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Biomass valorization via electrocatalytic carbon–carbon bond cleavage

Journal of Energy Chemistry 2024年第4期91卷 542-578页

作者： Keping Wang Zhenyan Guo Min Zhou Ying Yang Lanyun Li Hu Li Rafael Luque Shunmugavel Saravanamurugan National Key Laboratory of Green Pesticide Key Laboratory of Green Pesticide&Agricultural BioengineeringMinistry of EducationState-Local Joint Laboratory for Comprehensive Utilization of BiomassCenter for R&D of Fine ChemicalsGuizhou UniversityGuiyang 550025GuizhouChina departamento de quimica organica Universidad de CordobaCampus de RabanalesEdificio Marie Curie(C-3)Ctra Nnal IVKm.396E-14014 CordobaSpain Laboratory of Bioproduct Chemistry Centre of Innovative and Applied Bioprocessing(CIAB)Mohali 140306PunjabIndia

Renewable electrocatalytic upgrading of biomass feedstocks into valuable chemicals is one of the promising strategies to relieve the pressure of traditional energy-based *** electrocatalytic carbon–carbon bond cleavage of high selectivity,various functionalized molecules,such as organic acids,amides,esters,and nitriles,have great potential to be accessed from ***,it has merely received finite concerns and interests in the *** review first showcases the research progress on the electrocatalytic conversion of lipid/sugar-and lignin-derived molecules(e.g.,glycerol,mesoerythritol,xylose,glucose,1-phenylethanol,and cyclohexanol)into organic acids via specific carbon–carbon bond scission processes,with focus on disclosing reaction mechanisms,recognizing actual active species,and collecting feasible modification *** the guidance of further extensive studies on biomass valorization,organic transformations via a variety of reactions,including decarboxylation,ring-opening,rearrangement,reductive hydrogenation,and carboxylation,are also disclosed for the construction of similar carbon skeletons/*** remaining challenges,prospective applications,and future objectives in terms of biomass conversion are also *** review is expected to provide references to develop renewed electrocatalytic carbon–carbon bond cleavage transformation paths/strategies for biomass upgrading.

关键词： Electrocatalysis Biomass conversion Carbon-carbon bond cleavage Organic acids

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Carbon dioxide fixation into cyclic carbonates at room temperature catalyzed by heteroscorpionate aluminum complexes

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Green Chemical Engineering 2022年第3期3卷 280-287页

作者： Felipe de la Cruz-Martinez Jose A.Castro-Osma Agustin Lara-Sanchez Universidad de Castilla-La Mancha Departamento de Quimica InorganicaOrganica y Bioquimica-Centro de Innovacion en Quimica Avanzada(ORFEO-CINQA)Facultad de Ciencias y Tecnologias QuimicasCiudad Real13071Spain Instituto de Investigaciones quimicas(IIQ) Departamento de Quimica Inorganica and Centro de Innovacion en Quimica Avanzada(ORFEO-CINQA)Consejo Superior de Investigaciones Cientificas(CSIC)and University of SevillaSevilla41092Spain Universidad de Castilla-La Mancha Departamento de Quimica InorganicaOrganica y Bioquimica-Centro de Innovacion en Quimica Avanzada(ORFEO-CINQA)Facultad de FarmaciaAlbacete02071Spain

Novel mono-and bimetallic scorpionate aluminum compounds have been designed and characterized by spec-troscopic *** organometallics complexes,in combination with tetrabutylammonium bromide as cocatalyst,displayed good catalytic activity for the cycloaddition of styrene oxide and CO_(2) under ambient *** the compounds tested,monometallic complex 3 featuring diethylamino groups showed the highest catalytic *** catalytic system catalyzed the formation of cyclic carbonate products from their corresponding epoxides at room temperature and 1 bar of CO_(2) pressure in the absence of a solvent in good yields and excellent selectivities.

关键词： CO_(2) Epoxides Cyclic carbonates Aluminum complexes

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Synthesis of a pair of novel receptors and their properties of enantioselective recognition for amino acid zwitterions

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Chinese Journal of Chemistry 1999年第5期17卷 508-515,427页

作者：陆国元刘芳何卫江王志林胡宏纹 department of Chemistry Nanjing University Nanjing Jiangsu 210)93 China departament de quimica organica Universidad Autonoma de Madrid Madrid 28049 Spain

A pair of artificial enantiotopic receptors la and lb composed of (S,S) or (R,R) chiral bicyclic guanidinium, azacrown ether and (t-butyldiphenylsilyloxy) methyl group for amino acid zwitterions have been synthesized. The liquid-liquid competition experiments and 1 H NMR studies indicate that the receptor 1a with (S, S) configuration and 1b with (R,R) configuration selectively recognize L- and D-aromatic amino acids & respectively.

