CrystEngComm最新文献

{"title":"Deferasirox HOF and its in situ metallization affording a new family of lanthanide coordination polymer-based MHOFs†","authors":"Yue-Mei Cao, Ying He, Xin-Yue Pei, Jia-Xing Liang, Jing Feng, Hong-Yan Wang and Qi-Bing Bo","doi":"10.1039/D4CE01245C","DOIUrl":"https://doi.org/10.1039/D4CE01245C","url":null,"abstract":"<p >Pure organic HOFs (hydrogen-bonded organic frameworks) lack stronger coordination bonds and the presence of some functional sites in their parent structures. Therefore, it is important to graft functional metal ions into single HOF structures <em>via</em> coordination bonds in order to develop highly stable and multifunctional MHOFs (metallo hydrogen-bonded organic frameworks). Deferasirox (<strong>DFX</strong>), which is used as a trifurcated hydrogen-bonded linking agent, is suitable for the construction of dual-self-complementary HOFs. In the absence of deprotonated reagents, <em>in situ</em> metallization of <strong>DFX</strong> HOFs with lanthanide ions in aqueous solutions directly produced a new family of lanthanide coordination polymer-based MHOFs, namely, [Ln<small><sub>2</sub></small>(μ-H<small><sub>2</sub></small>O)(μ-H<small><sub>2</sub></small>L)<small><sub>6</sub></small>]<small><sub><em>n</em></sub></small> (Ln = Ce (<strong>DFX-Ce</strong>), Eu (<strong>DFX-Eu</strong>), Gd (<strong>DFX-Gd</strong>)) and [Tb<small><sub>4</sub></small>(μ-H<small><sub>2</sub></small>O)<small><sub>2</sub></small>(μ-H<small><sub>2</sub></small>L)<small><sub>10</sub></small>(H<small><sub>2</sub></small>O)(H<small><sub>2</sub></small>L)<small><sub>2</sub></small>·2H<small><sub>2</sub></small>O]<small><sub>2<em>n</em></sub></small> (<strong>DFX-Tb</strong>) (H<small><sub>2</sub></small>L = 4-[3,5-bis(2-hydroxyphenyl)-1,2,4-triazol-1-yl]-benzoate anion). Structural studies revealed that these four new compounds exhibited cruciform-like 1D coordination polymer chains with the MHOF structures owing to the presence of pendant flexible robust phenol groups. Solid-state photoluminescence of <strong>DFX-Ce</strong> exhibited the dominant emission of the free <strong>DFX</strong> ligand accompanied by the 5d → 4f transitions of Ce<small><sup>3+</sup></small>, while <strong>DFX-Eu</strong> and <strong>DFX-Tb</strong> displayed the obvious characteristic emissions for the corresponding lanthanide ions based on 4f → 4f transitions. In particular, since the lowest triplet-state energy levels of the <strong>DFX</strong> ligand matched well with the resonance level of Tb<small><sup>3+</sup></small>, <strong>DFX-Tb</strong> exhibited highly efficient photoluminescence compared with <strong>DFX-Eu</strong>. The strongly emissive characteristic of <strong>DFX-Tb</strong> indicated its potential application in fluorescent materials. Furthermore, magnetic property studies of <strong>DFX-Gd</strong> revealed the weak antiferromagnetic interaction between neighboring Gd<small><sup>3+</sup></small> ions and the significant magnetocaloric effect with a large magnetic entropy change. To the best of our knowledge, no lanthanide coordination polymers have been successfully synthesized from the <strong>DFX</strong> ligand or its derivatives thus far, and the presented <em>in situ</em> metallization of the <strong>DFX</strong> HOF with the corresponding lanthanide ions provides","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2175-2189"},"PeriodicalIF":2.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740570","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":"One-step solvothermal in situ synthesis of NiMOF nanosheets for high-performance supercapacitor applications†","authors":"Xiaojing Wang, Fenglian Lu, Zongjin Wu, Kuantao Zhang, Song Li, Rui Tu, Sha Luo, Hongyan Pan, Keliang Wang and Qian Lin","doi":"10.1039/D4CE01318B","DOIUrl":"https://doi.org/10.1039/D4CE01318B","url":null,"abstract":"<p >In this study, NiMOF nanosheets were successfully synthesised on nickel foam using a simple solvothermal method. The nanosheets self-assembled on the nickel foam to form a uniform open pore structure, which allowed the electrode material to expose more active sites. This method avoided the use of insulating binders and additional electrode treatments, simplified the preparation process of NiMOFs, and improved the conductivity and mechanical stability of the electrode materials. The prepared NMF-1 electrode exhibited a specific capacitance of 1238 F g<small>⁻¹</small> at 1 A g<small>⁻¹</small> and maintained a high specific capacitance of 840 F g<small>⁻¹</small> at 5 A g<small>⁻¹</small>. The assembled asymmetric supercapacitor (ASC) exhibited a specific capacitance of 126.56 F g<small>⁻¹</small> at 1 A g<small>⁻¹</small>, specific capacitance retention rate of 81.2% at 5 A g<small>⁻¹</small>, and an energy density of 45 W h kg<small>⁻¹</small> at a power density of 800 W kg<small>⁻¹</small>. These results indicate that mixed solvent-modulated <em>in situ</em> growth of NiMOF nanosheets on nickel foam has great potential in supercapacitor applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1806-1815"},"PeriodicalIF":2.