Chemistry of Materials最新文献

{"title":"Multi-Scale Computational Design of Metal–Organic Frameworks for Carbon Capture Using Machine Learning and Multi-Objective Optimization","authors":"Zijun Deng, Lev Sarkisov","doi":"10.1021/acs.chemmater.4c01969","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01969","url":null,"abstract":"In this article, we computationally design a series of metal–organic frameworks (MOFs) optimized for postcombustion carbon capture. Our workflow includes assembling building blocks and topologies into an initial set of hypothetical MOFs, using genetic algorithms to optimize this initial set for high CO₂/N₂ selectivity, and further evaluating the top materials through process-level modeling of their performance in a modified Skarstrom cycle. We identify two groups of MOFs that exhibit excellent process performance: one with relatively small pores in the range of 3–5 Å and another with larger pores of 6–30 Å. The performance of the first group is driven effectively by the exclusion of N₂ from adsorption, with binding sites able to accommodate only CO₂ molecules. The second group, with larger pores, features binding sites where CO₂ molecules form multiple interactions with oxygen and functional groups of several building blocks, leading to a high CO₂/N₂ selectivity. Within the employed process model and its assumptions, the materials generated in this study substantially outperform 13X reference zeolites, in silico optimized ion-exchanged LTA zeolites, and CALF-20. While this study does not address the synthesizability, stability, or water interactions of the proposed materials, it marks a significant step forward in developing practical MOFs for carbon capture in three key areas. First, it introduces a generative workflow based on the process-level performance of new materials. Second, it identifies structural features of optimal MOFs for carbon capture, which can serve as design guidelines for future development. Finally, the potential existence of numerous promising materials offers hope that some may progress to laboratory testing and eventual scale-up.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317381","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":"Optoelectronic Properties of PbS Nanocrystals Preserved through L-Type Ligand Surface Reactivity","authors":"Christian Y. Dones Lassalle, Jillian L. Dempsey","doi":"10.1021/acs.chemmater.4c01287","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01287","url":null,"abstract":"In this work, ¹H NMR and photoluminescence spectroscopies have been leveraged to identify how amine-terminated molecules react with the surface of oleate-capped PbS nanocrystals (NCs) and impact their optical properties. The alkyl amine undec-10-ene-1-amine binds weakly to the NC surface and promotes the displacement of the native Z-type ligand Pb(oleate)₂. Through systematic experiments, we deconvolute the parallel reaction mechanisms that drive this reactivity. The binding and displacement reactivity results in a net-zero change in the NC emission, attributed to preservation of the electronic structure of PbS NCs through surface restructuring. The photoluminescence of PbS NCs remains robust even when exposed to bulky chelating diamines that exclusively promote displacement of Z-type ligands, reactivity that slightly quenches NC emission by exposing undercoordinated chalcogenides and forming trap states. This work improves fundamental understanding of NC surface reactivity with L-type ligands and their potential impact in developing improved NCs.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313530","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":"Fast Sodium-Ion Conducting Amorphous Oxychloride Embedding Nanoparticles","authors":"Kota Motohashi, Hirofumi Tsukasaki, Shigeo Mori, Atsushi Sakuda, Akitoshi Hayashi","doi":"10.1021/acs.chemmater.4c02104","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02104","url":null,"abstract":"Developing materials with high sodium-ion conductivities is crucial for improving the electrochemical performance of all-solid-state batteries. Halide solid electrolytes are promising owing to their high conductivity, formability, and oxidation stability. However, state-of-the-art sodium-ion-conducting halides are not as high in conductivity as expected and lack reduction stability. In this study, we report oxychlorides in a ternary system NaCl–TaCl₅–Ta₂O₅ with high conductivities, formabilities, and oxidation and reduction stabilities. The mechanochemically prepared samples are composed of NaCl and Ta₂O₅ nanoparticles embedded in an Na–Ta–Cl–O amorphous matrix, possessing ionic conductivities of 2.5 × 10^–3 S cm^–1 at 25 °C and electrochemical potential windows of 0.4–4.1 versus Na⁺/Na. Compression tests reveal that the nanoparticles in the oxychloride electrolytes improve the mechanical strength. Our findings will facilitate the development of solid electrolytes composed of nanoparticles balanced with high ionic conductivities, formabilities, and electrochemical stabilities.