化学•材料最新文献

{"title":"Solid Solution Engineering via Zr Doping in the Pd/ZrInOx Catalyst Switches Reaction Pathways for Enhanced Methanol Production from CO2","authors":"Zhefeng Li,Hao Li,Zhuo Chen,Yongbin Zhong,Wentao Du,Tongyun Zhang,Jingwen Xu,Shengxuan Luo,Yuxiang Mao,Rongxin Xia,Jun Cheng","doi":"10.1021/acs.jpcc.6c05338","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c05338","url":null,"abstract":"The Pd/In2O3 catalyst is promising for CO2-to-methanol conversion, yet it is limited by poor stability and sluggish conversion of formate intermediates. Replacing the In2O3 support in Pd/In2O3 with an In2O3-based solid solution, such as ZrInOx, is an effective strategy to balance activity and stability. However, how the Zr species regulates the Pd/In2O3 catalyst, especially its effect on the reaction pathway, remains unclear. Herein, by introducing atomically dispersed Zr on the Pd/In2O3 catalyst, we demonstrate an electronic disparity strategy to tune the reaction pathway for efficient CO2-to-methanol production. Characterizations confirm that Zr promotes oxygen vacancy formation and enhances the dispersion of Pd nanoparticles. These enhance the electronic metal–support interaction between Pd and the support to accelerate the electron transfer from Pd to the support, thereby making the In sites more electron-rich and Pd more electron-deficient, as well as enhancing CO2 adsorption and H2 dissociation. Theoretical studies show that during the reaction, the In sites at the oxygen vacancy and Pd species work in synergy to induce cleavage of the C═O bond in CO2 and switch the formate pathway to the RWGS+CO* hydrogenation pathway. Consequently, the Pd/ZrInOx catalyst achieved an 18% CO2 conversion with 710 gMeOH kgcat–1 h–1 methanol space-time yield at 300 °C and 5 MPa. This work highlights the influence of the solid solution structure on the CO2 hydrogenation process.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"41 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374872","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Rapid and Green One-Pot Synthesis in Water: Accessing Polypeptides with Two Disulfide Bridges","authors":"Bin Zhang,Cunlin Wang,Zirui Lü,Yongbiao Guo,Zhenhua Gao,Yulong Li,Xiandong Dai,Fanhua Meng","doi":"10.1021/acs.joc.6c00846","DOIUrl":"https://doi.org/10.1021/acs.joc.6c00846","url":null,"abstract":"Regioselective assembly of multiple disulfide bonds in peptides remains a formidable challenge in synthetic peptide chemistry. In this work, a rapid, eco-friendly one-pot strategy for the regioselective synthesis of polypeptides bearing two disulfide bonds was developed. The first disulfide bond was formed via hydrogen peroxide-mediated oxidation of dithiol precursors in water, and the second was subsequently established through iodine-triggered deprotection of two acetamidomethyl (Acm) groups under acidic conditions. Using this protocol, a series of bioactive bicyclic peptides with diverse disulfide topologies were efficiently synthesized, with overall isolated yields ranging from 54% to 74%. Remarkably, this method exhibits excellent tolerance toward Trp- and Tyr-containing peptides with no detectable oxidative byproducts; nevertheless, it cannot be applied to Met-bearing peptides, as the thioether side chain of methionine undergoes preferential oxidation. In contrast to previously reported one-pot synthetic methodologies, this approach eliminates buffers and metallic reagents, simplifies the reaction workflow, and employs pure water as the exclusive solvent alongside inexpensive, commercially available reagents. Accordingly, it serves as a mild, efficient, and environmentally benign alternative for the synthesis of two-disulfide-bridged peptides.","PeriodicalId":57,"journal":{"name":"Journal of Organic Chemistry","volume":"1 1","pages":""},"PeriodicalIF":4.354,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374802","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Elucidation of Mg-Ion Diffusion Factors in Mg–O-Based Materials Using Machine-Learning Interatomic Potentials and Causal Analysis","authors":"Keisuke Makino,Koichi Gocho,Haruka Okada,Naoto Tanibata,Hayami Takeda,Ryo Kobayashi,Masayuki Karasuyama,Masanobu Nakayama","doi":"10.1021/acs.jpcc.6c04722","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c04722","url":null,"abstract":"Mg-ion batteries are promising next-generation energy-storage systems because Mg metal offers high volumetric capacity, abundant resources, and intrinsic safety. However, Mg2+ usually diffuses slowly in solids because of its strong interaction with surrounding anion frameworks and cation environments. Here, Mg–O-based candidate materials extracted from The Materials Project were investigated to clarify the compositional and structural factors governing Mg-ion diffusion. Representative materials were selected by clustering composition descriptors and structural descriptors derived from radial distribution functions (RDFs) and angular distribution functions (ADFs). High-throughput molecular dynamics simulations