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632288","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":"High crystal quality and purity Cu2O by consecutive in situ annealing and thermal oxidation of Cu under H2 and O2 at elevated temperatures†","authors":"Matthew Zervos, Ioannis Paschos, Pavlos Savvidis, Nikoletta Florini, Konstantinos Koutsokostas, Philomela Komninou, Nektarios N. Lathiotakis, P. M. Levendis and Sarantos Marinakis","doi":"10.1039/D4CE01276C","DOIUrl":"https://doi.org/10.1039/D4CE01276C","url":null,"abstract":"<p >Cu<small>₂</small>O has been obtained <em>via</em> the thermal oxidation of Cu foils with a maximum thickness of 120 μm under Ar and O<small>₂</small> at 1020 °C for 30 min. Care was taken to suppress the oxidation of Cu during the temperature ramp by using H<small>₂</small> prior to admitting O<small>₂</small> at 1020 °C. We suggest that the ruby red Cu<small>₂</small>O crystals are obtained in this way by strain-driven grain growth and consist of ∼500 μm grains that have a cubic crystal structure. More importantly we find that the crystal quality and purity of the Cu<small>₂</small>O is improved significantly by pre-annealing the Cu under Ar and H<small>₂</small> at 1000 °C and 10 mbar for up to 180 min. The Cu<small>₂</small>O exhibited photoluminescence at 6.5 K with a maximum at 2.01 eV corresponding to the direct energy gap in very good agreement with density functional theory calculations of the electronic band structure. No emission due to recombination of bound excitons to copper vacancies V<small>_Cu</small> and single V<small>_O</small> or double charged V<small>_O</small> oxygen vacancies was observed consistent with high crystal quality Cu<small>₂</small>O. We find that the Cu<small>₂</small>O crystals obtained in this way are p-type and the highest mobility measured at room temperature was <em>μ</em><small>_p</small> = 82 cm V<small>⁻¹</small> s<small>⁻¹</small> with a carrier density of 7.3 × 10 cm<small>³</small>.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 13","pages":" 1977-1985"},"PeriodicalIF":2.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce01276c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143688247","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exploring intermolecular interactions and energetics in crystalline substituted thieno[2,3-d]pyrimidines†","authors":"Pran Kishore Deb, Anila M. Menon, Fathima Nida PSR, Ipsha Shruti, Sara Nidal, Katharigatta N. Venugopala and Deepak Chopra","doi":"10.1039/D5CE00071H","DOIUrl":"https://doi.org/10.1039/D5CE00071H","url":null,"abstract":"<p >This study explores the synthesis and crystallographic characterization of eight thieno[2,3-<em>d</em>]pyrimidine derivatives. Keeping in mind their practical importance in different biological applications, the understanding of the crystal structure in terms of the existence of various intermolecular interactions is of relevance. The presence of strong N–H⋯N dimers in the crystal structures of five compounds, followed by N–H⋯O and C–H⋯O interactions in the remaining three compounds, due to the presence of the amide and the sulphonamide substituents, is ascertained from crystal packing analysis. In addition, several weak intermolecular interactions, including C–H⋯π/N/S, S⋯C (σ-hole/π-hole), and S⋯S contacts, contribute towards their additional stability in the crystal. To understand this, the nature and energetics associated with these intermolecular interactions were characterized <em>via Crystal Explorer21.5</em>. Further, the electrostatic complementarity amongst the robust N–H⋯N dimers are evidenced <em>via</em> noticing the large negative and positive molecular surface electrostatic potential (MESP) values across the nitrogen and the hydrogen atoms, respectively. Moreover, <em>carbon-bonding</em> was explicitly described for S⋯C interactions. This implied the participation of the <em>nucleophilic sulphur</em> with the <em>electrophilic carbon atom</em> (either mediated through a σ-hole or a π-hole on the carbon atom). Besides this, the change in the directionality of these interactions, from the linear to the orthogonal orientation for tetrel interactions, was observed and justified through an analysis of the MESP, the deformation density plots and the QTAIM analysis.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2070-2085"},"PeriodicalIF":2.6,"publicationDate":"2025-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d5ce00071h?