work was supported by National Natural Science Foundation of China （No.21673214）.
文摘A series of carbon nanotubes-supported K-Co-Mo catalysts were prepared by a sol-gel method combined with incipient wetness impregnation. The catalyst structures were characterized by X-ray diffraction, N2 adsorption-desorption, transmission electron microscopy and H2-TPD, and its catalytic performance toward the synthesis of higher alcohols from syngas was investigated. The as-prepared catalyst particles had a low crystallization degree and high dispersion on the outer and inner surface of CNTs. The uniform mesoporous structure of CNTs increased the diffusion rate of reactants and products, thus promoting the reaction conversion. Furthermore, the incorporation of CNTs support led to a high capability of hydrogen absorption and spillover and promoted the formation of alkyl group, which served as the key intermediate for the alcohol formation and carbon chain growth. Benefiting from these characteristics, the CNTs supported Mo-based catalyst showed the excellent catalytic performance for the higher alcohols synthesis as compared to the unsupported catalyst and activated carbon supported catalyst.
基金supported by the Program for Scientific Research Innovation Team in Colleges and Universities of Shandong Provincethe Ph.D.Programs Foundation of Liaocheng University(No.31805)the NSF of China(21263011,21376170)
文摘Cu-Co bi-metal catalysts derived from CuO/LaCoO3 perovskite structure were prepared by one-step citrate complexing method, and the structure evolution reaction from CuO/LaCoO3 to Cu-Co2C/La202CO3 under 1-12 pretreatment was investigated by techniques of XRD, TPR and TEM. The results suggest that a much higher dispersion of copper significantly enhanced the reduction of cobalt, and a stronger interaction between copper and cobalt ions in LaCoO3 particles led to the formation of bi-metallic Cu-Co particles in the reduced catalysts and the enrichment of Co on the surface of bimetallic particles. The prepared catalysts were highly active and selective for the alcohol synthesis from syngas due to the presence of copper-modified C02C species.
基金Natural Science Foundation of State Key Laboratory of Coal Conversion(No09-610)
文摘Ethanol induced method was applied to prepare Cu-Fe-Zr catalysts for conversion of syngas to higher alcohols. The catalytic performance of the catalysts induced by ethanol was superior to that of the catalyst prepared by the conventional precipitation method. Among various procedures for ethanol induced method, it was found that incorporation of ethanol in the precipitation process was the better. After incorporation of ethanol, the crystal size of CuO decreased and the reduction of copper species became easier. The better activity of Cu-Fe-Zr catalysts prepared by ethanol induced procedures was probably caused by the higher dispersion of Cu species.
基金supported by the National Natural Science Foundation of China(22138004 and 32001828).
文摘Higher alcohols are key factors affecting sensory quality and post-drinking comfort of alcoholic beverages. A strategy combining solid-phase extraction and gas chromatography-mass spectrometry(SPE-GC-MS) was established to analyze the metabolism pattern of higher alcohols in rat plasma after gavage of 4 common alcoholic beverages including huangjiu, baijiu, wine and brandy. 7 mL of dichloromethane was determined as the optimal extraction condition, and 8 higher alcohols were precisely quantified with detection limits of 1.82-11.65 μg/L, recoveries of 89.07%-110.89% and fine repeatability. The fastest absorption and elimination rates of plasma total higher alcohols were observed in baijiu and huangjiu group, respectively, and the highest peak concentration was found in brandy group. Additionally, the metabolic rate of plasma isoamyl alcohol in huangjiu group was faster than that in wine group at the same intragastric administration dosage. This study may provide potential insight for evaluation of alcoholic beverage quality.
基金support by the National Natural Science Foundation of China(21975173 and 21776195)the fund for Shanxi“1331 project”and Major Projects of Shanxi Province(201803D121043).
