ACS Materials Au最新文献

{"title":"Tuning Physicochemical Properties of Boron Nitride-Based Membranes via Scalable One-Step Exfoliation for Ionic and Molecular Nanofiltration","authors":"Aritsa Bunpheng,&nbsp;Thanit Saisopa,&nbsp;Pawin Iamprasertkun,&nbsp;Anusorn Seubsai,&nbsp;Adisak Boonchun,&nbsp;Weekit Sirisaksoontorn and Wisit Hirunpinyopas*,&nbsp;","doi":"10.1021/acsmaterialsau.5c00026","DOIUrl":"10.1021/acsmaterialsau.5c00026","url":null,"abstract":"<p >Two-dimensional (2D) nanomaterials, such as graphene, have been widely used in various applications, such as electrodes for energy storage and laminar membranes for separations. Hexagonal boron nitride (hBN), one of the 2D materials possessing properties similar to graphene, can be used as laminar stacking laminates for separation processes due to its high filtration efficiency and solvent flow. Herein, we prepared 2D-hBN nanosheets using different nitrogen-containing precursors via facile liquid-phase exfoliation for the preparation of hBN membranes. We found that the as-prepared hBN samples exhibit unique physicochemical properties, as determined by various spectroscopic techniques, particularly near-edge X-ray absorption fine structure spectroscopy, which was used to identify the presence of defects on the hBN nanosheets. The elemental compositions of each hBN nanosheet were also revealed by an X-ray photoelectron spectroscopic technique, indicating significant changes in the B:N and B:C ratios. The hBN membranes exhibit high stability in aqueous solutions without membrane deformation. The nanochannel height of the hBN membranes was found to be <i>∼</i>0.34 nm, as determined by X-ray diffraction analysis. The membranes demonstrate excellent rejection performance for charged dye molecules (acid orange 7 and methylene blue) with high water permeation rates. This is due to electrostatic repulsion between the negatively charged surface of the hBN membranes and the charged species, as well as size exclusion from the narrow capillary channels between the stacked layered hBN nanosheets. Therefore, the hBN membranes, with their unique physicochemical properties, are promising for applications in water purification.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 4","pages":"687–697"},"PeriodicalIF":6.5,"publicationDate":"2025-05-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12257375/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144643741","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Boron-Functionalized Graphitic Carbon Nitride Materials for Photocatalytic Applications: Effects on Chemical, Adsorptive, Optoelectronic, and Photocatalytic Properties","authors":"Ioanna Itskou,&nbsp;Sharminaz C. Sageer,&nbsp;Daniel M. Dawson,&nbsp;Andreas Kafizas,&nbsp;Irena Nevjestic,&nbsp;Catriona M. McGilvery,&nbsp;Matyas Daboczi,&nbsp;Gwilherm Kerherve,&nbsp;Salvador Eslava,&nbsp;Sandrine Heutz,&nbsp;Sharon E. Ashbrook* and Camille Petit*,&nbsp;","doi":"10.1021/acsmaterialsau.5c00007","DOIUrl":"10.1021/acsmaterialsau.5c00007","url":null,"abstract":"<p >Graphitic carbon nitride (gC₃N₄, or CN herein) is widely studied as a photocatalyst owing to its ease of synthesis, high stability, and optoelectronic properties. However, its photocatalytic performance often remains limited, and a common approach to tune its function and enhance its performance is by doping. Boron (B) functionalization of CN has showed a potential benefit on photocatalytic performance for several reactions. However, the reason for this improvement and the links between synthesis method, exact B chemical environment, and performance remain unclear. Here, we present a fundamental study that elucidates the influence of (i) B functionalization, (ii) B content, and (iii) choice of B precursor on the physicochemical, adsorptive, optoelectronic, and photocatalytic properties of bulk B-CN. We synthesized two sets of B-CN materials (0.5–11 at% B), using either elemental boron or boric acid as precursors. The samples were characterized using several imaging and spectroscopic techniques, which confirm the integration of B into the material through B–O bonding and the creation of B clusters in the case of the boron precursor, with density functional theory (DFT) calculations supporting our analyses. The distribution of B atoms within B-CN particles remained heterogeneous. Compared to CN, B-functionalized materials show enhanced porosity and CO₂ uptake, with similar degrees of light