ACS Materials Au最新文献

{"title":"Excellent Bifunctional Oxygen Evolution and Reduction Electrocatalysts (5A1/5)Co2O4 and Their Tunability","authors":"Xin Wang,&nbsp;Harish Singh,&nbsp;Manashi Nath,&nbsp;Kurt Lagemann and Katharine Page*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00088","DOIUrl":"10.1021/acsmaterialsau.3c00088","url":null,"abstract":"<p >Hastening the progress of rechargeable metal–air batteries and hydrogen fuel cells necessitates the advancement of economically feasible, earth-abundant, inexpensive, and efficient electrocatalysts facilitating both the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR). Herein, a recently reported family of nano (5A_1/5)Co₂O₄ (A = combinations of transition metals, Mg, Mn, Fe, Ni, Cu, and Zn) compositionally complex oxides (CCOs) [Wang et al., <i>Chemistry of Materials</i>, <b>2023,</b> <i>35 (17)</i>, 7283–7291.] are studied as bifunctional OER and ORR electrocatalysts. Among the different low-temperature soft-templating samples, those subjected to 600 °C postannealing heat treatment exhibit superior performance in alkaline media. One specific composition (Mn_0.2Fe_0.2Ni_0.2Cu_0.2Zn_0.2)Co₂O₄ exhibited an exceptional overpotential (260 mV at 10 mA cm^–2) for the OER, a favorable Tafel slope of 68 mV dec^–1, excellent onset potential (0.9 V) for the ORR, and lower than 6% H₂O₂ yields over a potential range of 0.2 to 0.8 V vs the reversible hydrogen electrode. Furthermore, this catalyst displayed stability over a 22 h chronoamperometry measurement, as confirmed by X-ray photoelectron spectroscopy analysis. Considering the outstanding performance, the low cost and scalability of the synthesis method, and the demonstrated tunability through chemical substitutions and processing variables, CCO ACo₂O₄ spinel oxides are highly promising candidates for future sustainable electrocatalytic applications.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 3","pages":"274–285"},"PeriodicalIF":0.0,"publicationDate":"2024-01-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00088","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139506347","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":"Stability of Bimetallic PtxRuy – From Model Surfaces to Nanoparticulate Electrocatalysts","authors":"Attila Kormanyos*,&nbsp;Pascal Büttner,&nbsp;Michael Bosch,&nbsp;Maria Minichova,&nbsp;Andreas Körner,&nbsp;Ken J. Jenewein,&nbsp;Andreas Hutzler,&nbsp;Karl J. J. Mayrhofer,&nbsp;Julien Bachmann and Serhiy Cherevko*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00092","DOIUrl":"10.1021/acsmaterialsau.3c00092","url":null,"abstract":"<p >Fundamental research campaigns in electrocatalysis often involve the use of model systems, such as single crystals or magnetron-sputtered thin films (single metals or metal alloys). The downsides of these approaches are that oftentimes only a limited number of compositions are picked and tested (guided by chemical intuition) and that the validity of trends is not verified under operating conditions typically present in real devices. These together can lead to deficient conclusions, hampering the direct application of newly discovered systems in real devices. In this contribution, the stability of magnetron-sputtered bimetallic Pt_<i>x</i>Ru_<i>y</i> thin film electrocatalysts (0 at. % to 100 at. % Ru content) along with three commercially available carbon-supported counterparts (50–67 at. % Ru content) was mapped under electrocatalytic conditions in acidic electrolytes using online ICP-MS. We found several differences between the two systems in the amount of metals dissolved along with the development of the morphology and composition. While the Pt-rich Pt_<i>x</i>Ru_<i>y</i> compositions remained unchanged, 30–50 nm diameter surface pits were detected in the case of the Ru-rich sputtered thin films. Contrastingly, the surface of the carbon-supported NPs enriched in Pt accompanied by the leaching of a significant amount of Ru from the alloy structure was observed. Change in morphology was accompanied by a mass loss reaching around 1–2 wt % in the case of the sputtered samples and almost 10 wt % for the NPs. Since Pt_<i>x</i>Ru_<i>y</i> has prime importance in driving alcohol oxidation reactions, the stability of all investigated alloys was screened in the presence of isopropanol. While Pt dissolution was marginally affected by the presence of isopropanol, several times higher Ru dissolution was detected, especially in the case of the Ru-rich compositions. Our results underline that trends in terms of electrocatalytic activity and stability cannot always be transferred from model samples to systems that are closer to the ones applied in real devices.