Chemistry of Materials最新文献

{"title":"Upcycling Polyethylene Terephthalate Plastic to C2 Chemicals in Parallel With Nitrate Reduction to Ammonia or Electric Energy Generation","authors":"Zhentao Tu, Xiaoyang He, Xuan Liu, Dengke Xiong, Shujie Xue, Deli Wu, Jianying Wang, Zuofeng Chen","doi":"10.1021/acs.chemmater.4c03111","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03111","url":null,"abstract":"The resource utilization of waste plastics and nitrogen-containing wastewater has an important environmental impact. Herein, we present self-supporting CuPd alloy nanosheets as bifunctional catalysts for selective electrooxidation of ethylene glycol (EG) from polyethylene terephthalate (PET) hydrolysate to glycolic acid (GA, a C–C bond preserved product with more than 20-time added value) and for efficient electroreduction of nitrate in wastewater to ammonium. Remarkable Faraday efficiencies of ∼93% for GA production and ∼92% for nitrate reduction were achieved. In situ Fourier transform infrared spectroscopy identified crucial intermediates in GA production, elucidating the C–C bond preserved C2 pathway for EG-to-GA conversion. Meanwhile, density functional theory calculations revealed a deeper d-band center arising from the synergistic interaction between Pd and Cu atoms, which facilitates GA desorption, thereby avoiding overoxidation for high selectivity. For nitrate reduction, differential electrochemical mass spectrometry and theoretical calculations were applied, identifying NO₂* hydrogenation as the rate-determining step. Furthermore, we propose an innovative electroforming architecture integrating EG oxidation with a nitrate reduction or oxygen reduction reaction. This architecture, activated by CuPd/NF electrodes, can operate in switching mode throughout the day. It allows the production of high-value GA from PET hydrolysate while simultaneously producing NH₄⁺ in the daytime by coupling with nitrate reduction, or generating electricity during the night by coupling with ORR, offering a competitive solution for resource utilization of wastes.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"82 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143035157","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":"A Metal–Organic Framework Designed for Separation of Liquid Organic Hydrogen Carriers","authors":"Michael T. Scalzo, Ashley L. Sutton, Muhammad Munir Sadiq, Huacheng Zhang, Benny D. Freeman, Timothy F. Scott, Matthew R. Hill","doi":"10.1021/acs.chemmater.4c03074","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03074","url":null,"abstract":"As implied by their name, liquid organic hydrogen carriers (LOHCs) have been proposed as liquid-phase hydrogen storage and transportation media, circumventing the cryogenic conditions and metal embrittlement associated with molecular hydrogen while enabling utilization of existing liquid hydrocarbon infrastructure. A common LOHC example is the methylcyclohexane–toluene system (MTS), where toluene is hydrogenated to afford methylcyclohexane for transport, while the reverse reaction recovers toluene and releases hydrogen at the point of use. Round-trip efficiency of the MTS is low because high conversion from methylcyclohexane to toluene consumes significant energy. Lower conversions produce a mixture of both compounds and separation of LOHC pairs is particularly difficult, owing to the similarity of their molecular sizes. Here, we detail the separation of aromatics and naphthenes with a unique metal–organic framework (MOF). By changing the aromatic ring in the Zr-based MOF UiO-66 to an aliphatic, cubane-based moiety, we found that the resulting MOF, Zr(cub), had consistent aromatic selectivity across a broad pressure range while retaining the high stability of Zr-based MOFs, demonstrated by exposure to both water and toluene. The capacity for LOHC mixture separation avoids the energy demands of high-conversion LOHC dehydrogenation, thereby improving the feasibility of hydrogen as an energy vector.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"13 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027008","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":"Structural and Li-Ion Conduction Properties of Ti- and W-Substituted LiTa2PO8","authors":"Souichi Shima, Takeshi Yajima, Norikazu Ishigaki, Yasutoshi Iriyama","doi":"10.1021/acs.chemmater.4c03139","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03139","url":null,"abstract":"Li⁺-conductive oxide solid electrolytes (SEs) are chemically stable and could potentially lead to safer all-solid-state batteries. However, practical applications of oxide SEs are limited in the current stage, and one of the crucial problems arises from 1 or 2 orders lower ionic conductivity of oxide SEs than sulfide and chloride SEs. Among the various