ACS Materials Au最新文献

{"title":"Tailoring Cu-Based Catalysts Supported on ZrO2–Al2O3 for Efficient and Selective Ethanol Conversion to Ethyl Acetate","authors":"Isabel C. Freitas,&nbsp;Davi D. Petrolini,&nbsp;Jean Marcel R. Gallo,&nbsp;Paula C. P. Caldas,&nbsp;Daniela C. de Oliveira,&nbsp;João B. O. Santos,&nbsp;Clelia Mara de Paula Marques and José Maria CorreaBueno*,&nbsp;","doi":"10.1021/acsmaterialsau.5c0001710.1021/acsmaterialsau.5c00017","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00017https://doi.org/10.1021/acsmaterialsau.5c00017","url":null,"abstract":"<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":"593–608 593–608"},"PeriodicalIF":5.7,"publicationDate":"2025-04-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.5c00017","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940706","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":"Functionalized Imidazolium Ether-Free Polymer Backbones with Ion Transport Channels and Catalytic Activity.","authors":"Bryan A Corzo, Hugo Hernández-Martínez, Eugenia Josefina Aldeco-Pérez, Jorge Cárdenas, Víctor Lara, Lilian I Olvera","doi":"10.1021/acsmaterialsau.4c00154","DOIUrl":"10.1021/acsmaterialsau.4c00154","url":null,"abstract":"<p><p>Novel ether-free bond polymer backbones were synthesized through polycondensation in a superacid medium by using <i>p</i>-terphenyl and 4-(1<i>H</i>-imidazol-1-yl)benzaldehyde. The presence of imidazolium groups enabled further modifications through a highly efficient nucleophilic substitution reaction introducing cationic sites essential for anionic transport. Characterization by NMR and FTIR analyses confirmed the structures and the complete functionalization of the base polymer. Critical properties for potential anion exchange membrane applications, including water uptake, ion exchange capacity, ion conductivity, morphology, and thermal and mechanical stabilities were investigated. Results indicated that these polymers form stable ion transport channels, with the formation of distinctive hydrophilic/hydrophobic microphase separation in the membranes observed through AFM, HR-TEM, and SAXS analyses. This structural configuration of the membranes exhibited high hydroxide conductivities of 61.33 and 80.33 mS/cm at 80 °C for 1AIM (quaternization with iodomethane) and 1ABPTA (quaternization with (3-bromopropyl)trimethylammonium bromide), respectively, with a thermal stability up to 240 °C, underscoring their suitability for electrochemical applications. Additionally, an organometallic polymer was successfully synthesized from the 1ABPTA polymer due to the presence of an imidazolium salt, <i>N</i>-heterocyclic carbene (NHC) ligand precursor. SEM images displayed the homogeneous distribution of metal atoms, and XPS spectra confirmed the formation of the C-M bond. The material obtained was utilized as a heterogeneous catalyst in a C-C Suzuki-Miyaura coupling reaction, achieving catalytic conversion percentages of 70% and 60% for the first and second cycles, respectively.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"508-521"},"PeriodicalIF":5.7,"publicationDate":"2025-03-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082359/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144094957","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":"Functionalized Imidazolium Ether-Free Polymer Backbones with Ion Transport Channels and Catalytic Activity","authors":"Bryan A. Corzo,&nbsp;Hugo Hernández-Martínez,&nbsp;Eugenia Josefina Aldeco-Pérez,&nbsp;Jorge Cárdenas,&nbsp;Víctor Lara and Lilian I. Olvera*,&nbsp;","doi":"10.1021/acsmaterialsau.4c0015410.1021/acsmaterialsau.4c00154","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.4c00154https://doi.org/10.1021/acsmaterialsau.4c00154","url":null,"abstract":"<p >Novel ether-free bond polymer backbones were synthesized through polycondensation in a superacid medium by using <i>p</i>-terphenyl and 4-(1<i>H</i>-imidazol-1-yl)benzaldehyde. The presence of imidazolium groups enabled further modifications through a highly efficient nucleophilic substitution reaction introducing cationic sites essential for anionic transport. Characterization by NMR and FTIR analyses confirmed the structures and the complete functionalization of the base polymer. Critical properties for potential anion exchange membrane applications, including water uptake, ion exchange capacity, ion conductivity, morphology, and thermal and mechanical stabilities were investigated. Results indicated that these polymers form stable ion transport channels, with the formation of distinctive hydrophilic/hydrophobic microphase separation in the membranes observed through AFM, HR-TEM, and SAXS analyses. This structural configuration of the membranes exhibited high hydroxide conductivities of 61.33 and 80.33 mS/cm at 80 °C for 1AIM (quaternization with iodomethane) and 1ABPTA (quaternization with (3-bromopropyl)trimethylammonium bromide), respectively, with a thermal stability up to 240 °C, underscoring their suitability for electrochemical applications. Additionally, an organometallic polymer was successfully synthesized from the 1ABPTA polymer due to the presence of an imidazolium salt, <i>N</i>-heterocyclic carbene (NHC) ligand precursor. SEM images displayed the homogeneous distribution of metal atoms, and XPS spectra confirmed the formation of the C–M bond. The material obtained was utilized as a heterogeneous catalyst in a C–C Suzuki–Miyaura coupling reaction, achieving catalytic conversion percentages of 70% and 60% for the first and second cycles, respectively.