using an M3GNet-based machine-learning interatomic potential were then performed to construct a Mg-ion diffusion-coefficient data set. LightGBM regression, SHAP-based feature importance analysis, and nonlinear NOTEARS causal discovery were integrated to analyze the hierarchical relationships among descriptors and log D. The inferred causal structure indicates that Mg-ion diffusion is not governed by a single compositional factor. Instead, composition affects the short- and medium-range order of the oxygen framework, which regulates the local Mg environment and migration-pathway connectivity. Excessively close-packed and ordered oxygen frameworks restrict Mg-ion migration, whereas moderately disordered oxygen frameworks can promote continuous migration-accessible sites around Mg ions. These results suggest that Mg-ion-conducting oxides should be designed by controlling the oxygen framework and Mg local environment through host-cation selection, particularly using lightweight host materials containing d-block cations with sizes similar to that of Mg.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"9 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374873","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Unveiling the Phase Transformation Mechanism in BN from Large-Scale Machine Learning Molecular Dynamics","authors":"Jaeyoung Cho,Nikhil Rampal,Stephen E. Weitzner,Graeme Henkelman,Liwen F. Wan","doi":"10.1021/acs.jpclett.6c02892","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02892","url":null,"abstract":"Boron nitride (BN) exhibits rich polymorphism, including cubic, hexagonal, rhombohedral, and wurtzite phases, whose dynamic transformations govern the stability and performance of BN-based materials in modern electronics, quantum photonics, and energy devices. Despite their technological importance, the atomistic mechanisms underlying its phase evolution remain poorly understood. Here, we use large-scale molecular dynamics simulations with a MACE-based machine learning interatomic potential. The potential is trained on high-fidelity density functional theory data and validated against ab initio molecular dynamics simulations to investigate phase transformation pathways in crystalline BN. We identify a layer-by-layer transformation mechanism that is initiated at heterogeneous BN interfaces, where local structural reconstruction propagates into neighboring crystalline regions. We further show that the transformation propensity depends on the interfacial structure and crystallographic orientation. These results provide atomistic insight into BN phase transformations under diverse thermodynamic conditions, while the associated MACE training workflow offers a generalizable framework for studying phase transformation mechanisms in other complex materials.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"18 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374868","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ionizing Radiation Sustains Fenton Oxidation through Radiolytic Fe Redox Cycling for Deep Mineralization of Refractory Pollutants","authors":"Shizong Wang,Yong Liu,Xiaoyong Shu,Zhiwen Jiang,Jianlong Wang","doi":"10.1021/acs.est.6c12956","DOIUrl":"https://doi.org/10.1021/acs.est.6c12956","url":null,"abstract":"The limited regeneration of Fe(II) from Fe(III) constrains sustained oxidation and mineralization in conventional Fenton processes. Here, we investigate an ionizing radiation-assisted Fenton process (IRFP) in which radiolytic Fe redox cycling sustains Fe-mediated oxidation. Using sulfasalazine as a model pollutant, we demonstrate that radiolytically generated hydrated electrons support two coupled pathways: rapid H2O2 activation and the conversion of Fe(III) to Fe(II). The resulting Fe redox cycling dynamically replenishes the Fe(II) pool alongside radiolytic H2O2 activation, thereby sustaining oxidative transformation beyond the initial degradation stage. Compared with irradiation and conventional Fenton treatment, IRFP promoted deeper fragmentation of azo, sulfonamide, and aromatic structures, resulting in enhanced mineralization. Transformation-product analysis further showed that continued transformation in IRFP reduced the persistence of complex intermediates with elevated predicted toxicity. In real pharmaceutical and coking wastewaters, IRFP achieved effective treatment under near-neutral conditions with substantially lower H2O2 and Fe(II) requirements than Fenton treatment and lower absorbed doses than irradiation alone. Although its electricity demand remained higher than short-time Fenton treatment, the markedly lower dosage of chemicals reduced the potential iron sludge burden and resulted in lower estimated COD-normalized treatment costs under the investigated conditions. These findings establish radiolytic Fe redox cycling as a strategy for sustaining Fe-mediated oxidation and promoting deeper transformation and mineralization of refractory pollutants.