Chemistry of Materials最新文献

{"title":"Enhanced Electrocatalytic Performance of BiFeO3/g-C3N4 Composites for the Two-Electron Oxygen Reduction Reaction","authors":"Sthitapragyan Patnaik, Lokesh Yadav, Amit Kumar Nayak, Srimanta Pakhira, Debabrata Pradhan","doi":"10.1021/acs.chemmater.5c00351","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00351","url":null,"abstract":"An efficient electrocatalyst for the eco-friendly synthesis of hydrogen peroxide (H₂O₂) via a two-electron oxygen reduction reaction (2e^– ORR) method, which serves as a viable alternative to the conventional anthraquinone process, is crucial for numerous applications. However, it remains a significant challenge for the electrocatalysis community, requiring an urgent demand for developing highly selective electrocatalysts for H₂O₂ generation. Herein, a cost-effective and nonprecious perovskite oxide composite material, BiFeO₃/g-C₃N₄ (BFO_gCN), has been successfully synthesized as an electrocatalyst for the 2e^– ORR through a simple physical mixing, followed by calcination, demonstrating its exceptional selectivity for H₂O₂ generation. The synthesis technique allows for altering the electronic structure of BiFeO₃ (BFO) and g-C₃N₄ (gCN), ensuring a high oxygen vacancy, increased hydroxyl adsorption on the surface of the BFO_gCN composite, and conductive gCN sheets that facilitate the ORR. The composite catalyst (50_BFO_gCN) exhibits high H₂O₂ selectivity, exceeding 70% throughout a broad potential range of 0.3–0.6 V versus RHE, compared to other composites for the ORR in an alkaline medium. The H₂O₂ selectivity of the synthesized electrocatalyst is consistently sustained for 50 h at 0.5 V during a durability assessment. The yield rate of H₂O₂ reaches a maximum of 1528.8 mmol g^–1 h^–1 at 0.5 V, exhibiting a faradaic efficiency (FE) of 94.9% after 3 h of electrocatalysis. To assist the experimental observation, the Perdew–Burke–Ernzerhof (PBE) functional with the Grimme’s third-order (-D3) dispersion corrections (in short PBE-D method) has been employed to explore the ORR mechanism. These calculations reveal that the improved performance of the subject material is due to the oxygen vacancy at the Fe site, and it also stabilizes the critical intermediates, such as OOH*, thereby preventing O–O bond breaking and suppressing the 4e^– pathway. This study introduces a highly selective electrocatalyst for the 2e^– ORR and offers an approach to electrocatalyst design.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"11 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Near-Infrared Light-Triggered Bacterial Eradication by Different Morphologies of NH2-MIL-101(Fe)@Ag","authors":"Dan Zhao, Wenjie Jiang, Wang Zhang, Chenhao Zhang, Wenjun Zhao, Zhizhou Chen, Yanan Liu, Jiajie Xu","doi":"10.1021/acs.chemmater.5c00958","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00958","url":null,"abstract":"Antibiotic overuse has led to drug-resistant bacteria and superbugs, necessitating urgent strategies. MOFs, although they are potential antimicrobial carriers, have limitations at low doses and in single therapy. Here, by adding different amounts of CTAB in the precursor solution, two different morphologies of NH₂-MIL-101(Fe)@Ag nanoagents were obtained, namely, NH₂-MIL-101(Fe)@Ag-1 (Cube) and NH₂-MIL-101(Fe)@Ag-2 (Octahedron). Antibacterial experiments showed that these two nano reagents with both photothermal and photodynamic effects exhibited nearly 100% bactericidal rate against high concentrations of <i>Staphylococcus aureus</i> and <i>Escherichia coli</i> (10⁷ CFU/mL) within 15 min. The combination of inactivation of intracellular proteins and disruption of cell membranes induced by Ag ions and high temperature resulted in NH₂-MIL-101(Fe)@Ag 100% in an octahedron showing durable and superior bactericidal performance at low doses (64 μg/mL), which is much better than other antibacterial reagents. Furthermore, the enhanced mechanism was discussed in detail by DFT calculations. A special electron transfer process occurred between Ag and NH₂-MIL-101 (Fe) under 880 nm NIR irradiation, which promoted the generation of ROS and enhanced the antibacterial effect. In addition, these two nano reagents have good therapeutic effects on wound healing <i>in vivo</i> due to silver ions and photothermal effects.