ACS Applied Energy Materials最新文献

{"title":"Na-Ion Storage and Diffusion Behavior in Coal-Based Hard Carbon on the View of Molecular Structure","authors":"Xiangyu Fan,&nbsp;Xirui Kong,&nbsp;Pengtang Zhang,&nbsp;Ben Chong and Jiulin Wang*,&nbsp;","doi":"10.1021/acsaem.4c0325410.1021/acsaem.4c03254","DOIUrl":"https://doi.org/10.1021/acsaem.4c03254https://doi.org/10.1021/acsaem.4c03254","url":null,"abstract":"<p >Sodium storage mechanisms and microstructures play a key role in improving the sodium storage capacity of hard carbon (HC) anodes; however, the storage mechanisms of sodium ions in coal-carbon-derived HC and the effective regulation of microstructures at the molecular level are still scarce. In this work, it is proposed for the first time that the coaling effect affects the microstructure and the Na⁺ diffusion coefficient in coal-derived HCs during their discharge by grafting aryl rings and oxygen-containing functional groups within and between the main chains of the precursors. We propose and confirm two Na⁺ storage mechanisms that are closely related to the coalisation effect. Aromatic rings and oxygen-containing functional groups induce Na⁺ aggregation during Na⁺ diffusion, leading to the formation of metal clusters in low-voltage regions. Therefore, the effects of aromatic rings and oxygen-containing functional groups on the local microstructure of HCs should be considered when designing HCs. In this work, HCs with specific graphite microcrystalline structures were prepared by screening coal precursors, and constraints between graphite microcrystalline parameters and precursors were revealed. This work provides theoretical guidance to study the storage mechanism of Na⁺ through the coalisation effect and offers new ideas for the development of high-performance coal-derived anodes for sodium-ion batteries.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3628–3637 3628–3637"},"PeriodicalIF":5.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675695","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Constructing N- and F-Dual-Doped Pt-Based Heterojunction Catalysts via Synergistic Electronic Modulation for Enhanced Hydrogen Evolution Reaction Activity and CO Tolerance","authors":"Yu Hao,&nbsp;Dongfang Chen*,&nbsp;Dongyi Pu,&nbsp;Song Hu,&nbsp;Pavese Doague Nguela,&nbsp;Pucheng Pei and Xiaoming Xu*,&nbsp;","doi":"10.1021/acsaem.4c0335010.1021/acsaem.4c03350","DOIUrl":"https://doi.org/10.1021/acsaem.4c03350https://doi.org/10.1021/acsaem.4c03350","url":null,"abstract":"<p >The development of efficient and durable hydrogen evolution reaction (HER) electrocatalysts is critical for sustainable energy conversion. Although platinum (Pt) serves as a benchmark HER catalyst, its practical application is hindered by the high cost, limited durability, and susceptibility to CO poisoning. In this work, we report a heterojunction Pt-based catalyst, Pt@NCL-MXene, synthesized by LiF etching of MXene and subsequent NH₃ calcination. This process introduces dual nitrogen (N) and fluorine (F) doping and yields a nitrogen-doped carbon layer (NCL) coating on Pt nanoparticles with an average size of only 3.4 nm. Compared with conventional Pt–C catalysts, Pt@NCL-MXene exhibits a larger specific surface area, enhanced electron transfer efficiency, and an optimized d-band center, thereby facilitating both H* adsorption and desorption. As a result, Pt@NCL-MXene achieves a significantly lower overpotential of 73 mV at a current density of 100 mA cm^–2, alongside improved kinetics and stability under operational conditions. Furthermore, the 9 wt % F-rich MXene support effectively suppresses CO adsorption on Pt, reducing the CO uptake to 0.224 mmol g^–1, which is purportedly lower than that of Pt–C (0.264 mmol g^–1), thereby mitigating CO poisoning and prolonging the catalyst’s service life. These findings offer insights into the rational design of advanced CO-resistant Pt-based HER electrocatalysts.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3745–3753 3745–3753"},"PeriodicalIF":5.