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 3","pages":"286–299"},"PeriodicalIF":0.0,"publicationDate":"2024-01-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00092","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139476608","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":"Redox-Active Organic Materials: From Energy Storage to Redox Catalysis","authors":"Jaehwan Kim,&nbsp;Jianheng Ling,&nbsp;Yihuan Lai and Phillip J. Milner*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00096","DOIUrl":"10.1021/acsmaterialsau.3c00096","url":null,"abstract":"<p >Electroactive materials are central to myriad applications, including energy storage, sensing, and catalysis. Compared to traditional inorganic electrode materials, redox-active organic materials such as porous organic polymers (POPs) and covalent organic frameworks (COFs) are emerging as promising alternatives due to their structural tunability, flexibility, sustainability, and compatibility with a range of electrolytes. Herein, we discuss the challenges and opportunities available for the use of redox-active organic materials in organoelectrochemistry, an emerging area in fine chemical synthesis. In particular, we highlight the utility of organic electrode materials in photoredox catalysis, electrochemical energy storage, and electrocatalysis and point to new directions needed to unlock their potential utility for organic synthesis. This Perspective aims to bring together the organic, electrochemistry, and polymer communities to design new heterogeneous electrocatalysts for the sustainable synthesis of complex molecules.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 3","pages":"258–273"},"PeriodicalIF":0.0,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00096","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139459300","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":"Quantitative Structure─Permittivity Relationship Study of a Series of Polymers","authors":"Yevhenii Zhuravskyi,&nbsp;Kweeni Iduoku,&nbsp;Meade E. Erickson,&nbsp;Anas Karuth,&nbsp;Durbek Usmanov,&nbsp;Gerardo Casanola-Martin,&nbsp;Maqsud N. Sayfiyev,&nbsp;Dilshod A. Ziyaev,&nbsp;Zulayho Smanova,&nbsp;Alicja Mikolajczyk* and Bakhtiyor Rasulev*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00079","DOIUrl":"10.1021/acsmaterialsau.3c00079","url":null,"abstract":"<p >Dielectric constant is an important property which is widely utilized in many scientific fields and characterizes the degree of polarization of substances under the external electric field. In this work, a structure–property relationship of the dielectric constants (ε) for a diverse set of polymers was investigated. A transparent mechanistic model was developed with the application of a machine learning approach that combines genetic algorithm and multiple linear regression analysis, to obtain a mechanistically explainable and transparent model. Based on the evaluation conducted using various validation criteria, four- and eight-variable models were proposed. The best model showed a high predictive performance for training and test sets, with <i>R</i>² values of 0.905 and 0.812, respectively. Obtained statistical performance results and selected descriptors in the best models were analyzed and discussed. With the validation procedures applied, the models were proven to have a good predictive ability and robustness for further applications in polymer permittivity prediction.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 2","pages":"195–203"},"PeriodicalIF":0.0,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00079","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139410925","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":"In Situ Engineering of Conducting Polymer Nanocomposites at Liquid/Liquid Interfaces: A Perspective on Fundamentals to Technological Significance","authors":"Mini Mol Menamparambath*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00068","DOIUrl":"10.1021/acsmaterialsau.3c00068","url":null,"abstract":"<p >The conducting polymers have continuously been hybridized with their counterparts to overcome the intrinsic functional limitations compared to the metallic or inorganic analogs. Remarkably, the liquid/liquid interface-assisted methods represent an efficient and facile route for developing fully tunable metamaterials for various applications. The spontaneous adsorption of nanostructures at a quasi-two-dimensional interface is energetically favorable due to the reduction in interfacial tension, interfacial area, and interfacial energy (Helmholtz free energy). This Perspective highlights the fundamentals of nanostructure adsorption leading to hierarchical architecture generation at the interface from an experimentalist’s point of view. Thereafter, the essential applications of the conducting polymer/nanocomposites synthesized at the interface emphasize the capability of the interface to tune functional materials. This Perspective also summarizes the future challenges and the use of the known fundamental aspects in overcoming the functional limitations of polymer/nanomaterial composites and also provides some future research directions.