oxide SEs, LiTa₂PO₈ exhibits a high Li⁺ conductivity of 2.5 × 10^–1 mS cm^–1 at room temperature. Because most high Li⁺ conductive oxide SEs such as Li_7–<i>x</i>La₃Zr_2–<i>x</i>Nb_<i>x</i>O₁₂ and Li_1+<i>x</i>Al_<i>x</i>Ti_2–<i>x</i>(PO₄)₃ have been achieved by chemical substitutions from parent compounds (Li₇La₃Zr₂O₁₂ and LiTi₂(PO₄)₃), chemical substitutions for LiTa₂PO₈ will be an effective way for further increasing Li⁺ conductivity. Here, we synthesized single-phase Ti- and W-substituted LiTa₂PO₈ and investigated their Li⁺ conductivities. Both of these substitutions decreased unit cell volume. Ti-substitutions decreased activation energy for Li⁺ conduction in the bulk (<i>E</i>_a) and almost doubled both the total Li⁺ conductivity (σ_total) and bulk Li⁺ conductivity (σ_bulk)_. W-substitutions also decreased <i>E</i>_a, but both the σ_total and the σ_bulk slightly decreased. The calculated <i>E</i>_a of σ_bulk by bond valence energy assuming single-ion hopping increased in both substitutions due to their smaller unit cell volume. On the other hand, experimentally obtained <i>E</i>_a decreased for both substitutions. This discrepancy may arise from the ionic correlation of the Li⁺ ion in LiTa₂PO₈, providing further insight into enhancing the ionic conductivity.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"74 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143026854","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":"Nanomechanical Investigations of Crystals of Copper Nanocluster Isomorphs: Enhanced Hardness of the Low-Density Analogue","authors":"Amoghavarsha Ramachandra Kini, Sanghamitra Debta, Arijit Jana, C. Aparna, Vivek Yadav, Nataliia Kusiak, Tomas Base, Umesh V. Waghmare, Pijush Ghosh, Thalappil Pradeep","doi":"10.1021/acs.chemmater.4c03265","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03265","url":null,"abstract":"Atomically precise cluster crystals, with constituent units composed of tens to hundreds of atoms, are important for the construction of miniaturized solid-state devices. Understanding the mechanical characteristics of such crystals is crucial for these applications. In this study, we focused on the nanomechanical properties of crystals of two isomorphic copper nanoclusters (Cu₄L₄), protected by <i>ortho</i>-carborane-9-thiol, Cu₄(<i>o</i>CBT)₄, and <i>meta</i>-carborane-9-thiol, Cu₄(<i>m</i>CBT)₄. These two clusters possess identical square planar Cu₄ cores embedded in butterfly-shaped Cu₄S₄ staples. Load–displacement measurements indicated that the crystals of Cu₄(<i>o</i>CBT)₄ (hardness of ∼534.31 MPa) were harder than those of Cu₄(<i>m</i>CBT)₄ (hardness of ∼335.49 MPa). Despite their lower density, crystals of Cu₄(<i>o</i>CBT)₄ demonstrated increased hardness, owing to the presence of locked slanted layers that efficiently interacted with each other through various short contact supramolecular interactions. During indentation studies, multiple “pop-in” events were observed for the crystals of both clusters, suggesting the dislocation of molecular layers within the crystal lattice. Dynamic mechanical analysis conducted at different loading frequencies indicated that crystals of Cu₄(<i>o</i>CBT)₄ have a higher storage modulus than Cu₄(<i>m</i>CBT)₄. Both the crystals are thermally robust, as evident from thermogravimetric analysis and attenuated total reflection-IR analysis. Using density functional theory, we calculated Young’s modulus (<i>E</i>_r) for both crystals at 1 and 2% strain and found that the high-density isomorph had a lower <i>E</i>_r, consistent with experimental data showing <i>E</i>_r of Cu₄(<i>o</i>CBT)₄ and Cu₄(<i>m</i>CBT)₄ to be 9.79 and 8.54 GPa, respectively. These findings highlight the significant role of subtle structural differences in governing the nanomechanical behavior of isomorphic cluster crystals, paving the way for their rational design in advanced solid-state device applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"32 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020222","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":"Tracking the Formation of High Entropy Solid Solutions and High Entropy Intermetallics by In Situ X-ray Diffraction and Spectroscopy","authors":"Nicolas Schlegel, Stefanie Punke, Christian M. Clausen, Ulrik Friis-Jensen, Adam F. Sapnik, Dragos Stoian, Olivia Aalling-Frederiksen, Divyansh Gautam, Jan Rossmeisl, Rebecca K. Pittkowski, Matthias Arenz, Kirsten M. Ø. Jensen","doi":"10.1021/acs.chemmater.4c02470","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02470","url":null,"abstract":"The recent focus on high entropy alloys in the field of electrocatalysis has led to a corresponding increase in the interest in nanosizing these materials. Nevertheless, the precise mechanism by which they are formed at low temperatures