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675937","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Lithium-Mediated Nitrogen Reduction in a Flow Electrolyzer Cell Using a Gas-Diffusion Cathode with Carbonaceous Reaction Layers","authors":"Wei Bi,&nbsp;Wenbo Bao,&nbsp;Elod L. Gyenge* and David Pentreath Wilkinson*,&nbsp;","doi":"10.1021/acsaem.5c0000810.1021/acsaem.5c00008","DOIUrl":"https://doi.org/10.1021/acsaem.5c00008https://doi.org/10.1021/acsaem.5c00008","url":null,"abstract":"<p >Lithium-mediated nitrogen reduction (LNRR) shows promise for sustainable NH₃ production, but flow electrolyzers incorporating gas-diffusion electrodes (GDEs) have rarely been studied toward this application. This work investigates cathode GDEs using inexpensive carbonaceous reaction layers to achieve stable and active NH₃ electrosynthesis for over 8 h under pulsed currents. Particularly, the amorphous C45 demonstrates superior durability over Vulcan, Vulcan-supported Pt, and graphitic SFG6L at −5 mA cm^–2. Replacing Nafion with polyvinylidene fluoride as the binder improves the NH₃ production rate (3.11 ± 0.41 μmol h^–1 cm^–2) and Faradaic efficiency (5.0 ± 0.65%), outperforming prior precious-metal-free cathode results.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3294–3300 3294–3300"},"PeriodicalIF":5.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675939","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Synergistic Effect of Fluoroethylene Carbonate and Propylene Carbonate on the Calendar Life of Silicon-Based Lithium-Ion Batteries","authors":"Yuhan Yang,&nbsp;Yong Xie,&nbsp;Xueyin Wu,&nbsp;Yiling Huang,&nbsp;Zhida Chen,&nbsp;Yajuan Ji*,&nbsp;Ronghua Zeng* and Zhongzhi Yuan*,&nbsp;","doi":"10.1021/acsaem.5c0013110.1021/acsaem.5c00131","DOIUrl":"https://doi.org/10.1021/acsaem.5c00131https://doi.org/10.1021/acsaem.5c00131","url":null,"abstract":"<p >The energy density and cycling life of silicon-based lithium-ion batteries (LIBs) rapidly approach their designed targets. However, their calendar life still fails to meet the requirements for long-term stability. In this study, Si/C||LiNi_0.8Mn_0.1Co_0.1O₂ (NCM811) batteries have been constructed from Si/C composites with no graphite and Ni-rich NCM811. The electrolytes used propylene carbonate (PC) or ethylene carbonate (EC) as the base solvent, supplemented with fluoroethylene carbonate (FEC). After 800 cycles, the PC-based electrolyte battery retained 79.7% capacity compared to 70.2% for the EC-based electrolyte. Following storage at 60 °C for 7 days, the PC-based electrolyte battery exhibited a 95% capacity recovery, 56% resistance growth, and 51% gas generation. The EC-based electrolyte battery showed 91%, 70%, and 101%, respectively. Atomic force microscopy (AFM) analyses and Young’s modulus measurements revealed that the PC-based electrolyte facilitated the formation of a thinner, smoother, and denser solid electrolyte interphase (SEI) on the Si/C surface. Furthermore, for the PC-based electrolyte, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) results showed PC promoted FEC reactions, forming a dense, LiF-rich SEI. In contrast, for the EC-based electrolyte, the EC and FEC jointly reacted to form a thicker SEI. Molecular dynamics (MD) simulations showed that for the PC-based electrolyte, approximately 20.4% of the FEC molecules participated in the Li⁺ solvation structure, which was more than the 17.1% obtained for the EC-based electrolyte. Thus, the synergistic effect of PC and FEC resulted in an effective formation of a more stable SEI, which enhanced the cycling performance and calendar life of Si/C. This study offers an economical and effective commercial electrolyte solution for high-energy-density Si/C-based LIBs.