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 2","pages":"115–128"},"PeriodicalIF":0.0,"publicationDate":"2024-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00068","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139083880","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 Principles Guiding Solvent Size Selection in ZIF-Based Type 3 Porous Liquids for Permanent Porosity","authors":"Matthew J. Hurlock,&nbsp;Matthew S. Christian,&nbsp;Jessica M. Rimsza and Tina M. Nenoff*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00094","DOIUrl":"10.1021/acsmaterialsau.3c00094","url":null,"abstract":"<p >Porous liquids (PLs), which are solvent-based systems that contain permanent porosity due to the incorporation of a solid porous host, are of significant interest for the capture of greenhouse gases, including CO₂. Type 3 PLs formed by using metal–organic frameworks (MOFs) as the nanoporous host provide a high degree of chemical turnability for gas capture. However, pore aperture fluctuation, such as gate-opening in zeolitic imidazole framework (ZIF) MOFs, complicates the ability to keep the MOF pores available for gas adsorption. Therefore, an understanding of the solvent molecular size required to ensure exclusion from MOFs in ZIF-based Type 3 PLs is needed. Through a combined computational and experimental approach, the solvent-pore accessibility of exemplar MOF ZIF–8 was examined. Density functional theory (DFT) calculations identified that the lowest-energy solvent–ZIF interaction occurred at the pore aperture. Experimental density measurements of ZIF–8 dispersed in various-sized solvents showed that ZIF–8 adsorbed solvent molecules up to 2 Å larger than the crystallographic pore aperture. Density analysis of ZIF dispersions was further applied to a series of possible ZIF-based PLs, including ZIF–67, −69, −71(RHO), and −71(SOD), to examine the structure–property relationships governing solvent exclusion, which identified eight new ZIF-based Type 3 PL compositions. Solvent exclusion was driven by pore aperture expansion across all ZIFs, and the degree of expansion, as well as water exclusion, was influenced by ligand functionalization. Using these results, a design principle was formulated to guide the formation of future ZIF-based Type 3 PLs that ensures solvent-free pores and availability for gas adsorption.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 2","pages":"224–237"},"PeriodicalIF":0.0,"publicationDate":"2023-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00094","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139064364","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":"Tuning the Mechanical and Dynamic Properties of Elastic Vitrimers by Tailoring the Substituents of Boronic Ester","authors":"Zoriana Demchuk,&nbsp;Xiao Zhao,&nbsp;Zhiqiang Shen,&nbsp;Sheng Zhao,&nbsp;Alexei P. Sokolov and Peng-Fei Cao*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00074","DOIUrl":"10.1021/acsmaterialsau.3c00074","url":null,"abstract":"<p >Elastic vitrimers, i.e., elastic polymers with associative dynamic covalent bonds, can afford elastomers with recyclability while maintaining their thermal and chemical stability. Herein, we report a series of boronic ester-based vitrimers with tunable mechanical properties and recyclability by varying the substitute groups of boronic acid in polymer networks. The dynamic polymer networks are formed by reacting diol-containing tetra-arm poly(amidoamine) with boronic acid-terminated tetra-arm poly(ethylene glycol), which possesses different substituents adjacent to boronic acid moieties. Varying the substituent adjacent to the boronic ester unit will significantly affect the binding strength of the boronic ester, therefore affecting their dynamics and mechanical performance. The electron-withdrawing substituents noticeably suppress the dynamics of boronic ester exchange and increase the activation energy and relaxation time while enhancing the mechanical strength of the resulting elastic vitrimers. On the other hand, the presence of electron-rich substituent affords relatively reduced glass transition temperature (<i>T</i>_g), faster relaxation, and prominent recyclability and malleability at lower temperatures. The developed pathway will guide the rational design of elastomers with well-tunable dynamics and processabilities.