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"508–521 508–521"},"PeriodicalIF":5.7,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.4c00154","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940702","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":"Continuous Sustainable Production of Biobased Multicomponent Enhanced Resin for SLA 3D Printing.","authors":"Vojtěch Jašek, Otakar Bartoš, Veronika Lavrinčíková, Jan Fučík, Silvestr Figalla, Eliška Kameníková, Radek Přikryl","doi":"10.1021/acsmaterialsau.5c00014","DOIUrl":"10.1021/acsmaterialsau.5c00014","url":null,"abstract":"<p><p>This work focuses on biobased reactive diluents' synthesis, continuing with optimized oil-based resin precursor production. Our approach introduces vanillin methacrylate (VanMMA), cinnamyl methacrylate (CinMMA), and vanillyl dimethacrylate (VanDiMMA) synthesis using methacrylic anhydride. The introduced approach involves an innovative and available catalyst, potassium acetate, which possesses much suitable potential compared with the usually used 4-dimethylaminopyridine (DMAP). Moreover, we separated the formed secondary product, methacrylic acid (MA), and used it to modify rapeseed oil to prepare a curable thermoset. All synthesized products were structurally verified via complex cross-analysis (NMR, ESI-MS, and FTIR). The reactive systems were mixed to form a multicomponent mixture appropriate for stereolithography (SLA) and 3D printing. It was found that VanDiMMA exhibited comparable diluting properties to the commercially available and used compound, isobornyl methacrylate (IBOMA), while achieving better mechanical, thermo-mechanical, and thermal properties than IBOMA. VanDiMMA-containing SLA resin reached a tensile strength of 12.7 ± 0.3 MPa, a flexural strength of 16.8 ± 0.4 MPa, a storage modulus of 570 MPa at 30 °C, a glass-transition temperature of 83.7 °C, and the heat-resistant index of 169.5 °C.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"580-592"},"PeriodicalIF":5.7,"publicationDate":"2025-03-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082353/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144094950","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":"Continuous Sustainable Production of Biobased Multicomponent Enhanced Resin for SLA 3D Printing","authors":"Vojtěch Jašek*,&nbsp;Otakar Bartoš,&nbsp;Veronika Lavrinčíková,&nbsp;Jan Fučík,&nbsp;Silvestr Figalla,&nbsp;Eliška Kameníková and Radek Přikryl,&nbsp;","doi":"10.1021/acsmaterialsau.5c0001410.1021/acsmaterialsau.5c00014","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00014https://doi.org/10.1021/acsmaterialsau.5c00014","url":null,"abstract":"<p >This work focuses on biobased reactive diluents’ synthesis, continuing with optimized oil-based resin precursor production. Our approach introduces vanillin methacrylate (VanMMA), cinnamyl methacrylate (CinMMA), and vanillyl dimethacrylate (VanDiMMA) synthesis using methacrylic anhydride. The introduced approach involves an innovative and available catalyst, potassium acetate, which possesses much suitable potential compared with the usually used 4-dimethylaminopyridine (DMAP). Moreover, we separated the formed secondary product, methacrylic acid (MA), and used it to modify rapeseed oil to prepare a curable thermoset. All synthesized products were structurally verified via complex cross-analysis (NMR, ESI-MS, and FTIR). The reactive systems were mixed to form a multicomponent mixture appropriate for stereolithography (SLA) and 3D printing. It was found that VanDiMMA exhibited comparable diluting properties to the commercially available and used compound, isobornyl methacrylate (IBOMA), while achieving better mechanical, thermo-mechanical, and thermal properties than IBOMA. VanDiMMA-containing SLA resin reached a tensile strength of 12.7 ± 0.3 MPa, a flexural strength of 16.8 ± 0.4 MPa, a storage modulus of 570 MPa at 30 °C, a glass-transition temperature of 83.7 °C, and the heat-resistant index of 169.5 °C.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"580–592 580–592"},"PeriodicalIF":5.7,"publicationDate":"2025-03-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.5c00014","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940699","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":"Nickel-Doped Titanium Oxide with the Rutile Structure for High-Performance Sodium Storage","authors":"Hiroyuki Usui*,&nbsp;Yasuhiro Domi,&nbsp;Yuma Sadamori,&nbsp;Ryuto Tanaka,&nbsp;Takeo Hoshi,&nbsp;Toshiyuki Tanaka and Hiroki Sakaguchi*,&nbsp;","doi":"10.1021/acsmaterialsau.5c0000810.1021/acsmaterialsau.5c00008","DOIUrl":"https://doi.org/10.1021/acsmaterialsau.5c00008https://doi.org/10.1021/acsmaterialsau.5c00008","url":null,"abstract":"<p >We prepared rutile TiO₂ particles doped with Ni²⁺, Al³⁺, Nb⁵⁺, and Ta⁵⁺ by hydrothermal synthesis as anode materials for Na-ion batteries and investigated the effect of doping