absorption and deeper energy band positions. Transient absorption spectroscopy (TAS) measurements showed that charge carrier populations, lifetimes, and kinetics were not significantly affected by B functionalization; however, at 5 at% B doping, an increase in the concentration of charge carriers was seen. Higher B content enhances the photocatalytic NO_<i>x</i> removal under UVA irradiation (almost two-fold) and the selectivity to NO₃^– from NO_<i>x</i> photooxidation, but has no significant effect on CO₂ photoreduction, compared to pristine CN. Overall, this study provides fundamental insights to build on and more rationally produce better-performing B-CN photocatalysts.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 4","pages":"656–674"},"PeriodicalIF":6.5,"publicationDate":"2025-05-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12257377/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144643732","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring Functional Graphene-Derived Geopolymer Nanocomposites: Interfacial Interactions and Mechanical Strength Enhancement","authors":"Manali Rathee,&nbsp;Harikrishnan K. Surendran,&nbsp;Aditya Thakur,&nbsp;Chandrabhas Narayana,&nbsp;Rabindranath Lo,&nbsp;Anurag Misra* and Kolleboyina Jayaramulu*,&nbsp;","doi":"10.1021/acsmaterialsau.5c00028","DOIUrl":"10.1021/acsmaterialsau.5c00028","url":null,"abstract":"<p >Geopolymers are emerging as sustainable alternatives to Ordinary Portland Cement (OPC), offering high strength, lightweight properties, and a lower environmental impact, making them promising materials for green concrete technologies. In this study, we synthesized graphene-based geopolymer nanocomposites using various functional graphene derivatives, such as graphene oxide (GO), sulfonated graphene oxide (G-SO₃H) thiographene (G-SH), and phosphate graphene (G-PO₃H), along with alumina- and silica-rich waste materials, such as fly ash and dolomite, to enhance mechanical properties, including setting time, flowability, compressive strength, and water absorption. The functional groups on graphene derivatives improve the particle dispersion and matrix density, enhancing compressive strength, while Raman spectroscopy reveals spectral shifts at interfaces of phosphate graphene with dolomite and fly ash, indicating interactions. The resultant FDGP exhibits a significantly higher compressive strength of 45.60 MPa at 7 days and 50.20 MPa at 28 days compared to GO, G-SH, and G-SO₃H. The high concentration of phosphate functional groups promotes strong interactions with the geopolymer matrix, improving its workability. Furthermore, density functional theory (DFT) calculations elucidate the role of functional groups in graphene-based geopolymer concrete, enhancing molecular interactions and promoting robust interfacial adhesion with the geopolymer matrix for a superior performance. We studied the time-dependent interactions of functionalized graphene oxide phosphate using DFT and other characterization methods, revealing strong hydrogen bonding that enhances dispersion and reinforcement within the geopolymer matrix.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 4","pages":"698–708"},"PeriodicalIF":6.5,"publicationDate":"2025-05-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12257412/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144643739","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Interfacial Microenvironment Effects at Laser-Made Gold Nanoparticles Steer Carbon Dioxide Reduction Product Generation.","authors":"Connor P Cox, Qishen Lyu, Madeleine K Wilsey, Likun Cai, Lydia R Schultz, Jason R Maher, Astrid M Müller","doi":"10.1021/acsmaterialsau.4c00161","DOIUrl":"10.1021/acsmaterialsau.4c00161","url":null,"abstract":"<p><p>This study emphasizes the critical importance of using surfactant-free gold nanoparticles to gain mechanistic insights and improve the energy efficiency and carbon monoxide selectivity in aqueous carbon dioxide reduction electrocatalysis. We utilized pulsed laser in liquid synthesis to prepare surfactant-free gold nanoparticles with a nonequilibrium cauliflower morphology, which demonstrated superior catalytic performance compared to conventionally synthesized citrate-capped gold nanoparticles. By functionalizing gold nanoparticles with nine <i>n</i>-alkanethiols and two nitrogen-containing thiols, we investigated how the chemical identity of interfacial ligands and their corresponding