文摘Direct conversion of syngas from those non-petroleum carbon resources to higher alcohols are very attractive due to the process simplicity with low energy consumption.However,the reaction always suffers from low yield as well as low selectivity.Herein,effective increase of higher alcohols proportion in the product is realized by direct conversion of syngas over electronically-modulated ZnO semiconductor via Cu doping.It is considered that the lower Fermi level and narrower band gap of catalysts by embedding Cu^(2+)into ZnO lattice could facilitate donor reaction by boosting the process for the reactants to obtain electrons on the catalyst surface for the formation of CH_(x) species and carbon chain growth,in which the Cu doping on ZnO lattice play important role in the promotion of CO adsorption.As a result,4 mol%Cu doped ZnO exhibits a highest C_(2+) OH/ROH fraction of 48.1%.Selectivity of catalysts from straight chain alcohol is better than from branch chain alcohol,which is different from promoted Cu/ZnO based catalyst.However,over-doping of Cu(7 mol%)on ZnO results in the aggregation Cu species on ZnO surface,leading to a sharp decrease of higher alcohols proportion to 3.2%.The results shed light on the nature that a direct correlation between semiconductor Fermi level and synthesis of higher alcohols,and the semiconductor-based catalysts mainly accelerate the hydrogenation reactions by enhancing thermally excited electron transfer.
基金funded by the Federal Ministry of Education and Research(Bundesministerium für Bildung und Forschung,BMBF,Verbundvorhaben Carbon2Chem■,FKZ:03EK3041)
文摘Co-Cu-based catalysts are widely applied in higher alcohol synthesis (HAS) from synthesis gas. Although the nature of the active sites is still not fully understood, the formation of Co2C under HAS conditions seems to play a major role. A CO pretreatment procedure was developed allowing a systematic investigation of the influence of cobalt carbidization on the structural properties and catalytic performance of the catalysts. By exposing the catalyst to a CO-containing atmosphere prior to HAS, Co enrichment of the catalyst surface occurred followed by carbide formation. This surface modification decreased the formation of hydrocarbons and enhanced the formation of C2+OH. The catalyst pretreated with CO at 20 bar achieved the highest selectivity to ethanol and the lowest hydrocarbon selectivity.
基金the National Natural Science Foundation of China (No. 21476118)Major Projects of Inner Mongolia Natural Science Foundation (2019ZD01)+2 种基金Inner Mongolia Science & Technology Plan (Nos. 30500515330303)Inner Mongolia Major Science and Technology Project (No. 21300-5193901)Prairie Excellence Innovation and Entrepreneurial Team of Inner Mongolia (No. 12000-12102413)。
文摘In this paper, the molybdenum phosphide(MoP) catalysts(TPR-MoP and TPR-MoP-Pla) were prepared by the traditional method and the RF(radio frequency) thermal plasma technique respectively and characterized by x-ray diffraction(XRD), x-ray photoelectron spectroscopy(XPS), transmission electron microscope(TEM), hydrogen temperature-programmed desorption(H_2-TPD) and carbon monoxide temperature-programmed desorption(CO-TPD) measurements,and their catalytic performance for HAS was evaluated. The results showed that the total and C_(2+) alcohols selectivity of the catalyst after plasma treatment(TPR-MoP-Pla) were enhanced.The enhanced catalytic performance could be related to more dislocation defects and the synergistic effect between Mo^(0–2+) and Mo^(4+) valence species in the TPR-MoP-Pla catalyst. In addition, this work suggests that thermal plasma treatment can be used as a new preparation technique for the synthesis of materials with rich species.
基金supported by the National Natural Science Foundation of China(21673214,U1732272)
文摘The nanosheets structured K–Co–MoS_2 catalyst was prepared through a one-step hydrothermal synthesis combined with the wetness impregnation. The fresh catalyst has a high dispersion of Co–Mo–S active phase and no Co_9S_8 is found. The pure H_2 activated catalyst shows a higher intrinsic activity, especially the C_(2+) OH selectivity for the higher alcohol synthesis compared to the one activated by 5% H_2/N_2 atmosphere. The reason is attributed to that the pure H_2 activation more effectively suppresses the formation of Co_9S_8 and stabilizes the Co–Mo–S active phase during the reaction due to the formation of SH species.