关键词： Enantioselective Recognition amino acid zwitterions artificial receptor

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Minimizing sperm oxidative stress using nanotechnology for breeding programs in rams

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Journal of Animal Science and Biotechnology 2023年第6期14卷 2395-2410页

作者： Alejandro Jurado‑Campos Pedro Javier Soria‑Meneses Maria Arenas‑Moreira Carlos Alonso‑Moreno Virginia Rodriguez‑Robledo Ana Josefa Soler Jose Julian Garde Maria del Rocio Fernandez‑Santos SaBio IREC(CSIC-UCLM-JCCM) Campus UniversitarioS/N02071 AlbaceteSpain. departamento de quimica Inorganica Organica Y Bioquimica‑Centro de Innovacion en Quimica Avanzada(ORFEO‑CINQA)Facultad de FarmaciaUniversidad de Castilla-La Mancha02008 AlbaceteSpain. Centro Regional de Investigacion Biomedicas Unidad nanoDrugUniversidad de Castilla-La Mancha02008 AlbaceteSpain. Facultad de Farmacia Universidad de Castilla La Mancha02071 AlbaceteSpain.

Background Artificial insemination(AI)is a routine breeding technology in animal ***,the temperature-sensitive nature and short fertile lifespan of ram sperm samples hamper its use in *** this sense,nanotechnology is an interesting tool to improve sperm protection due to the development of nanomaterials for AI,which could be used as delivery *** this work,we explored the feasibility of vitamin E nanoemulsion(NE)for improving sperm quality during *** With the aim of evaluating this proposal,ejaculates of 7 mature rams of Manchega breed were collected by artificial vagina and extended to 60×10^(6)spz/mL in *** containing control and NE(12 mmol/L)with and without exogenous oxidative stress(100μmol/L Fe2+/ascorbate)were stored at 22 and 15℃and motility(CASA),viability(YO-PRO/PI),acrosomal integrity(PNA-FITC/PI),mitochondrial membrane potential(Mitotracker deep Red 633),lipoperoxidation(C11 BODIPY 581/591),intracellular reactive oxygen species(ROS)production and DNA status(SCSAR)monitored during 96 *** results show that NE could be used to maintain ram spermatozoa during transport at 15 and 22℃for up to 96 h,with no appreciable loss of kinematic and physiological characteristics of freshly collected *** The storage of ram spermatozoa in liquid form for 2-5 d with vitamin E nanoemulsions may lead more flexibility to breeders in AI *** view of the potential and high versatility of these nanodevices,further studies are being carried out to assess the proposed sperm preservation medium on fertility after artificial insemination.

关键词： Breeding technology Nanoemulsions Nanotechnology Sperm oxidative stress Vitamin E

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Solid-state synthesis of LnOCl/Ln_2O_3(Ln=Eu, Nd) by using chitosan and PS-co-P4VP as polymeric supports

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Journal of Rare Earths 2018年第12期36卷 1326-1332页

作者： C.Diaz D.Carrillo R.de la Campa A.Presa Soto M.L.Valenzuela departamento de quimica Facultad de Quimica Universidad de Chile departamento de quimica organica e Inorganica (IUQOEM) Facultad de Quimica Universidad de Oviedo Universidad Autonoma de Chile Facultad de Ingenieria Instituto de Ciendas Quimicas Aplicadas Inorganic Chemistry and Molecular Material Center

A series of lanthanide materials of type LnOCl or Ln2O3(Ln = Eu, Nd) were successfully prepared via a convenient and straightforward two-step procedure. Firstly, and by using chitosan and PS-co-P4 VP as polymeric supports, macromolecular complexes of type chitosan ·LnCl3and PS-co-P4 VP·LnCl3 were prepared. These macro molecular complexes were treated in solid state at 800 ℃ under air, leading to the corresponding LnOCl or Ln2O3materials(Ln = Eu, Nd) with moderate to good yields. The nature of the asprepared lanthanide materials(LnOCl and/or Ln2O3) is strongly influenced by the polymeric template(i.e.,chitosan or PS-co-P4 VP), the lanthanide salt precursor, and the polymer/lanthanide molar ratio. Thus, when chitosan · EuCl3and PS-co-P4 VP·EuCl3are used as macromolecular precursors, a mixture of crystalline phases of both EuOCl and Eu2O3are obtained. However, when chitosan· NdCl3and PS-co-P4 VP· NdCl3are used, a sole pure crystalline phase of NdOCl is obtained. The nano structured lanthanide materials were characterized by means of XRD(X-ray diffraction of powder), SEM, EDS, TEM, and HRTEM. The luminescent spectra of the asprepared EuOCI/Eu2O3mixture materials show an emission pattern whose intensity is strongly influenced by the nature of the polymeric precursor, as well as on the metal/polymer molar ratios.