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 2","pages":"185–194"},"PeriodicalIF":0.0,"publicationDate":"2023-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00074","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139064214","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":"Activation Energies of Heterogeneous Electrocatalysis: A Theoretical Perspective","authors":"Zachary Levell,&nbsp; and ,&nbsp;Yuanyue Liu*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00071","DOIUrl":"10.1021/acsmaterialsau.3c00071","url":null,"abstract":"<p >Heterogeneous electrochemistry is important for various applications. However, currently, there is limited information about activation energies. In this invited review, we review the challenges associated with calculating these activation energies. Specifically, we highlight three key difficulties in atomistic modeling: liquid structure, electrode potential, and electrolyte ions, along with state-of-the-art methods to address them. We aim to inspire more studies in the field of activation energies to better understand and design heterogeneous electrocatalysts.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 2","pages":"129–132"},"PeriodicalIF":0.0,"publicationDate":"2023-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00071","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138823786","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":"Achieving Precision Healthcare through Nanomedicine and Enhanced Model Systems","authors":"Elin Svensson,&nbsp;Ula von Mentzer and Alexandra Stubelius*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00073","DOIUrl":"10.1021/acsmaterialsau.3c00073","url":null,"abstract":"<p >The ability to customize medical choices according to an individual’s genetic makeup and biomarker patterns marks a significant advancement toward overall improved healthcare for both individuals and society at large. By transitioning from the conventional one-size-fits-all approach to tailored treatments that can account for predispositions of different patient populations, nanomedicines can be customized to target the specific molecular underpinnings of a patient’s disease, thus mitigating the risk of collateral damage. However, for these systems to reach their full potential, our understanding of how nano-based therapeutics behave within the intricate human body is necessary. Effective drug administration to the targeted organ or pathological niche is dictated by properties such as nanocarrier (NC) size, shape, and targeting abilities, where understanding how NCs change their properties when they encounter biomolecules and phenomena such as shear stress in flow remains a major challenge. This Review specifically focuses on vessel-on-a-chip technology that can provide increased understanding of NC behavior in blood and summarizes the specialized environment of the joint to showcase advanced tissue models as approaches to address translational challenges. Compared to conventional cell studies or animal models, these advanced models can integrate patient material for full customization. Combining such models with nanomedicine can contribute to making personalized medicine achievable.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 2","pages":"162–173"},"PeriodicalIF":0.0,"publicationDate":"2023-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00073","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138717558","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":"Tunable Photocatalytic Activity of CoFe Prussian Blue Analogue Modified SrTiO3 Core–Shell Structures for Solar-Driven Water Oxidation","authors":"Naeimeh Sadat Peighambardoust,&nbsp;Sina Sadigh Akbari,&nbsp;Rana Lomlu,&nbsp;Umut Aydemir* and Ferdi Karadas*,&nbsp;","doi":"10.1021/acsmaterialsau.3c00090","DOIUrl":"10.1021/acsmaterialsau.3c00090","url":null,"abstract":"<p >This study presents a pioneering semiconductor-catalyst core–shell architecture designed to enhance photocatalytic water oxidation activity significantly. This innovative assembly involves the in situ deposition of CoFe Prussian blue analogue (PBA) particles onto SrTiO₃ (STO) and blue SrTiO₃ (bSTO) nanocubes, effectively establishing a robust p–n junction, as demonstrated by Mott–Schottky analysis. Of notable significance, the STO/PB core–shell catalyst displayed remarkable photocatalytic performance, achieving an oxygen evolution rate of 129.6 μmol g^–1 h^–1, with stability over an extended 9-h in the presence of S₂O₈^2– as an electron scavenger. Thorough characterization unequivocally verified the precise alignment of the band energies within the STO/PB core–shell assembly. Our research underscores the critical role of tailored semiconductor-catalyst interfaces in advancing the realm of photocatalysis and its broader applications in renewable energy technologies.</p>","PeriodicalId":29798,"journal":{"name":"ACS Materials Au","volume":"4 2","pages":"214–223"},"PeriodicalIF":0.0,"publicationDate":"2023-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsmaterialsau.3c00090","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"138820024","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}