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3854–3865 3854–3865"},"PeriodicalIF":5.4,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675936","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Pyrene-Linked Covalent Organic Polymer/Single-Walled Carbon Nanotubes Hybrids as High-Performance Electrodes for Supercapacitive Energy Storage","authors":"Mohamed Gamal Mohamed*,&nbsp;Abdul Basit,&nbsp;Chen-Yu Shih,&nbsp;Santosh U. Sharma,&nbsp;Tapomay Mondal and Shiao-Wei Kuo*,&nbsp;","doi":"10.1021/acsaem.5c0005210.1021/acsaem.5c00052","DOIUrl":"https://doi.org/10.1021/acsaem.5c00052https://doi.org/10.1021/acsaem.5c00052","url":null,"abstract":"<p >Among energy storage devices, covalent organic polymers (COPs) are the prime choice as active electrode materials, which are held together by strong covalent bonds and offer notable advantages such as high specific surface area and exceptional chemical durability. However, certain COPs have limited conductivity and underwhelming electrochemical properties, which hinders their application in supercapacitors (SCs). To address these challenges, we successfully synthesized two types of porous organic polymers, PyTB-BBT COP and PyTB-Py COP, along with graphene oxide (GO) and single-walled carbon nanotubes (SWCNTs) named PyTB-BBT COP/GO, PyTB-BBT COP/SWCNTs, PyTB-Py COP/GO and PyTB-Py COP/SWCNTs, respectively via physical interaction [π–π stacking interactions]. The PyTB-BBT COP and PyTB-Py COP were initially prepared through a Schiff base reaction, using 4,4′,4″,4‴-(pyrene-1,3,6,8-tetrayltetrakis(ethyne-2,1-diyl))tetraaniline (PyTB-4NH₂) as a building block, which was reacted with 4,4′-(benzo[<i>c</i>][1,2,5]thiadiazole-4,7-diyl)dibenzaldehyde (BBT-2CHO) for PyTB-BBT COP, and with 4,4′,4″,4‴-(pyrene-1,3,6,8-tetrayl)tetrabenzaldehyde for PyTB-Py COP. The successful synthesis of PyTB-BBT COP/GO, PyTB-BBT COP/SWCNTs, PyTB-Py COP/GO, and PyTB-Py COP/SWCNTs through π–π stacking interactions were verified using TEM and photoluminescence (PL) measurements. Notably, compared to their pristine counterparts, as well as PyTB-BBT COP/GO (5 wt %) and PyTB-Py COP/GO (5 wt %), the PyTB-BBT COP/SWCNTs (5 wt %) and PyTB-Py COP/SWCNTs (5 wt %) hybrids demonstrate remarkable promise as supercapacitor electrode materials. They exhibit specific capacitances of 185 and 342 F g^–1 at a current density of 0.5 A g^–1, retaining approximately 85% and 92% of their capacity after 10,000 cycles in a three-electrode supercapacitor setup. The outstanding electrochemical performance of the PyTB-Py COP/SWCNTs (5 wt %) hybrid could be caused by three key elements: strong π–π stacking interactions of SWCNTs and PyTB-Py COP, facilitated by the presence of two pyrene units in the PyTB-Py COP framework; the porous structure of PyTB-Py COP, which improves ion transport; and the excellent electron conductivity provided by the SWCNTs.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3764–3778 3764–3778"},"PeriodicalIF":5.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsaem.5c00052","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675797","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Sm Doping-Enhanced Li3VO4/C Electrode Kinetics for High-Performance Lithium-Ion Batteries","authors":"Yuanlang Wan,&nbsp;Xuefang Xie,&nbsp;Shuang Zhou,&nbsp;Weihang Li,&nbsp;Jingkang Ma,&nbsp;Yaqin Zhou,&nbsp;Yijian Song,&nbsp;Ji Zhou and Anqiang Pan*,&nbsp;","doi":"10.1021/acsaem.4c0316610.1021/acsaem.4c03166","DOIUrl":"https://doi.org/10.1021/acsaem.4c03166https://doi.org/10.1021/acsaem.4c03166","url":null,"abstract":"<p >Li₃VO₄ (LVO) presents significant advantages in cost and capacity, making it a promising candidate for next-generation lithium-ion battery (LIB) anodes. However, its low electronic conductivity hampers practical applications. Herein, we report a Sm-modified Li₃VO₄/C composite (LSVO/C) designed for high-performance LIBs. Sm doping introduces additional defects and optimizes the electronic structure of Li₃VO₄, resulting in a significantly enhanced electronic conductivity (2.94 × 10^–3 S cm^–1) of the composites. Furthermore, the carbon-fiber-based framework effectively maintains structural stability during cycling, facilitating superior ion transport kinetics. Benefiting from these enhancements, the LSVO/C composite achieves remarkable discharge capacities of 379.5 mAh g^–1 at 0.25 C and 260.1 mAh g^–1 at 12.5 C. Additionally, an LSVO/C||NCM111 full cell, using LiNi_1/3Co_1/3Mn_1/3O₂ (NCM111) as the cathode, retains a discharge capacity of 50.5 mAh g^–1 after 1000 cycles at 3.0 C, highlighting the potential of LSVO/C for practical applications. This unique method in preparing anode material will open new gates for highly efficient LIBs.