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"13 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305197","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photocatalyzed Spatioselective, Orthogonal, and Covalent Immobilization of Biomolecules onto Cellulose-Based Paper","authors":"Ingo Bork, Adrian Bloch, Carolin S. Dombrowsky, Dominic Happel, Sejal Kapoor, Susanne S. Klinke, Enis M. Saritas, Lukas Neuenfeld, Tobias Meckel, Markus Biesalski, Harald Kolmar","doi":"10.1021/acs.chemmater.5c00308","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00308","url":null,"abstract":"In this study, a three-step approach for the immobilization of biomolecules on commercially available filter paper is presented. Photocatalytic coupling of a linker moiety to the paper fibers allows for spatiotemporal control of the immobilization site. An appropriate linker was attached to the biomolecule, allowing catalyst-free, site-specific, and covalent attachment of the biomolecule. Orthogonal linker pairs were evaluated, and five conjugation strategies were identified as providing robust and orthogonal attachment of the desired biomolecule. The suitability of these methods for the generation of complex biofunctionalized papers was demonstrated through premodification of a single sheet of paper with the respective linkers in a spatioselective manner. Application of a mixture of proteins containing the respective linker moieties resulted in successful immobilization of the proteins at the desired sites.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144305162","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Catalytic Poly(ethylene terephthalate) Aromatic C–H Hydroxylation for Upcycling to Specialty Chemicals and Multivariate Metal–Organic Frameworks","authors":"Jason Y. C. Lim, Tristan T. Y. Tan, Jerald Y. Q. Teo, Wei Wei Loh, Hazel Lau","doi":"10.1021/acs.chemmater.5c00513","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00513","url":null,"abstract":"Poly(ethylene terephthalate) (PET), the most produced and recovered aromatic polyester worldwide, offers numerous opportunities for upcycling into functional materials and chemicals. The aromatic terephthalate segment makes up the bulk of the total PET mass and offers opportunities to access valuable highly substituted oxygenated aromatics that are important precursors to a host of specialty chemicals and functional materials. However, chemical modification of the terephthalate segment has thus far achieved limited success due to the aromatic ring’s electron deficiency, which deactivates it toward electrophilic attack. Herein, we demonstrate the usage of transition-metal-catalyzed C–H activation as a viable strategy for direct functionalization of PET’s aromatic C–H bonds in this proof-of-concept study. Ruthenium-catalyzed C–H hydroxylation afforded the useful, yet synthetically challenging, highly substituted oxygenated aromatic compound 2-hydroxyterephthalic acid in high selectivity and synthetically useful conversions directly from PET. Notably, this procedure was tolerant to a range of PET plastic wastes, including dye-containing textiles and other non-PET plastic contaminants, and was also amenable to gram-scale aromatic functionalization of used real-life PET beverage bottles. The resulting 2-hydroxyterephthalic acid product can be further upcycled into multivariate hydroxylated MOFs with high porosity and crystallinity, which have proven to be useful for many known applications. With our aromatic C–H activation strategies, we expand the diversity and possibilities of value-added materials and chemicals accessible from PET.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"27 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144296251","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electron-Enhanced Deposition of Titanium-, Silicon- and Tungsten-Containing Films at Low Temperatures Using Volatile Precursors with Various Reactive Background Gases","authors":"Zachary C. Sobell, Andrew S. Cavanagh, Steven M. George","doi":"10.1021/acs.chemmater.5c00264","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00264","url":null,"abstract":"Electron-enhanced atomic layer deposition (EE-ALD) and electron-enhanced chemical vapor deposition (EE-CVD) can be employed for the low temperature deposition of thin films using volatile precursors with various reactive background gases (RBGs). EE-CVD expands on the previous demonstration of TiN EE-ALD using alternating Ti(N(CH₃)₂)₄ (tetrakisdimethylamino titanium (TDMAT)) and electron beam exposures with NH₃ RBG. During EE-CVD, the electron beam and the RBG are present continuously. Together with the RBG and electron beam incident on the surface, the volatile precursor is pulsed into the vacuum chamber to control the film growth. In this survey, the metal or metalloid precursors were TDMAT, Si₂H₆, and W(CO)₆. The RBGs were O₂, NH₃, CH₄, and H₂. The study focused on TiO₂ EE-ALD and SiN, SiO₂, SiC_<i>x</i>, SiH_<i>x</i>, W₂N, WO_<i>x</i>, and WC_<i>x</i> EE-CVD. Thin film growth was monitored using in situ 4-wavelength ellipsometry. To