self-assembled monolayers (SAMs) influence the selectivity and activity of gold nanoparticle-catalyzed CO₂ reduction. This approach enabled a detailed understanding of how SAM characteristics at gold nanocatalyst interfaces affect key aspects of CO₂ electrocatalysis, including CO₂ mass transport and interfacial water behavior. The laser-synthesized gold nanoparticles exhibited improved performance across all surface modifications. Our findings highlight the significance of precise control over material surfaces in understanding catalyst microenvironments, which is essential for optimizing CO₂ reduction processes and forming a foundation for sustainable syngas production through tailored nanomaterial design and functionalization strategies.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"522-536"},"PeriodicalIF":5.7,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082361/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144095003","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Interfacial Microenvironment Effects at Laser-Made Gold Nanoparticles Steer Carbon Dioxide Reduction Product Generation","authors":"Connor P. Cox,&nbsp;Qishen Lyu,&nbsp;Madeleine K. Wilsey,&nbsp;Likun Cai,&nbsp;Lydia R. Schultz,&nbsp;Jason R. Maher and Astrid M. Müller*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0016110.1021/acsmaterialsau.4c00161","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00161https://doi.org/10.1021/acsmaterialsau.4c00161","url":null,"abstract":"<p >This study emphasizes the critical importance of using surfactant-free gold nanoparticles to gain mechanistic insights and improve the energy efficiency and carbon monoxide selectivity in aqueous carbon dioxide reduction electrocatalysis. We utilized pulsed laser in liquid synthesis to prepare surfactant-free gold nanoparticles with a nonequilibrium cauliflower morphology, which demonstrated superior catalytic performance compared to conventionally synthesized citrate-capped gold nanoparticles. By functionalizing gold nanoparticles with nine <i>n</i>-alkanethiols and two nitrogen-containing thiols, we investigated how the chemical identity of interfacial ligands and their corresponding self-assembled monolayers (SAMs) influence the selectivity and activity of gold nanoparticle-catalyzed CO₂ reduction. This approach enabled a detailed understanding of how SAM characteristics at gold nanocatalyst interfaces affect key aspects of CO₂ electrocatalysis, including CO₂ mass transport and interfacial water behavior. The laser-synthesized gold nanoparticles exhibited improved performance across all surface modifications. Our findings highlight the significance of precise control over material surfaces in understanding catalyst microenvironments, which is essential for optimizing CO₂ reduction processes and forming a foundation for sustainable syngas production through tailored nanomaterial design and functionalization strategies.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"522–536 522–536"},"PeriodicalIF":5.7,"publicationDate":"2025-04-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00161","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143941027","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Direct Correlation of the Crystalline Phases of La0.9Sr0.1Co1–yFeyO3−δ with the Partial Oxidation of Methane via In Situ Neutron and Synchrotron Diffraction","authors":"Dennis D. Nguyen,&nbsp;Mara J. Milhander,&nbsp;Elizabeth M. Hitch,&nbsp;Dmitri Leo M. Cordova,&nbsp;Jose L. Gonzalez Jimenez,&nbsp;Juana Mora,&nbsp;Daniel Sandoval,&nbsp;Maxx Q. Arguilla and Allyson M. Fry-Petit*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0017710.1021/acsmaterialsau.4c00177","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00177https://doi.org/10.1021/acsmaterialsau.4c00177","url":null,"abstract":"<p >Oxygen transport membranes find broad usage in many technologies, but due to the harsh conditions under which such technologies operate, detailed structural analysis under operational conditions has been limited. This work details the <i>in situ</i> neutron and synchrotron diffraction of the industrially relevant family of compounds, La_0.9Sr_0.1Co_1–<i>y</i>Fe<i>_y</i>O_3−δ (<i>y</i> = 0, 0.25, 0.75, 1), under reductive and oxidative conditions at elevated temperatures ranging from 723 to 1123 K. Quantitative Rietveld refinements determine the molar fraction of all crystalline intermediates and products that form during the reactions of La_0.9Sr_0.1Co_1–<i>y</i>Fe<i>_y</i>O_3−δ (<i>y</i> = 0, 0.25, 0.75, 1) with methane and then air. Coupling <i>in situ</i> diffraction analysis with catalytic product analysis of the partial oxidation of methane allows for the catalytically active phases to be determined. This work shows the strength of <i>in situ</i> diffraction under extreme conditions and the insights it can give about reactions in the solid state that have previously been elusive.