基金support from the National Natural Science Foundation of China(Nos.U1462204,21706184)the National Postdoctoral Program for Innovative Talents of China(No.BX20180221)。
文摘Surface chemical properties of supports have an important influence on active sites and their catalytic behavio r.Here,we fabricated a series of cobalt-based catalysts supported by carbon layer-coated ordered mesoporous silica(OMS) composites for higher alcohol synthesis(HAS).The carbon layers were derived from different sources and uniformly coated on the porous surface of OMS.Combined with the characterization results of carbonized catalysts,it is demonstrated that the carbon layer-coated supports significantly enhanced the metal dispersion and increased the ratio of Co2+ to Co0 sites,which further increased the CO conversion and alcohols selectivity.Moreover,it is found that the catalytic activity changed in line with the amount of defects and surface oxygenic groups of carbon layers,which re sulted from the different carbon sources.The highest space time yield of C2+OH was 27.5 mmol gcat-1h-1)obtained by the catalyst coated with glucose-derived carbon layer.But the carbon source is not the key factor influencing the distribution of Co-Co2+ dual sites and shows little effect on selectivity in HAS.These results may guide for further design of carbon supported catalysts.
基金supported by the National Natural Science Foundation of China(NSFC)(grants 32172176,32201981)National First-class Discipline Program of Light Industry Technology and Engineering(QGJC20230301).
文摘Excessive levels of higher alcohols have negative impacts on the quality of Baijiu.Understanding the key mi-croorganisms responsible for producing higher alcohols and their assembly processes is crucial for controlling higher alcohols in multi-species Baijiu fermentation.This study investigated the changes in volatile compounds,including higher alcohols,and microbial communities in the four fermentation cycles of Jiang-flavor Baijiu.Higher alcohols were the most abundant in the first cycle.Through metatranscriptomic and culture-dependent analysis,Saccharomyces cerevisiae and four non-Saccharomyces yeasts(Pichia kudriavzevii,Zygosaccharomyces bailii,Schizosaccharomyces pombe,and Torulaspora delbrueckii)were demonstrated to be the main contributors to higher alcohol(isobutanol,isoamylol,and 1-propanol)production,with S.cerevisiae producing the highest levels.A higher abundance of Saccharomyces resulted in the highest levels of higher alcohols in the first cycle.Moreover,our results revealed that yeast community was assembled from stochastic to deterministic processes with the increase of fermentation cycles,driven by lactic acid.These findings provide valuable insights into controlling higher alcohol production in Baijiu fermentation.
基金supported by the National Natural Science Foundation of China(Grant No.:32172333)。
文摘Spontaneous fermentation(SF)is a fermentation strategy used to enhance the aromatic complexity of wine.However,studies on the application of SF to enhance icewine aroma remain limited.In this study,headspace solid-phase microextraction and gas chromatography-mass spectrometry(HS-SPME-GC-MS),combined with an electronic nose(E-nose),were used to investigate the effect of SF on the aromatic profile of icewine.The results indicated that SF completed fermentation successfully and produced lower acetic acid levels compared to fermentation with commercial yeast(BV818).GC-MS analysis revealed that SF increased the total volatile compound content by 23.75%.SF increased the alcohol and ester contents by 43%and 35%,respectively.The key aroma compounds identified through odor activity value analysis included phenylethyl alcohol,ethyl decenoate,ethyl caprylate,ethyl laurate,2,4-di-tert-butylphenol,and octanoic acid.E-nose analysis showed that the differences between SF and BV818 were mainly in response to the sensors W1S and W2S.SF was strongly associated with key aromatic compounds,predominantly contributing to the honey,fruity,and floral notes.Consequently,SF more effectively transforms the raw green flavor of must into the characteristic aroma of icewine.These findings provide insights into the use of SF for developing icewines with unique regional characteristics.
基金funded by the Key Research and Development Project of Xinjiang Uygur Autonomous Region(2023B02027-1-4)the Shaanxi Provincial Science and Technology Project for Innovation Team(2023-CX-TD-59)+1 种基金the Fundamental Research Funds of the Central Universities of Ministry of the Education of China(XYTD2023-12)the Key Project for Experimental Technology Innovation of Northwest A&F University(A1070023104).