first illustrate EE-ALD, TiO₂ EE-ALD was performed at <i>T</i> &lt; 80 °C using alternating TDMAT and electron beam exposures together with O₂ RBG. The growth rate for the TiO₂ EE-ALD was ∼0.7 Å/cycle. The TiO₂ EE-ALD films were nearly stoichiometric, displayed crystallinity, and were smooth as measured by atomic force microscopy (AFM). Other Ti-containing EE-ALD films were deposited using CH₄ and H₂ RBGs. Subsequently, to demonstrate EE-CVD, SiC_<i>x</i> EE-CVD was performed at <i>T</i> &lt; 100 °C using repeating Si₂H₆ pulses with continuous electron beam and CH₄ RBG exposures. XPS revealed a 1:1 Si/C stoichiometry for a CH₄ RBG pressure of 0.45 mTorr and C-rich films for higher CH₄ RBG pressures. The SiC EE-CVD growth rate was ∼0.4 Å per Si₂H₆ pulse. The stoichiometric SiC EE-CVD films were smooth as measured by AFM. Other Si-containing EE-CVD films that were deposited included SiO₂, SiN and SiH_<i>x</i>. In addition, W₂N was deposited with EE-CVD at <i>T</i> &lt; 120 °C using repeating W(CO)₆ pulses with continuous electron beam and NH₃ RBG exposures. The W₂N EE-CVD growth rate was ∼0.17 Å per W(CO)₆ pulse. The W₂N films had a resistivity of ∼450 μΩ cm. The W₂N EE-CVD films also displayed crystallinity and high purity. Other W-containing EE-CVD films that were deposited included WO_<i>x</i> and WC_<i>x</i>. This survey shows that the EE-ALD technique can be extended to EE-CVD with various RBGs to deposit a broad range of materials at low temperatures including oxides, nitrides and carbides.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"227 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144296250","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Aziridinium 3D Perovskites: Toward Semiconducting Films with Tunable Band Gaps","authors":"Olesia I. Kucheriv, Hanna R. Petrosova, Valerii Y. Sirenko, Oleksandr A. Semenikhin, Maryam Choghaei, Klaus Meerholz, Selina Olthof, Il’ya A. Gural’skiy","doi":"10.1021/acs.chemmater.5c00671","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00671","url":null,"abstract":"Halide organic–inorganic perovskites are used as highly efficient semiconducting layers in photovoltaic and optoelectronic devices. However, the selection of known 3D organic–inorganic perovskites that have been processed into thin films is very limited. Here, we offer a route toward thin films of (AzrH)PbBr₃ and (AzrH)PbCl₃ (AzrH = aziridinium). The aziridinium perovskite films were deposited via a solution-based approach and make a contribution toward extension of the set of functional halide perovskite thin films. The developed procedure allows achieving thin films that keep the perovskite crystal structure up to 60 °C as confirmed by X-ray diffraction measurements. UV–vis absorption and photoluminescence measurements show that these bromide and chloride containing aziridinium perovskites form semiconducting thin films with optical band gaps of 2.40 and 3.20 eV and display emission at 545 and 407 nm, respectively. Interestingly, (AzrH)PbBr₃ thin films show an increased value of Stokes shift at room temperature (up to 80 meV) that makes this material promising for applications where reabsorption has to be avoided. UV and inverse photoelectron spectroscopies yield energy level positions that are in good agreement with calculations by density functional theory. This work uncovers the potential of aziridinium-based perovskite thin films regarding their semiconducting properties, thus widening the range of perovskites suitable for optoelectronic applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"4 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144278857","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pauling’s Third Rule as a Guide for Designing Low Thermal Conducting Chalcogenides","authors":"Riddhimoy Pathak, Mridul Krishna Sharma, Kanishka Biswas","doi":"10.1021/acs.chemmater.5c01050","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01050","url":null,"abstract":"Linus Pauling’s third empirical rule, which describes the destabilizing effect of shared polyhedral units in crystal structures, now provides a novel basis for understanding and predicting lattice thermal conductivity (κ_lat) in extended solids. In this perspective, we investigate ∼65 ternary metal chalcogenides with corner-shared (CS), edge-shared (ES), or face-shared (FS) polyhedral units, uncovering a monotonous decline in κ_lat as polyhedral connectivity shifts from CS to ES to FS in the structure. This trend arises from increasing cationic repulsion, leading to local lattice instability and enhanced phonon scattering in structures particularly having either ES or FS polyhedra. Comparative analysis of metal chalcogenides having the same constituent atoms further validates that materials possessing ES and FS configurations consistently exhibit lower κ_lat than materials having CS subunits. While a few exceptions exist, our findings establish Pauling’s third rule as a chemical guide for identifying materials with intrinsically ultralow κ_lat, a key requirement for high thermoelectric performance. We believe that this insight would accelerate the discovery of efficient thermoelectric materials by leveraging fundamental crystal chemistry principles.