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3581–3591 3581–3591"},"PeriodicalIF":5.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675923","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Complexation-Regulated Molecular Ferroelectric Film for Photovoltaic Devices","authors":"Chen Wang,&nbsp;Ruonan Wang,&nbsp;Jiating Li,&nbsp;Chaoran Huang,&nbsp;Xinyu Du,&nbsp;Ruijie Li,&nbsp;Zhicheng Zhou,&nbsp;Guoxiang Zhao,&nbsp;Sihan Zhang,&nbsp;Weiyu Cheng,&nbsp;Hengyu Cao,&nbsp;Xiangle Sun,&nbsp;Qiang Zhang,&nbsp;Lutao Li*,&nbsp;Guifu Zou* and Shan Cong*,&nbsp;","doi":"10.1021/acsaem.4c0305210.1021/acsaem.4c03052","DOIUrl":"https://doi.org/10.1021/acsaem.4c03052https://doi.org/10.1021/acsaem.4c03052","url":null,"abstract":"<p >Large-size grains play a crucial role in enhancing the properties of ferroelectric films and improving device performance. In this work, hydroiodic acid is used as an additive to promote the crystallization of a narrow-band gap molecular ferroelectric film (hexane-1,6-diammonium pentadiammonium). The complex-regulated processes resulted in a significant increase in grain size from 0.2 to 6.4 μm (32-fold enhancement), accompanied by a reduction in band gap, optimization of the energy level structure, and enhancement of ferroelectric properties. The optimized film exhibited nearly a 10-fold improvement in the performance of ferroelectric photovoltaic devices, which is further enhanced after polarization. This study introduces complex regulation strategies for optimizing molecular ferroelectrics, offering valuable insights for future research on molecular ferroelectrics.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3509–3518 3509–3518"},"PeriodicalIF":5.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675799","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Impact of Thin Film Thickness on the Structural, Energetic and Optoelectronic Properties of Two-Dimensional FPEA2(MAn–1)PbnI3n+1 Perovskites","authors":"Israel C. Ribeiro,&nbsp;Felipe D. Picoli,&nbsp;Pedro Ivo R. Moraes,&nbsp;André F. V. Fonseca,&nbsp;Luiz N. Oliveira,&nbsp;Ana Flávia Nogueira and Juarez L. F. Da Silva*,&nbsp;","doi":"10.1021/acsaem.4c0280010.1021/acsaem.4c02800","DOIUrl":"https://doi.org/10.1021/acsaem.4c02800https://doi.org/10.1021/acsaem.4c02800","url":null,"abstract":"<p >Perovskite solar cell devices, composed of solution-processed perovskite layers with thicknesses of a few hundred angstroms, represent a leading technology in thin-film photovoltaics. Here, we performed a theoretical investigation based on <i>ab initio</i> calculations to explore the role of perovskite thin film thickness, with the general formula FPEA₂(MA_<i>n</i>–1)Pb_<i>n</i>I_3<i>n</i>+1, where FPEA represents 4-fluorophenylethylammonium cations and <i>n</i> ranges from 1 to 4 layers. Our findings reveal that increasing the thickness of the inorganic layer significantly influences the structural, energetic, and optoelectronic properties. Enhanced charge transfer within the inorganic framework and stronger organic–inorganic interactions are observed as the effective charge distribution shifts with increasing thickness. Exothermic trends in adsorption and interaction energies highlight the stabilizing effects of van der Waals forces and hydrogen bonding. The PbI₆-octahedra play a critical role in determining the optical activity and the formation of valence and conduction bands. Thicker films exhibit more intense absorption, emphasizing the importance of PbI₆-octahedra in driving optical properties. Moreover, the work function (ϕ) decreases with increasing thickness due to reduced quantum confinement effects, while the nature of polar FPEA molecules induces deviations in ϕ, underscoring the interaction between molecular composition and thickness. Band alignment further reveals strong spin–orbit coupling effects on the conduction band minimum (CBM), influenced by charge-transfer variability from FPEA to halides. These findings provide insights into thickness-dependent properties that are essential for optimizing perovskite-based devices.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3346–3359 3346–3359"},"PeriodicalIF":5.