文摘Non-Saccharomyces yeasts have attracted great oenological interest due to their contribution to wine aroma,while the underlying mechanisms remain complex and insufficiently understood.To elucidate the potential mechanisms responsible for the high fruity esters production by P.kluyveri PK-19,a non-Saccharomyces yeast strain known for its aroma production,the nitrogen assimilation profile,fermentation capacity,and volatile production were compared with those of three other yeast strains,namely Saccharomyces cerevisiae SC-19,Pichia fermentans Z9Y-3,and Hanseniaspora uvarum Yun268.Despite the intermediate fermentation capacity,P.kluyveri PK-19 showed strong nitrogen consumption and rapid uptake of Ehrlich pathway-related amino acids during the early stages of alcoholic fermentation.Moreover,P.kluyveri demonstrated a high efficiency in converting Ehrlich pathway-related amino acids into their corresponding higher alcohol acetates(HAAs),indicating an enhanced ability to synthesize HAAs from Ehrlich pathway precursors.The rapid assimilation of Ehrlich pathway-related amino acids and efficient transformation to HAAs potentially contributed to the high production of HAAs in P.kluyveri PK-19.These results suggest that supplementing P.kluyveri-involved fermentation with Ehrlich pathway-related amino acids can increase HAA production and modify wine aroma profiles.
基金he financial supports of the National Key R&D Program of China (2023YFB4103700)National Natural Science Foundation of China (21991090, 21991092, 22272195, 22322208, U1910203, U22A20431)+2 种基金Natural Science Foundation of Shanxi Province of China (202203021224009)Innovation Foundation of Institute of Coal Chemistry, Chinese Academy of Sciences (SCJC-DT-2023-06)Youth Innovation Promotion Association CAS (2021172)。
文摘CO_(2)hydrogenation to higher alcohols(C^(2+)OH) is an effective way to realize carbon recycling, which can not only reduce the CO_(2)amounts in atmosphere and mitigate the greenhouse effect, but also provides a new route to synthesize important chemicals.However, this process is a challenge because the inert CO_(2)molecule is difficult to be activated and undergo C–C coupling. The key to achieve selective conversion of CO_(2)to C^(2+)OH is to design high-performance catalytic systems and unravel the reaction mechanism. In this review, we report several typical CO_(2)hydrogenation-to-C^(2+)OH catalyst materials, including noble-metal catalysts, Cu-based catalysts, Co-based catalysts and Mo-based catalysts, and evaluate the effects of various promoters on the catalytic performance and reaction mechanism. It will provide not only fundamental insights into the CO_(2)hydrogenation-to-C^(2+)OH reaction mechanism, but also guidance for the development of related high-performance catalysts.
基金Supported by Tianjin Science and Technology Project(22ZYJDSS00050)Project Program of Key Laboratory of Industrial Fermentation Microbiology,Ministry of Education,and Tianjin Key Laboratory of Industrial Microbiology,China(No.2020KF002)+2 种基金National Natural Science Foundation of China(31771969)Liquor Making Biological Technology and Application of key laboratory of Sichuan Province(NJ2020-02)Project Program of Tianjin Graduate Research and Innovation(No.2020YJSB124).
文摘High alcohols are important flavor compounds in alcoholic beverages,but high concentration of high alcohols is harmful to human health.Higher alcohol synthesis pathways in brewing microorganisms have been investigated,but the interactions between key genes remain to be explored,especially in industrial strains of Saccharomyces cerevisiae.The PDC1 gene was considered to be the main encoding gene ofα-keto acid decarboxylase,and its deletion resulted in a 92.23%increase in isobutanol production and a 14.89%decrease in isoamyl alcohol production.Transcriptome sequencing was used to explore the effects of PDC1 gene deletion on global gene transcription levels,and deletion strategies were utilized to verify the effects of differential genes on higher alcohol production.Deletion of differential gene HMLALPHA2 increased isobutanol production by 26.23%,and decreased isoamyl alcohol and 2-phenylethanol production by 30.31%and 22.35%,respectively.The THI2,THI4,THI20 genes were proved to be related to n-propanol synthesis.In addition,HMRA2 and SIR3 genes were found to influence isoamyl alcohol synthesis pathways,and their deletion increased isoamyl alcohol production by 25.18%and 21.76%.Our discovery of new target genes is useful for elucidating the molecular mechanisms of higher alcohols and the construction of novel low-producing higher alcohol strains.