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"20 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374757","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Charge Transfer from Ammonia Neutralizes Propylene Oxide Cations: Implications for the Astrochemistry of Chiral Molecules","authors":"Sanjana Maheshwari,Darya Kisuryna,Leah G. Dodson","doi":"10.1021/acs.jpclett.6c02696","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c02696","url":null,"abstract":"Propylene oxide is the first of only two chiral species observed to date in the interstellar medium but little is known about the chemistry that leads to a detectable abundance of this molecule in Sagittarius B2. We used a glow-discharge ion source and a room-temperature ion trap to study the neutralization reactions necessary to convert propylene oxide cation (PpO+)─the assumed precursor for propylene oxide in space─into the observed astrochemical. We found that the charge-transfer reaction between PpO+ and ammonia (NH3) proceeds with a pressure-independent rate coefficient of (1.39 ± 0.03) × 10–12 cm3 s–1 to neutralize PpO+ and form the radical cation NH3+ ⁠. Although this measured rate coefficient is much slower than that predicted by capture theories, the high abundance of NH3 in Sagittarius B2 motivates the inclusion of this reaction in astrochemical models. We hypothesize that the low ionization energies of many chiral molecules important to origin-of-life theories means these species may exist as cations in the interstellar medium.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"64 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374869","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Photoregulated Oxidase-Mimicking and Antibacterial Activity with Cascade Catalysis Probed by Copper Nanoclusters","authors":"Khokan Paria,Paritosh Mahato,Preeti Sagarika,Chandan Sahi,Saptarshi Mukherjee","doi":"10.1021/acs.jpclett.6c03102","DOIUrl":"https://doi.org/10.1021/acs.jpclett.6c03102","url":null,"abstract":"The development of light-responsive metal nanoclusters (MNCs) for showcasing photoregulated biomimicking catalysis and developing light-mediated potent antibacterial agents remains a central attraction of the present research. However, strategic modulation of the electronic structure in MNCs to impart light-triggered biocatalysis and antibacterial activity is associated with formidable challenges. In this study, the multidimensionally served enzymatic features in tyramine-protected CuNCs (Cu@Tyra NCs) have been comprehensively investigated, which display efficient peroxidase-like activity and a biocatalytic cascade upon coupling with a suitable natural enzyme. Upon visible light activation, photoexcited charge carriers in the Cu@Tyra NCs promote the generation of a hydroxyl radical (•OH) as a reactive oxygen species (ROS), which significantly enhances the catalytic efficiency. The photoinduced ROS also imparts strong antibacterial effects against Gram-negative bacteria (Escherichia coli) by inducing oxidative damage to cell membranes and intracellular components, exclusively in the presence of light.","PeriodicalId":62,"journal":{"name":"The Journal of Physical Chemistry Letters","volume":"17 1","pages":""},"PeriodicalIF":6.475,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374897","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Thermal Activation under Electrochemical Conditions: CO and N2 Bond Dissociation on Co(B5)","authors":"Mohd Riyaz,Alexander Bagger","doi":"10.1021/acs.jpcc.6c06722","DOIUrl":"https://doi.org/10.1021/acs.jpcc.6c06722","url":null,"abstract":"In aqueous electrocatalytic environments, the protonation of stable *CO and *N2 to *COH/*CHO and *NNH is fundamentally challenged by the competing hydrogen evolution reaction (HER). In this context, direct dissociation of these molecules offers an alternative pathway, forming reactive *C or *N fragments that can be reduced further if surface bonding is not too strong. However, the strong C≡O and N≡N bonds make dissociation challenging under ambient electrochemical conditions, and the extent to which solvent, local field, and electrolyte ions can promote bond dissociation remains unclear. In this work, we quantify these dissociation pathways at a Co(B5) step site using density functional theory, implicit-solvent calculations, and explicit-solvent calculations using enhanced sampling with machine-learned interatomic potential (MLIP). Implicit-solvent calculations reveal only weak sensitivity to dielectric constant, dipole moment, and solvent radius, with barrier variations typically ≤0.1 eV. In contrast, the local H-bonding network in explicit-solvent simulations lowers the dissociation barrier by ∼0.3 eV relative to vacuum by stabilizing the dissociating atoms. Across different solvents and aqueous solutes, the barrier correlates qualitatively with hydrogen-bond donor strength, pKa, and the local H-coordination number near the transition-state region. Interfacial cations (Li+ and Cs+) modify the work function but do not significantly change the dissociation barrier compared with pure water, suggesting that