关键词： EuOCl/Eu_2O_3 NdOCl Solventless method Luminescence Lanthanides Rare earths

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The importance of the bite angle of metal(Ⅲ) salen catalysts in the sequestration of CO_(2) with epoxides in mild conditions

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Green Chemical Engineering 2022年第2期3卷 180-187页

作者： Anna Vidal-Lopez Sergio Posada-Perez Miquel Sola Valerio D'Elia Albert Poater Institut de quimica Computacional i Catalisi and departament de quimica Universitat de GironaC/Maria Aurelia Capmany6917003GironaCataloniaSpain department of Chemistry Universitat Autonoma de BarcelonaCerdanyola del VallesCatalonia08193Spain department of Materials Science and Engineering School of Molecular Science and EngineeringVidyasirimedhi Institute of Science and Technology(VISTEC)21210PayupnaiWang ChanThailand

Located in the middle of the fever to solve the problem of CO_(2)emissions in the environment,CO_(2)sequestration by reaction with epoxides is one of the key tools,as it not only fixes CO_(2),but also makes it functional by leading to cyclic ***,the results are focused specifically on the formation of cyclic organic carbonates catalyzed by metal-salen complexes,previously achieved with yttrium and scandium,that are compared with those of analogous complexes containing metals from the first transition series,such as cobalt or *** functional theory(DFT)calculations allow to determine whether this switch of metals will be feasible and provide the basis for instigating future experimental efforts in this *** calculations analyzing the structure and electronics of the catalysts allow us to give not only a clear picture of whether these catalysts will be efficient,but also allow us to assess which metal center is the most convenient and/or whether the catalytic reaction will occur under mild *** buried volume calculations with the SambVca packages shed light on the different catalytic pockets of monometallic first row transition metals *** III salen *** predictive catalysis results show that the bite O-M-O angle plays an essential role in the catalysis.

关键词： CO_(2)fixation Salen catalyst CO_(2)functionalization Cyclic carbonate DFT calculations Predictive catalysis

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Pyrenetetraone-based covalent organic framework as an effective electrocatalyst for oxygen reduction reaction

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Nano Research 2022年第5期15卷 3907-3912页

作者： Paloma Garcia-Arroyo Emiliano Martinez-Perinan Jorge J.Cabrera-Trujillo Elena Salagre Enrique G.Michel Jose I.Martinez Encarnacion Lorenzo Jose L.Segura departamento de quimica organica I Facultad de CC.QuimicasUniversidad Complutense de Madrid28040 MadridSpain departamento de quimica Analitica y Analisis Instrumental Facultad de CienciasUniversidad Autónoma de Madrid28049 MadridSpain departamento de Fisica de la Materia Condensada Universidad Autónoma de Madrid28049 MadridSpain Condensed Matter Physics Center(IFIMAC) Universidad Autónoma de Madrid28049 MadridSpain departamento de Nanoestructuras SuperficiesRecubrimientos y Astrofisica MolecularInstituto de Ciencia de Materiales de Madrid(ICMMCSIC)28049 MadridSpain Instituto Madrileno de Estudios Avanzados en Nanociencia(IMdeA-Nanociencia) 28049 MadridSpain Institute for Advanced Research in Chemical Sciences(IAdChem) Universidad Autonoma de Madrid28049 MadridSpain

A novel porous and crystalline two-dimensional(2D)electrochemically active covalent organic framework(COF)based on ortho-quinone units has been prepared as an innovative approach towards the development of organic cathode materials with multiple redox sites as an efficient electrocatalyst for the oxygen reduction reaction(ORR).In contrast with most of the previously reported COFs as electrocatalysts for the ORR,the electrocatalytic application of this material towards ORR has been investigated without adding any metal or conductive supporting material and avoiding any additional carbonization ***,the electrochemical properties of the COF material have been compared with two analogue amorphous frameworks with similar chemical composition,which points out the important role of the enhanced crystallinity and porosity of the COF network in its superior performance as an electrocatalyst towards ORR.