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"547–557 547–557"},"PeriodicalIF":5.7,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00177","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940750","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Direct Correlation of the Crystalline Phases of La_0.9Sr_0.1Co_1-<i>y</i> Fe <i>_y</i> O_3-δ with the Partial Oxidation of Methane via <i>In Situ</i> Neutron and Synchrotron Diffraction.","authors":"Dennis D Nguyen, Mara J Milhander, Elizabeth M Hitch, Dmitri Leo M Cordova, Jose L Gonzalez Jimenez, Juana Mora, Daniel Sandoval, Maxx Q Arguilla, Allyson M Fry-Petit","doi":"10.1021/acsmaterialsau.4c00177","DOIUrl":"10.1021/acsmaterialsau.4c00177","url":null,"abstract":"<p><p>Oxygen transport membranes find broad usage in many technologies, but due to the harsh conditions under which such technologies operate, detailed structural analysis under operational conditions has been limited. This work details the <i>in situ</i> neutron and synchrotron diffraction of the industrially relevant family of compounds, La_0.9Sr_0.1Co_1-<i>y</i> Fe <i>_y</i> O_3-δ (<i>y</i> = 0, 0.25, 0.75, 1), under reductive and oxidative conditions at elevated temperatures ranging from 723 to 1123 K. Quantitative Rietveld refinements determine the molar fraction of all crystalline intermediates and products that form during the reactions of La_0.9Sr_0.1Co_1-<i>y</i> Fe <i>_y</i> O_3-δ (<i>y</i> = 0, 0.25, 0.75, 1) with methane and then air. Coupling <i>in situ</i> diffraction analysis with catalytic product analysis of the partial oxidation of methane allows for the catalytically active phases to be determined. This work shows the strength of <i>in situ</i> diffraction under extreme conditions and the insights it can give about reactions in the solid state that have previously been elusive.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"547-557"},"PeriodicalIF":5.7,"publicationDate":"2025-04-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082351/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144094879","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Design Strategies for Coupling CO₂ Reduction Molecular Electrocatalysts to Silicon Photocathodes.","authors":"Simran S Saund, Melissa K Gish, Jeremiah Choate, Trung H Le, Smaranda C Marinescu, Nathan R Neale","doi":"10.1021/acsmaterialsau.5c00010","DOIUrl":"10.1021/acsmaterialsau.5c00010","url":null,"abstract":"<p><p>We explore strategies for enhancing the electronic interaction between silicon nanocrystals (Si NCs) and surface-tethered molecular Re electrocatalysts ([Re]) as models for CO₂-reducing photocathodes. Using density functional theory (DFT) combined with electrochemical, spectroscopic, and photocatalytic measurements, we determine that the intrinsic Si (ⁱSi) NC conduction band energy in ⁱSi-[Re] assemblies is below the [Re] lowest unoccupied molecular orbital (LUMO) and singly occupied molecular orbital energies even for strongly quantum-confined 3.0-3.9 nm diameter hydrogen- and methyl-terminated ⁱSi NCs, respectively. We computationally analyze design strategies to align the semiconductor conduction band edge and electrocatalyst frontier molecular orbitals by varying the ⁱSi NC size, introducing boron as a dopant in the Si NC, and modifying the attachment chemistry to the [Re] complex aryl ligand framework. Our DFT analysis identifies a target hybrid structure featuring B-doped silicon (B:Si) NCs and a direct bond between a surface atom and an sp²-hybridized carbon of the electrocatalyst bipyridine aryl ring ligand (B:Si-C_Ar[Re]). We synthesize the B:Si-C_Ar[Re] NC assembly and find evidence of direct hybridization between the B:Si NC and the surface [Re] electrocatalyst LUMO using electrochemical measurements and transient absorption spectroscopy. This work provides a blueprint for the design of new Si photocathode-molecular electrocatalyst hybrids for CO₂ reduction and related fuel-forming photocatalytic conversions.