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313563","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":"Enhanced Performance of La2NiO4+δ Oxygen-Transporting Membranes Using Crystal Facet Engineering via Microemulsion-Based Synthesis","authors":"Giamper Escobar Cano, Merle Wellmann, Frank Steinbach, Moritz Thiem, Wenjie Xie, Anke Weidenkaff, Armin Feldhoff","doi":"10.1021/acs.chemmater.4c01570","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01570","url":null,"abstract":"La<sub>2</sub>NiO<sub>4+δ</sub> nanorods, synthesized via reverse microemulsion─a crystal facet engineering method─served as building blocks for developing oxygen transport membranes. Comparisons were drawn with ceramic membranes derived from commercial La<sub>2</sub>NiO<sub>4+δ</sub> nanoparticles. The membrane manufacturing process involved either conventional sintering or the field-assisted sintering technique/spark plasma sintering. The microstructure analysis of the initial powders and the resulting ceramics was thoroughly assessed by X-ray diffraction, scanning and transmission electron microscopy as well as energy-dispersive X-ray spectroscopy. As a consequence of the reaction conditions, the nanorods possess an orthorhombic crystal structure, with LaOBr present as a minor phase. Furthermore, the surface structure of the La<sub>2</sub>NiO<sub>4+δ</sub> nanorods was discerned via selected area electron diffraction, revealing a composition of (001)<sub>o</sub>-type and (1<i></i><span style=\"color: inherit;\"></span><span data-mathml='<math xmlns=\"http://www.w3.org/1998/Math/MathML\" display=\"inline\"><mover><mi mathvariant=\"normal\">1</mi><mo accent=\"true\" stretchy=\"false\">¯</mo></mover></math>' role=\"presentation\" style=\"position: relative;\" tabindex=\"0\"><nobr aria-hidden=\"true\"><span style=\"width: 0.571em; display: inline-block;\"><span style=\"display: inline-block; position: relative; width: 0.514em; height: 0px; font-size: 110%;\"><span style=\"position: absolute; clip: rect(1.139em, 1000.4em, 2.332em, -999.997em); top: -2.156em; left: 0em;\"><span><span><span style=\"display: inline-block; position: relative; width: 0.514em; height: 0px;\"><span style=\"position: absolute; clip: rect(3.128em, 1000.4em, 4.151em, -999.997em); top: -3.974em; left: 0em;\"><span style=\"font-family: STIXMathJax_Main;\">1</span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span><span style=\"position: absolute; clip: rect(3.185em, 1000.34em, 3.582em, -999.997em); top: -4.259em; left: 0.06em;\"><span style=\"font-family: STIXMathJax_Main;\">¯</span><span style=\"display: inline-block; width: 0px; height: 3.98em;\"></span></span></span></span></span><span style=\"display: inline-block; width: 0px; height: 2.162em;\"></span></span></span><span style=\"display: inline-block; overflow: hidden; vertical-align: -0.059em; border-left: 0px solid; width: 0px; height: 1.066em;\"></span></span></nobr><span role=\"presentation\"><math display=\"inline\" xmlns=\"http://www.w3.org/1998/Math/MathML\"><mover><mi mathvariant=\"normal\">1</mi><mo accent=\"true\" stretchy=\"false\">¯</mo></mover></math></span></span><script type=\"math/mml\"><math display=\"inline\"><mover><mi mathvariant=\"normal\">1</mi><mo accent=\"true\" stretchy=\"false\">¯</mo></mover></math></script>0)<sub>o</sub>-type facets on the sides and (110)<sub>o</sub>-type facets at the end, with additional facets observed between these surfaces. Among the sintering techniqu","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142313529","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":"Simultaneous Co-localized TiO2 Etching and W Atomic Layer Deposition Using WF6 as a Dual-Functional Reactant","authors":"Hannah R. M. Margavio, Noel Arellano, Ishwar Singh, Rudy Wojtecki, Gregory N. Parsons","doi":"10.1021/acs.chemmater.4c01773","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01773","url":null,"abstract":"Thin film deposition and etching are two of the most widely used chemical processes in semiconductor manufacturing, and they are commonly carried out in distinct processing steps. In this work, we investigate low-temperature (250 °C) surface reactions that occur when a TiO₂ surface undergoes chemical vapor etching, while at the same time, a layer of W metal is deposited at the location where the TiO₂ was etched. The W deposition is performed using SiH₄/WF₆ exposures in an atomic layer deposition (ALD) sequence, where the WF₆ provides a dual function as a precursor for W ALD and a reactant for TiO₂ etching. Exposing TiO₂ to WF₆ leads to the formation of a mixed TiWO_<i>x</i>F_<i>y</i> surface layer that can be volatilized (i.e., etched) by further WF₆ exposure. However, exposing the TiWO_<i>x</i>F_<i>y</i> to SiH₄ promotes surface reduction so that subsequent WF₆ exposure promotes W deposition. Introducing a controlled partial pressure of SiH₄ in a SiH₄/WF₆ ALD sequence allows etching of TiO₂ to continue but also promotes simultaneous W ALD so that the deposition and etch reactions “compete” for available WF₆. Notably, the resulting W layer is formed at the location originally occupied by TiO₂, thereby demonstrating “etch-replacement deposition.” In this case, the etch reactants are able to diffuse through the deposited W layer allowing more than 15 nm of TiO₂ etching and 20 nm of W deposition. The results presented here provide insights into the interactions between deposition and etching reaction mechanisms, creating new opportunities for integrated atomic layer processing.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306232","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":"Strong Magnetic Exchange Interactions and Delocalized Mn–O States Enable High-Voltage Capacity in the Na-Ion Cathode P2–Na0.67[Mg0.28Mn0.72]O2","authors":"Euan N. Bassey, Howie Nguyen, Teresa Insinna, Jeongjae Lee, Anne-Laure Barra, Giannantonio Cibin, Peter Bencok, Raphaële J. Clément, Clare P. Grey","doi":"10.1021/acs.chemmater.4c01320","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01320","url":null,"abstract":"The increased capacity offered by oxygen-redox active cathode materials for rechargeable lithium- and sodium-ion batteries (LIBs and NIBs, respectively) offers a pathway to the next generation of high-gravimetric-capacity cathodes for use in devices, transportation and on the grid. Many of these materials, however, are plagued with voltage fade, voltage hysteresis and O₂ loss, the origins of which can be traced back to changes in their electronic and chemical structures on cycling. Developing a detailed understanding of these changes is critical to mitigating these cathodes’ poor performance. In this work, we present an analysis of the redox mechanism of P2–Na_0.67[Mg_0.28Mn_0.72]O₂, a layered NIB cathode whose high capacity has previously been attributed to trapped O₂ molecules. We examine a variety of charge compensation scenarios, calculate their corresponding densities of states and spectroscopic properties, and systematically compare the results to experimental data: ²⁵Mg and ¹⁷O nuclear magnetic resonance (NMR) spectroscopy, <i>operando</i> X-band and <i>ex situ</i> high-frequency electron paramagnetic resonance (EPR), <i>ex situ</i> magnetometry, and O and Mn <i>K</i>-edge X-ray Absorption Spectroscopy (XAS) and X-ray Absorption Near Edge Spectroscopy (XANES). <i>Via</i> a process of elimination, we suggest that the mechanism for O redox in this material is dominated by a process that involves the formation of strongly antiferromagnetic, delocalized Mn–O states which form after Mg²⁺ migration at high voltages. Our results primarily rely on noninvasive techniques that are vital to understanding the electronic structure of metastable cycled cathode samples.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306484","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":"The Recovery of All-Metals and Fluorine Resources from Used Lithium-Ion Batteries","authors":"Le Ma, Ziwei Zhang, Sisi Liu, Xuan Qin, Weidong Zhou","doi":"10.1021/acs.chemmater.4c01513","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01513","url":null,"abstract":"Lithium-ion battery (LIB) recycling is of critical importance, but previous efforts mainly focused on recovering transition metals (TMs), while overlooking the regaining of Li-resources and the control of fluorine pollution. Here, we propose a strategy for recovering both lithium and TMs from the electrolyte and cathode of used LIBs while simultaneously addressing fluorine pollution. The recovery process involves extracting lithium and 1/6 of F from LiPF₆ in the electrolyte, forming LiF at a yield of 93.0%. The remaining 5/6 F in LiPF₆ is captured by NaOH and transforms into NaF in a yield of 93.9%. Different recovery routes of Li and TMs in the cathode were compared, including formic-acid leaching, and following direct recalcination, formic-acid leaching and then separating TM and Li using different precipitants. Furthermore, the recovered salts can be used in the repreparation of LiNi_<i>x</i>Co_<i>y</i>Mn_<i>z</i>O₂ (<i>x</i> + <i>y</i> + <i>z</i> = 1). This work presents a cost-efficient strategy for the comprehensive recovery of all-metals from used LIBs and fixation of fluorine simultaneously.