solvent-mediated interactions dominate under the studied conditions.","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"151 1 1","pages":""},"PeriodicalIF":4.126,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374899","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Far-UVC Activation of Performic Acid Enables Concurrent Oxidative and Reductive Micropollutant Abatement","authors":"Hailin Wen,Senhao Lu,Chii Shang,Chuanjing Lin,Zijun Dong,Jingyun Fang,Ran Yin","doi":"10.1021/acs.est.6c11907","DOIUrl":"https://doi.org/10.1021/acs.est.6c11907","url":null,"abstract":"Conventional UV-driven advanced oxidation and reduction processes generally emphasize one redox regime and can be inhibited by wastewater constituents. Here, we characterize the photochemistry of performic acid (PFA) under 222 and 254 nm irradiation and evaluate the capacity of PFA solution, prepared from H2O2 and formic acid and thus containing residual H2O2 and formate, to generate concurrent oxidative and reductive pathways. Relative to 254 nm, 222 nm irradiation increased the fluence-normalized photodecay rate constants of neutral PFA (PFA0) and its conjugate base (PFA–) by 1.21- and 3.81-fold, respectively. The increase arose from 16.1- and 10.1-fold larger molar absorption coefficients at 222 nm, despite lower fitted innate quantum yields (0.367 and 0.804 molecule photon–1 at 222 nm versus 0.587 and 0.819 molecule photon–1 at 254 nm). The UV222/PFA solution system generated the reductant •CO2– together with oxidative HO• and oxygen-centered organic radicals. Pathway analysis attributed 34% of carbamazepine removal to •CO2– and 19% of naproxen removal to R-O• at 222 nm. Chloride and bromide enhanced fluence-normalized degradation through reactive-halogen chemistry; the largest increases were observed for carbamazepine (47.5-fold at 254 nm and 21.9-fold at 222 nm). In real municipal wastewater, UV222/PFA solution decreased total organic carbon by 33.5% within 60 min, compared with 21.6% under UV254/PFA solution, at an initial PFA concentration of 80 μM. These results suggest far-UVC activation of PFA solution as a dual-redox treatment platform, with the observed advantages maintained in the tested wastewater effluents.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"37 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374756","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Microplastics Rapidly Sink and Beach in a Whole-Lake Experiment","authors":"Chelsea M. Rochman,Matthew J. Hoffman,Diane M. Orihel,Michael D. Rennie,Michael J. Paterson,Jennifer F. Provencher,Rebecca Rooney,Francis Nuamah,Desiree Langenfeld,Rachel N. Cable,Garth A. Covernton,Mira Ghosh,Stephanie D. Graves,Eden K. Hataley,Ludovic Hermabessiere,Emily Johnson,Jihyun Olivia Kim,Celia Konowe,Yael Lewis,Brenda Li Ludena,Rachel McNamee,Madeleine H. Milne,Katie Massue-Monat,Émilie C. Montreuil Strub,Keenan Munno,Ashlyn Nance,Natasha de Almeida Neves,Meredith Omer,J. Drew Thompson,Cody Veneruzzo,Hannah Vonberg,Jessica Wilson,Susanne Brander,Melissa Duhaime,Paul Helm,Scott N. Higgins,Timothy Hoellein,Kenneth M. Jeffries,Barbara A. Katzenback,Mark L. Mallory,Bailey McMeans,Matthew Robertson,Dimple Roy,Anna Christina Tyler,Tony R. Walker","doi":"10.1021/acs.est.6c09040","DOIUrl":"https://doi.org/10.1021/acs.est.6c09040","url":null,"abstract":"Although advances in oceanographic and limnological modeling have increased our understanding of microplastic transport and persistence, we require more knowledge to effectively protect biodiversity. We initiated a whole-lake experiment (the pELAstic project) to measure the real-world fate and transport of microplastics. We added microplastics to a boreal lake, simulating stormwater input, at loading concentrations predicted to achieve environmentally relevant concentrations. Here, we introduce our experiment and describe the particle budget from the first microplastic addition. We observed rapid transport of microplastics to different ecosystem compartments. Transport patterns could not be fully explained by initial particle size and density, highlighting how natural processes modify plastic fate in real-world systems. Microplastic fragments rapidly redistributed─exiting the water column and settling on the bottom and shorelines. A particle budget across the water column, bottom sediments, and beaches accounted for 77% of the polyethylene, 48% polystyrene, and >100% polyethylene terephthalate. “Missing” plastic was likely in the nearshore littoral. Our observations suggest that if we prevent further inputs to aquatic ecosystems, microplastics will quickly disappear from the water column─washing up on shorelines and settling on the bottom. Thus, understanding rates of microplastic deposition and burial is critical to forecast the legacy of microplastic pollution.","PeriodicalId":36,"journal":{"name":"环境科学与技术","volume":"88 1","pages":""},"PeriodicalIF":9.028,"publicationDate":"2026-11-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149374762","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}