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsaem.4c02800","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675838","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tailoring Ca2+/Li+ Dual-Cation Gel Polymer Electrolytes via Cross-Linking for Reductive and Oxidative Stability in Ca-Metal Batteries","authors":"Takara Shinohara,&nbsp;Kazuaki Kisu*,&nbsp;Shohichi Furukawa,&nbsp;Kenji Zushida and Shin-ichi Orimo*,&nbsp;","doi":"10.1021/acsaem.4c0306510.1021/acsaem.4c03065","DOIUrl":"https://doi.org/10.1021/acsaem.4c03065https://doi.org/10.1021/acsaem.4c03065","url":null,"abstract":"<p >Calcium–metal batteries with polymer electrolytes are emerging as promising next-generation energy systems owing to their high energy density, natural abundance of Ca in the Earth’s crust, and inherent safety. However, developing suitable polymer electrolytes for Ca-metal batteries remains challenging owing to compatibility issues with Ca-metal anodes and high-voltage cathodes. Herein, we report a dual-cation (Ca²⁺/Li⁺) gel polymer electrolyte (GPE), designed using calcium monocarborane (Ca(CB₁₁H₁₂)₂) and adjusting the lithium borohydride (LiBH₄) concentration, which enhanced oxidation stability while maintaining compatibility with Ca metal. The incorporation of the CB₁₁H₁₂^– anion improved the oxidation stability of the electrolyte, increasing the oxidation potential from 2.2 to 2.6 V (vs Ca²⁺/Ca). Cyclic voltammetry and galvanostatic tests demonstrated reversible plating/stripping properties and high stability against Ca-metal anodes. The reversible operation of the Ca-metal battery was confirmed using a titanium disulfide (TiS₂) cathode, which achieved an initial discharge capacity of 188.5 mA h g^–1. Exsitu X-ray diffraction analysis corroborated this finding by revealing crystallographic changes in TiS₂. This Ca-GPE, with its enhanced oxidation stability, paves the way for developing high-voltage Ca metal–polymer batteries.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3519–3527 3519–3527"},"PeriodicalIF":5.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675922","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tuning Intrinsic Electronic Properties via Size-Controlled Hydrothermal Crystalline Transformation from Tetragonal BiVO4 Spheroids to Monoclinic Plates","authors":"Miquel Torras*,&nbsp;Marie-Anne Dourges,&nbsp;Justine Quinet,&nbsp;Anaëlle Demange,&nbsp;Thomas Cottineau,&nbsp;Jean-Pierre Delville,&nbsp;Marie-Helène Delville and Thierry Toupance*,&nbsp;","doi":"10.1021/acsaem.5c0021510.1021/acsaem.5c00215","DOIUrl":"https://doi.org/10.1021/acsaem.5c00215https://doi.org/10.1021/acsaem.5c00215","url":null,"abstract":"<p >This study reports the synthesis of monoclinic clinobisvanite BiVO₄ crystals with well-defined {010} and {110} facets and nanometer sizes through controlled reactant addition and hydrothermal treatment. By adjustment of the Bi³⁺ precursor addition rate, nanoplates with significantly reduced edge length and thickness were obtained compared to conventional microplates. The formation process involves the nucleation of surfactant-coated tetragonal zircon BiVO₄ nanocrystals, which aggregate into spheroids before being transformed into monoclinic clinobisvanite plates. A proposed model explains this size-tuning mechanism through partial dissolution, phase transformation, and facet-selective growth. Reducing the size of tetragonal zircon BiVO₄ spheroids enhanced photocatalytic water oxidation, while for monoclinic clinobisvanite BiVO₄ plates, size reduction had the opposite effect. Photoelectrochemical analysis revealed a shift from n-type behavior in microplates to p-type behavior in nanoplates under negative bias. These findings highlight the need to integrate size control with surface chemistry, bulk doping, and defect engineering to optimize BiVO₄ for catalytic and electronic applications.</p>","PeriodicalId":4,"journal":{"name":"ACS Applied Energy Materials","volume":"8 6","pages":"3929–3941 3929–3941"},"PeriodicalIF":5.4,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143675798","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}