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306257","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":"Luminescent Thermometer Systems Dy3+/Eu3+ and Tb3+/Sm3+ Based on Coordination Compounds: New Pairs to the Approved Tb3+/Eu3+?","authors":"Maksim A. Zhernakov, Alexander E. Sedykh, Yuriy G. Denisenko, Maxim S. Molokeev, Ildar I. Mirzayanov, Jonathan Becker, Valery G. Shtyrlin, Klaus Müller-Buschbaum","doi":"10.1021/acs.chemmater.4c01851","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01851","url":null,"abstract":"This work addresses a comprehensive study of six new complexes of the constitution [Ln(MeDPQ)₂Cl₃] (Ln³⁺ = Sm³⁺, Eu³⁺, Gd³⁺, Tb³⁺, Dy³⁺, and Y³⁺; MeDPQ─2-methyldipyrido-[3,2-f:2′,3′-h]-quinoxaline) with good thermal stability up to 446 °C. Statistical substitution of Sm³⁺, Tb³⁺, Gd³⁺, and Dy³⁺ with a second Ln³⁺ ion led to [Ln_1–<i>x</i>Ln′_<i>x</i>(MeDPQ)₂Cl₃] solid solutions, which exhibit temperature-dependent luminescent properties. Their visible emission and intensity ratios of transitions vary with temperature in the range of 253–353 K. In the case of the composition [Tb_1–<i>x</i>Eu_<i>x</i>(MeDPQ)₂Cl₃], the maximum relative thermal sensitivity <i>S</i>_r values were determined as 3.77% K^–1, 3.97% K^–1, and 3.97% K^–1 for <i>x</i>(Eu³⁺) = 0.01, 0.05, and 0.1, respectively. The compositions [Dy_1–<i>x</i>Eu_<i>x</i>(MeDPQ)₂Cl₃] and [Tb_1–<i>x</i>Sm_<i>x</i>(MeDPQ)₂Cl₃] also showed significant performance. For the pair Dy³⁺–Eu³⁺, the <i>S</i>_r values were determined as 3.88%K^–1, 3.91% K^–1, and 3.80% K^–1 for <i>x</i>(Eu) = 0.01, 0.05, and 0.1, respectively. For the pair Sm³⁺–Tb³⁺, the <i>S</i>_r values are 3.28% K^–1 and 3.82% K^–1 for <i>x</i>(Sm) = 0.9 and 0.1, respectively. The largest thermal sensitivity value <i>S</i>_r of 4.11% K^–1 was achieved for the composition [Gd_0.8Tb_0.18Eu_0.02(MeDPQ)₂Cl₃]. In addition, patterns of thermometric performance are bound to the energy transfer efficiency Tb³⁺ → Eu³⁺, Dy³⁺ → Eu³⁺ → Dy³⁺, and Tb³⁺ → Sm³⁺, as this characteristic is strongly temperature-dependent in the studied range.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246853","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":"Interpenetrated Metal–Organic Framework Glass","authors":"Cheng Luo, Yong-Sheng Wei, Zeyu Fan, Ellan K. Berdichevsky, Taichi Nishiguchi, Haoyang Shi, Siquan Zhang, Yusuke Nishiyama, Hiroki Yamada, Satoshi Horike","doi":"10.1021/acs.chemmater.4c01912","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01912","url":null,"abstract":"Metal–organic framework (MOF) glass having a three-dimensional interpenetrated structure was prepared by a mechanical milling treatment of the corresponding interpenetrated crystal structure. Synchrotron X-ray analyses, solid-state NMR spectroscopy, and infrared/impedance spectroscopies support that the mechanical milling treatment weakened the intermolecular hydrogen bonds between the adjacent networks while maintaining the original coordination bond connectivity found in the crystalline state. The interpenetrated structure in a glassy state allows for high molecular dynamics, resulting in a soft bulk glass with lower Young’s modulus and hardness compared to most MOF glasses reported.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246854","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":"p–d Orbital Hybridization in Pd3Sn Metallic Aerogels Boosts Alcohol Electrooxidation","authors":"Liheng Guan, Hui Fu, Ting Zhu, Cun Chen, Zhe Zhang, Yecan Pi, Nan Zhang, Tianxi Liu","doi":"10.1021/acs.chemmater.4c01878","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c01878","url":null,"abstract":"Orbital engineering of nanomaterials has been proven to be a compelling strategy, which stimulates the synthesis of palladium (Pd)-based nanomaterials with p–d orbital hybridization and the exploration of their electrocatalytic properties. Herein, Pd₃Sn metallic aerogels (Pd₃Sn MAs) with p–d orbital hybridization were reasonably constructed as efficient electrocatalysts for alcohol electrooxidation. In particular, the mass activity and specific activity of Pd₃Sn MAs for the ethylene glycol oxidation reaction are 1.69 A mg_Pd^–1 and 3.56 mA cm_Pd^–2, respectively, superior to Pd MAs and commercial Pd/C. Meanwhile, benefiting from the excellent antipoisoning properties, Pd₃Sn MAs still maintain satisfactory activity after long-term durability tests. Moreover, the same trend can be observed in reactions such as the methanol oxidation reaction, the ethanol oxidation reaction, and the glycerol oxidation reaction. Furthermore, density functional theory calculations reveal that the p–d orbital hybridization of Pd₃Sn MAs precisely regulates the electronic structure and d-band center of Pd and also decreases the reaction energy barrier in the rate-determining step, thus reactivating the surface of Pd₃Sn MAs. This study provides a broad prospect for the design of efficient fuel cell electrocatalysts through orbital engineering.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":null,"pages":null},"PeriodicalIF":8.6,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142246299","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}