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"569-579"},"PeriodicalIF":5.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082352/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144094875","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Design Strategies for Coupling CO2 Reduction Molecular Electrocatalysts to Silicon Photocathodes","authors":"Simran S. Saund,&nbsp;Melissa K. Gish,&nbsp;Jeremiah Choate,&nbsp;Trung H. Le,&nbsp;Smaranda C. Marinescu and Nathan R. Neale*,&nbsp;","doi":"10.1021/acsmaterialsau.5c0001010.1021/acsmaterialsau.5c00010","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00010https://doi.org/10.1021/acsmaterialsau.5c00010","url":null,"abstract":"<p >We explore strategies for enhancing the electronic interaction between silicon nanocrystals (Si NCs) and surface-tethered molecular Re electrocatalysts ([Re]) as models for CO₂-reducing photocathodes. Using density functional theory (DFT) combined with electrochemical, spectroscopic, and photocatalytic measurements, we determine that the intrinsic Si (ⁱSi) NC conduction band energy in ⁱSi–[Re] assemblies is below the [Re] lowest unoccupied molecular orbital (LUMO) and singly occupied molecular orbital energies even for strongly quantum-confined 3.0–3.9 nm diameter hydrogen- and methyl-terminated ⁱSi NCs, respectively. We computationally analyze design strategies to align the semiconductor conduction band edge and electrocatalyst frontier molecular orbitals by varying the ⁱSi NC size, introducing boron as a dopant in the Si NC, and modifying the attachment chemistry to the [Re] complex aryl ligand framework. Our DFT analysis identifies a target hybrid structure featuring B-doped silicon (B:Si) NCs and a direct bond between a surface atom and an sp²-hybridized carbon of the electrocatalyst bipyridine aryl ring ligand (B:Si–C_Ar[Re]). We synthesize the B:Si–C_Ar[Re] NC assembly and find evidence of direct hybridization between the B:Si NC and the surface [Re] electrocatalyst LUMO using electrochemical measurements and transient absorption spectroscopy. This work provides a blueprint for the design of new Si photocathode-molecular electrocatalyst hybrids for CO₂ reduction and related fuel-forming photocatalytic conversions.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"569–579 569–579"},"PeriodicalIF":5.7,"publicationDate":"2025-04-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.5c00010","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940746","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring Cu-Based Catalysts Supported on ZrO₂-Al₂O₃ for Efficient and Selective Ethanol Conversion to Ethyl Acetate.","authors":"Isabel C Freitas, Davi D Petrolini, Jean Marcel R Gallo, Paula C P Caldas, Daniela C de Oliveira, João B O Santos, Clelia Mara de Paula Marques, José Maria Correa Bueno","doi":"10.1021/acsmaterialsau.5c00017","DOIUrl":"10.1021/acsmaterialsau.5c00017","url":null,"abstract":"<p><p>Selective conversion of ethanol to ethyl acetate is of significant industrial and environmental relevance, providing a sustainable route for adding value to ethanol. This study investigated Cu-based catalysts supported on ZrO₂-Al₂O₃, focusing on the relationships among copper loading, metal-oxide interactions, and catalytic performance. Systematic variation of the copper content revealed that the Cu⁺/Cu⁰ ratio and the particle size distribution are crucial determinants of product selectivity. Lower copper loadings favored acetaldehyde production due to a higher Cu⁺/Cu⁰ ratio, while higher loadings favored Cu⁰ species and enhanced ethyl acetate selectivity by facilitating the formation of acyl species at the metal-oxide interface. The incorporation of ZrO₂ was important for the creation of active sites necessary for condensation reactions. Advanced characterization techniques ((diffuse reflectance infrared Fourier transform spectroscopy DRIFTS)-CO, X-ray photoelectron spectroscopy (XPS), and extended X-ray absorption fine structure (EXAFS)) elucidated key electronic and structural properties, showing the need to tailor the copper loading and the composition of the support to ensure efficient and sustainable ethanol conversion.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"593-608"},"PeriodicalIF":5.7,"publicationDate":"2025-04-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082363/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144095059","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}