remains unclear. In this study, we investigate the formation and subsequent growth of PtFeCoNiPd particles following a facile and industrial-scalable incipient wetness impregnation approach using quasi-simultaneous in situ powder X-ray diffraction and X-ray absorption near-edge structure spectroscopy. The initial formation of crystallite domains with a size of 2–3 nm and an fcc structure, which are rich in Pt and Pd, was observed. A continuous incorporation of the nonprecious elements at elevated temperatures leads to crystallite domain growth while maintaining an fcc structure. Upon reaching a temperature of 330 °C, Bragg peaks corresponding to a face-centered tetragonal phase emerge, indicating a transition to an intermetallic species. The degree of ordering was found to be dependent on the atomic ratio of precious to nonprecious elements in the samples, with the synthesis temperature program also influencing this degree of ordering. This suggests the possibility of a synthetic control.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"9 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020218","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":"Adsorption Kinetics-Driven Humidity-Resistant C2H2/CO2 Separation by a Hydrophilic Metal–Organic Framework","authors":"Beibei Sun, Cheng Zeng, Suyun Deng, Yuewen Gu, Lei Gan, Huajun Yang","doi":"10.1021/acs.chemmater.4c03017","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03017","url":null,"abstract":"The separation of C₂H₂/CO₂ under highly humid conditions by using metal–organic frameworks (MOFs) is extremely challenging because water vapor would reduce the C₂H₂ adsorption capacity or even degrade the structure of MOFs. In this work, a zirconium zeolitic metal–organic framework (<b>NNM-5</b>) with a small aperture and large cavities exhibits commendable C₂H₂/CO₂ selectivity (16.6 at 298 K and 1 bar) and a high uptake ratio (3.13 at 298 K and 1 bar). More importantly, <b>NNM-5</b> could maintain at least five breakthrough cycles under highly humid conditions (around 100% RH) without performance degradation compared to that under dry conditions. Our studies indicate that the kinetic mechanism is the key to excellent separation performance under highly humid conditions based on the fact that the material is hydrophilic with a high water uptake, but the diffusion rate of H₂O is 2 orders slower than that of C₂H₂ and CO₂ in <b>NNM-5</b>.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"49 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020220","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":"Metal-Phenolic Chemistry Mediates Assembly of Single-Atom Nanozymes for Cancer Therapy","authors":"Zhiliang Gao, Hongning Sun, Hao-Xin Liu, Han Yang, Yue Hong, Jiwei Cui","doi":"10.1021/acs.chemmater.4c03193","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03193","url":null,"abstract":"Metal-phenolic networks (MPNs) composed of metal ions and polyphenols have gained significant attention as promising approaches for material engineering due to the diverse properties of the ligands and metal ions. Herein, we present a versatile approach for the synthesis of single-atom nanozymes (SAzymes) based on metal-phenolic chemistry. By leveraging the chelating properties of polyphenols with various metal ions, we synthesized a variety of SAzymes (e.g., Fe, Cu, Mn, and Co) via coating metal–organic frameworks with MPNs, followed by pyrolysis. In particular, the engineered Fe single-atom-incorporated nanoparticles, with an FeN₅ nanostructure, exhibit exceptional peroxidase-like activity. This feature makes the engineered FeN₅ SAzymes a potent tool for suppressing tumor cell growth through a synergistic effect with glucose oxidase. This research highlights the desirable coordination chemistry between metal ions and polyphenols for the engineering of SAzymes in biological applications.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"12 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020221","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":"Schizophrenic Shape Memory Hydrogel with Hidden Morphological Information for Transient Encryption","authors":"Jianlei Lu, Chujun Ni, Xin Wen, Xin Guan, Baoyi Wu, Nan Hai, Yang Li, Jiawei Zhang","doi":"10.1021/acs.chemmater.4c02883","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02883","url":null,"abstract":"Inspired by sign language, responsive materials construct an efficient encryption channel via programmable shape morphing, offering a potential solution to the decryption vulnerabilities of existing optical anticounterfeit. However, these pioneering approaches often fail to conceal morphological information due to predictable shape-shifting, let alone achieve higher-level encryption such as multiple and transient information storage. Herein, we