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"17 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269245","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to “Screening High-Performance Hybrid Halides Scintillators: A Comprehensive Analysis and Prediction Model”","authors":"Maxim Molokeev, Nicolay Golovnev, Andrey Zolotov, Shuai Zhang, Zhiguo Xia","doi":"10.1021/acs.chemmater.5c01149","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01149","url":null,"abstract":"The caption of Figure 7 was incorrect in the published Article. The correct caption should read as follows: <b>Figure 7.</b> (a) Dependence of the RL intensity of [DMe]MnBr₄ on the X-ray irradiation dose rate; (b) Linear relationship between the SNR and the X-ray irradiation dose rate; (c) Comparison of the X-ray (top) and visible-light (bottom) images of a data cable; (d) MTF curve of the [DMe]MnBr₄ scintillation film, measured using the slanted edge method. This correction does not change any other parts, including data analysis and conclusions, of the published work. This article has not yet been cited by other publications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"42 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144290011","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of the M- and A-Elements on the Oxidation Stability of Solid Solution MAX Phases V2Ga1–xGexC and Cr2Ga1–xGexC","authors":"Suneet Kale, Alexander E. Sedykh, Prajna Bhatt, Aysha A. Riaz, Pardeep K. Thakur, Tien-Lin Lee, Anna Regoutz, Maren Lepple, Christina S. Birkel","doi":"10.1021/acs.chemmater.5c00888","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c00888","url":null,"abstract":"MAX phase carbides have attracted much attention due to their unique combination of metallic and ceramic properties, making them promising materials for high-temperature applications. Understanding how the materials fail is a crucial step in working toward implementing them into devices outside of the laboratory setting. Their stability toward oxidation at high temperatures, while also being electronically and thermally conductive, sets MAX phases apart from other materials. Some aluminum-containing compounds form a protective alumina layer that contributes to the oxidation resistance of the respective MAX phase. However, a broader understanding of how other MAX phases, especially those with <i>M</i>-elements beyond titanium and <i>A</i>-elements beyond aluminum, oxidize is lacking. Therefore, we synthesized two <i>A</i>-site solid solutions (gallium and germanium as the <i>A</i>-elements) based on chromium and vanadium as <i>M</i>-elements by high-temperature solid-state syntheses. Their composition, structural properties, and bonding characteristics are investigated by synchrotron powder X-ray diffraction, electron microscopy with elemental analysis, and Raman and X-ray photoelectron spectroscopy. Thermal analysis reveals the influence of the <i>M</i>- and <i>A</i>-elements on the oxidation behavior: phases with Cr on the <i>M</i>-site have higher oxidation stability than with V, and solid solutions Cr₂Ga_1–<i>x</i>Ge_<i>x</i>C have improved oxidation resistance compared to the individual phases Cr₂GaC and Cr₂GeC.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"26 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144269241","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction to “Effect of La Addition to Ceria on the Oxygen Storage Capacity and the Energetics of Water Adsorption”","authors":"Noa Azaria, Danielle Schweke, Lee Shelly, Shmuel Hayun","doi":"10.1021/acs.chemmater.5c01187","DOIUrl":"https://doi.org/10.1021/acs.chemmater.5c01187","url":null,"abstract":"The following statement was inadvertently omitted from the Acknowledgments in the originally published article: N.A. sincerely thanks Maisam Nassar for her valuable assistance in testing the OSC of doped ceria and in the preparation of Figure 6 during her B.Sc. studies. This article has not yet been cited by other publications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"61 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144260621","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}