关键词： electrocatalysis oxygen reduction reaction metal free pyrenetetraone covalent organic framework

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Recent progress in flexible Zn-ion hybrid supercapacitors: Fundamentals, fabrication designs, and applications

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Carbon Energy 2023年第1期5卷 82-122页

作者： Muhammad Sufyan Javed Sumreen Asim Tayyaba Najam Muhammad Khalid Iftikhar Hussain Awais Ahmad Mohammed A.Assiri Weihua Han School of Physical Science and Technology Lanzhou UniversityLanzhouGansuChina Institute of Chemistry Khwaja Fareed University of Engineering and Information TechnologyPunjabPakistan College of Chemistry and Environmental Engineering Shenzhen UniversityShenzhenGuangdongChina department of Mechanical Engineering City University of Hong KongKowloonHong KongChina departamento de quimica organica Universidad de CordobaCordobaSpain department of Chemistry Faculty of ScienceKing Khalid UniversityAbhaSaudi Arabia

One of the most exciting new developments in energy storage technology is flexible Zn-ion hybrid supercapacitors(f-ZIHSCs),which combine the high energy of Zn-ion batteries with high-power supercapacitors to satisfy the needs of portable flexible ***,the development of f-ZHSCs is still in its infancy,and there are numerous barriers to overcome before they can be widely implemented for practical *** review gives an up-to-date description of recent achievements and underlying concepts in energy storage mechanisms of f-ZIHSCs and emphasizes the critical role of cathode,anode,and electrolyte materials systems in speeding the prosperity of *** innovative nanostructured-based cathode materials for f-ZIHSCs include carbon(e.g.,porous carbon,heteroatom-doped carbon,biomass-derived porous carbon,graphene,etc.),metal-oxides,MXenes,and metal/covalentorganic frameworks,and other materials(e.g.,activated carbon,phosphorene,etc.)are mainly ***,the latest developments in flexible anode and electrolyte frameworks and impacts of electrolyte compositions on the electrochemical properties of f-ZIHSC are ***,the advancements based on fabrication designs,including quasi-solid-state,micro,fiber-shaped,and all climate-changed f-ZIHSCs,are discussed in ***,a summary of current challenges and recommendations for the future progress of advanced f-ZIHSC are *** review article is anticipated to further understand the viable strategies and achievable approaches for assembling high-performance f-ZIHSCs and boost the technical revolutions on cathode,anode,and electrolytes for f-ZIHSC devices.

关键词： electrode electrolyte flexible MOFs MXenes Zn-ion hybrid supercapacitor

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Carbonaceous residues from biomass gasification as catalysts for biodiesel production

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Journal of Natural Gas Chemistry 2012年第3期21卷 246-250页

作者： Rafael Luque Antonio Pineda Juan C. Colmenares Juan M. Campelo Antonio A. Romero Juan Carlos Serrano-Ruiz Luisa F. Cabeza Jaime Cot-Gores departamento de quimica organica Universidad de Cardoba Campus de Rabanales Edif icio Marie Curie E-14014 Cardoba Spain Universitat de Lleida GREA lnnovacio Concurrent Lleida Spain Universitat de Lleida GREA lnnovacio Concurrent Lleida Spain

Tars and alkali ashes from biomass gasification processes currently constitute one of the major problems in biomass valorisation, generating clogging of filters and issues related with the purity of syngas production. To date, these waste residues find no useful applications and they are generally disposed upon generation in the gasification process. A detailed analysis of these residues pointed out the presence of high quantities of Ca （〉30 wt%）. TG experiments indicated that a treatment under air at moderate temperatures （400-800 ~C） decomposed the majority of carbon species, while XRD indicated the presence of a crystalline CaO phase. CaO enriched valorized materials turned out to be good heterogeneous catalysts for biodiesel production from vegetable oils, providing moderate to good activities （50%-70% after 12 h） to fatty acid methyl esters in the transesterification of sunflower oil with methanol.

关键词： biomass gasification residues biodiesel catalyst calcium oxide

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Palladium(Ⅱ) and Platinum(Ⅱ) Compounds derived From Potentially Terdentate Ligands

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复旦学报（自然科学版） 2005年第5期44卷 726-727页

作者： O. López departament de quimica Inorgdlnica Facultat de Quimica. Universitat de Barcelona. Marti i Franquès 1 - 11. 08028- Barcelona. Spain

Transition metalcomplexes derived from potentially terdentate ligands have attracted great interest in the late years. Among all the examples described so far, those containing palladium(Ⅱ) or platinum(Ⅱ) and ligands holding three heteroatoms with different donor abilities are particularly relevant. In compounds of this kind, the potential hemilability[1] of one of the terminal σ(M-donor atom) bonds, plays an important role in the view of their applications in homogeneous catalysis[2]. On the other hand, it is well-known that in dimetallic complexes the presence of two different metals in a close vicinity may influence their mutual cooperation in a wide variety of processes[3]. Besides that, some examples of the utility of chiral palladium( Ⅱ ) as well as platinum( Ⅱ ) complexes as precursors for organic and/or organometallic synthesis, as chiral recognitors or discriminators, or even in Bio-Medicine have also been reported[4- 6]. However, chiral heterodimetallic compounds holding ferrocenyl units and potentially terdentate ligands are scarce.

关键词：钯化合物手性复合三合配位体金属杂件二络铁

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