cation valence on the anode performance and the Na⁺ diffusion behavior. <i>In situ</i> X-ray diffraction analyses confirmed the insertion and extraction of Na⁺ while maintaining the rutile structure. Among the various doped TiO₂ electrodes, the Ni-doped TiO₂ one exhibited the best anode performance with a high reversible capacity of 135 mA h g^–1 even at 50<i>C</i> (16.75 A g^–1). This electrode showed a very long cycle life: the capacity of 225 mA h g^–1 could be attained even after 10,000 cycles. The first-principles calculation suggested the formation of impurity levels in the forbidden band of TiO₂ by various cation dopings. Electrochemical impedance analyses revealed that the Ni-doped TiO₂ electrode showed lower charge-transfer resistance (<i>R</i>_ct) compared with other cation-doped TiO₂ electrodes. Measurements using the galvanostatic intermittent titration technique found that the Na⁺ diffusion coefficient (<i>D</i>_Na+) of Ni-doped TiO₂ has a higher value of 1.2 × 10^–13 cm² s^–1 compared with <i>D</i>_Na+ of 4.8 × 10^–14 cm² s^–1 in the case of undoped TiO₂. The first-principle calculation supported this result: the Ni²⁺ doping could reduce the activation energy required for Na⁺ diffusion in rutile TiO₂. Therefore, we suggest that an easier migration of Na⁺ was promoted in the Ni-doped TiO₂, effectively enhancing the charge–discharge capacity and the cycle life. Although rutile TiO₂ as an anode has had a difficult history, this study proved that impurity element doping such as Ni²⁺ can transform it into a very attractive anode material.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"558–568 558–568"},"PeriodicalIF":5.7,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.5c00008","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143940698","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":"Nickel-Doped Titanium Oxide with the Rutile Structure for High-Performance Sodium Storage.","authors":"Hiroyuki Usui, Yasuhiro Domi, Yuma Sadamori, Ryuto Tanaka, Takeo Hoshi, Toshiyuki Tanaka, Hiroki Sakaguchi","doi":"10.1021/acsmaterialsau.5c00008","DOIUrl":"10.1021/acsmaterialsau.5c00008","url":null,"abstract":"<p><p>We prepared rutile TiO₂ particles doped with Ni²⁺, Al³⁺, Nb⁵⁺, and Ta⁵⁺ by hydrothermal synthesis as anode materials for Na-ion batteries and investigated the effect of doping cation valence on the anode performance and the Na⁺ diffusion behavior. <i>In situ</i> X-ray diffraction analyses confirmed the insertion and extraction of Na⁺ while maintaining the rutile structure. Among the various doped TiO₂ electrodes, the Ni-doped TiO₂ one exhibited the best anode performance with a high reversible capacity of 135 mA h g^-1 even at 50<i>C</i> (16.75 A g^-1). This electrode showed a very long cycle life: the capacity of 225 mA h g^-1 could be attained even after 10,000 cycles. The first-principles calculation suggested the formation of impurity levels in the forbidden band of TiO₂ by various cation dopings. Electrochemical impedance analyses revealed that the Ni-doped TiO₂ electrode showed lower charge-transfer resistance (<i>R</i> _ct) compared with other cation-doped TiO₂ electrodes. Measurements using the galvanostatic intermittent titration technique found that the Na⁺ diffusion coefficient (<i>D</i> _Na+) of Ni-doped TiO₂ has a higher value of 1.2 × 10^-13 cm² s^-1 compared with <i>D</i> _Na+ of 4.8 × 10^-14 cm² s^-1 in the case of undoped TiO₂. The first-principle calculation supported this result: the Ni²⁺ doping could reduce the activation energy required for Na⁺ diffusion in rutile TiO₂. Therefore, we suggest that an easier migration of Na⁺ was promoted in the Ni-doped TiO₂, effectively enhancing the charge-discharge capacity and the cycle life. Although rutile TiO₂ as an anode has had a difficult history, this study proved that impurity element doping such as Ni²⁺ can transform it into a very attractive anode material.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 3","pages":"558-568"},"PeriodicalIF":5.7,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC12082360/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144095020","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":"","authors":"","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":5.7,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/mgv005i002_1910209","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144430893","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":"","authors":"Pavel Ludačka,&nbsp;Vojtěch Liška,&nbsp;Jan Sýkora,&nbsp;Pavel Kubát and Jiří Mosinger*,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":5.7,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsmaterialsau.4c00137","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144430900","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":"","authors":"Stephanie L. Brock*,&nbsp;Maksym V. Kovalenko and Mary Ann Meador,&nbsp;","doi":"","DOIUrl":"","url":null,"abstract":"","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"5 2","pages":"XXX-XXX XXX-XXX"},"PeriodicalIF":5.7,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acsmaterialsau.5c00020","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144430887","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}