report a schizophrenic shape memory hydrogel that can be applied for transient information encryption. In particular, two opposite shape fixation mechanisms, heating-induced aggregation of poly(acrylic acid)-Ca²⁺ (PAAc-Ca²⁺) coordination and cooling-induced clustering of alkyl chain-modified poly(vinyl alcohol) (PVA-C6), are coupled in one system. Through a two-step shape programming process involving alternating heating and cooling, complex morphological information can be hidden within an initially simple shape. During its temperature-triggered shape morphing process, the hydrogel rapidly undergoes shape-shifting to reveal the hidden morphological information, followed by an onset recovery to erase it, thereby achieving a transient information display. This single-triggered multiple shape-shifting system opens an unprecedented pattern-independent channel for existing encryption strategies and can motivate the development of advanced anticounterfeiting materials with integrated multifunctionality.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"25 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143026958","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":"First-Principles High-Throughput Screening and Experimental Verification of III-VIB Transition Metal Chalcogenides Nonlinear Optical Crystals","authors":"Miao Song, Hongbo Huang, Baoli Gao, Yumiao Niu, Ying Wang, Daqing Yang, Bingbing Zhang","doi":"10.1021/acs.chemmater.4c03537","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c03537","url":null,"abstract":"Infrared nonlinear optical materials (IR NLO) have shown important and useful applications in industries and science research. Transition-metal (TM)-based chalcogenides have diverse coordination and broad transparent windows, which make them excellent candidates for IR NLO crystals. However, III-VIB TM-based chalcogenides have been little explored as IR NLO materials. Herein, a first-principles high-throughput screening pipeline (FHSP) has been used for searching promising IR NLO materials in III-VIB TM-based chalcogenides. 89 known TM-based chalcogenides have been selected from 330 noncentrosymmetric (NCS) materials included in the Inorganic Crystal Structure Database (ICSD), which have been systematically surveyed for further investigation. Finally, we successfully synthesized two materials Na₃VS₄ and CuScS₂ with superior predicted performances. The results show that Na₃VS₄ owns balanced properties, such as giant SHG response (4.19 × AGS), reasonable band gap (2.18 eV), suitable birefringence (0.03 @1064 nm), and long shortest IR absorption (abs.) mode (21.7 μm). CuScS₂ has no obvious vibration absorption peak in the region of 4000–400 cm^–1 (2.5–25 μm) and exhibits moderate SHG response (1.44 × AGS). In addition, this work will afford an orientation to discover more crystal materials.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"13 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143026855","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":"Spontaneous Reactions by Atomic Hydrogen – An Extraordinary Reactant for Atomic Layer Deposition of Platinum","authors":"Huong Thi Thuy Ta, Ngoc Linh Nguyen, Anh Kiet Tieu, Hao Van Bui","doi":"10.1021/acs.chemmater.4c02524","DOIUrl":"https://doi.org/10.1021/acs.chemmater.4c02524","url":null,"abstract":"Atomic layer deposition (ALD) has been widely used for the deposition of platinum (Pt) nanostructures, which is conducted by using an organometallic precursor in conjunction with a reactant, commonly oxygen or hydrogen. Whereas the oxygen-based ALD processes might result in the formation of Pt oxides, especially at low temperatures, the use of hydrogen requires a relatively high temperature to initiate the chemical reactions. In this work, we investigate atomic hydrogen as a reactant for ALD of Pt using the MeCpPtMe₃ precursor by density functional theory (DFT) calculations. By calculating the reaction and activation energies for the removal of the precursor ligands by three different reactants, i.e., molecular hydrogen (H₂), molecular oxygen (O₂), and atomic hydrogen (H) following several possible pathways, we find that the reactions with atomic hydrogen are mostly barrierless and spontaneous, which contrast with the high activation and reaction energies required for the reactions with O₂ and H₂. Our study provides insights into the mechanism of the surface reactions between the precursor molecule and the reactant and highlights the significant potential of atomic hydrogen, which could pave a new way for the development of ALD of metals.","PeriodicalId":33,"journal":{"name":"Chemistry of Materials","volume":"24 1","pages":""},"PeriodicalIF":8.6,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020219","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}