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Conformational analysis of biomineral proteins interacting with inorganic minerals using dispersive mineral particles for solution NMR","authors":"Kei Futagawa, Yugo Kato and Michio Suzuki","doi":"10.1039/D4CE01253D","DOIUrl":"https://doi.org/10.1039/D4CE01253D","url":null,"abstract":"<p >Minerals formed by living organisms are referred to as biominerals, and the process of their formation is known as biomineralization. These biominerals result from organic–inorganic interactions involving biomineral proteins and minerals. However, the detailed molecular mechanisms underlying these interactions remain unclear due to the lack of established methods for analyzing the conformations of biomineral proteins. Existing conformational analysis techniques, such as X-ray crystallography and cryo-electron microscopy, are insufficient for studying these proteins, as they cannot reveal protein structures on solid surfaces. Solution nuclear magnetic resonance spectroscopy offers high-resolution capabilities for determining protein structures but requires solubilized proteins that can move and rotate freely in liquid solutions. Dispersive mineral particles provide a solid surface for proteins while allowing rotation in solution without inducing anisotropic effects. This novel conformational analysis method using dispersive mineral particles presents a promising approach to elucidate the molecular mechanisms of various biomineral proteins. Furthermore, this insight may enable the synthesis of valuable and eco-friendly mineral materials by mimicking biomineralization processes.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2043-2063"},"PeriodicalIF":2.6,"publicationDate":"2025-02-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ce/d4ce01253d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740537","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Effect of molar ratios on formation, dissolution and physical stability of co-amorphous naringenin–meglumine by integrating theoretical–modeling–experimental techniques†","authors":"Jiawei Han, Wen Sun, Jiaxin Chen, Zhimin Yue, Weitao Fang, Xiaoqian Liu, Jue Wang and Gaorong Wu","doi":"10.1039/D4CE01321B","DOIUrl":"https://doi.org/10.1039/D4CE01321B","url":null,"abstract":"<p >Although the molar ratio is a crucial parameter for co-amorphous formulations, the selection of the molar ratio for their formation and important physicochemical properties is rarely studied during the development process. Herein, this study attempted to explore the influence of molar ratios (3 : 1–1 : 3) on the formation, dissolution and physical stability of co-amorphous naringenin–meglumine (<em>i.e.</em>, NAR–MEG CM) by integrating theoretical–modeling–experimental techniques. The formed NAR–MEG CMs with molar ratios of 1 : 1, 1 : 2 and 1 : 3 were driven by the strong hydrogen bond interactions between the C<img>O group of NAR and the –OH/–NH groups of MEG as confirmed by FTIR and RDF analyses. Among them, NAR–MEG CM (1 : 1) showed significantly enhanced dissolution with long-term supersaturated concentration compared to crystalline NAR, while NAR–MEG CM (1 : 2) and NAR–MEG CM (1 : 3) easily aggregated into clumps during dissolution with the increase of the MEG ratio, causing the gradual decrease in dissolution performance. Meanwhile, NAR–MEG CM (1 : 1) exhibited superior physical stability to NAR–MEG CM (1 : 2) and NAR–MEG CM (1 : 3), because of the decreased binding energy of NAR–MEG molecules with the increase of the MEG ratio from a molecular dynamics perspective. Therefore, 1 : 1 as the optimal molar ratio for NAR–MEG CMs could effectively overcome the water solubility problem of NAR and maintain excellent physical stability. This study offers a unique perspective on the influence of molar ratios on the formation, dissolution and stability of co-amorphous systems through theory–model–experiment techniques, which can be employed as a practicable methodology to guide the further design and performance forecast for co-amorphous formulations.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2124-2135"},"PeriodicalIF":2.6,"publicationDate":"2025-02-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740545","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":"Metal–organic framework-based catalysts toward the electrosynthesis of urea","authors":"Krishna Chattopadhyay, Mousumi Bhul, Prajita Kundu, Manas Mandal and Dilip K. Maiti","doi":"10.1039/D5CE00139K","DOIUrl":"https://doi.org/10.1039/D5CE00139K","url":null,"abstract":"<p >Nitrogen-based fertilizer, primarily urea, production generates 2.1% of global CO<small>₂</small> emissions through the energy-intensive Bosch–Meiser process. Electrochemical urea synthesis offers a sustainable alternative by significantly reducing greenhouse gas emissions and energy consumption. While numerous review articles have focused on the electrocatalytic synthesis of urea using nanostructures or heterostructures composed of transition metal alloys that leverage the synergistic effects of distinct metal catalytic sites, no comprehensive reviews have explored the application of metal–organic frameworks (MOFs) in this context. Following the publication of the <em>Nature Synthesis</em> paper in 2024, which reported a nearly fivefold increase in yield rate compared to existing catalysts, we revisited the electrosynthesis of urea using MOF materials. Over the past two years, a few high-impact papers have been published on MOF-based materials, which have emerged as promising catalysts for electrochemical urea synthesis, demonstrating notable efficiency and stability. This review aims to highlight these MOF-based materials, their catalytic performance, and underlying mechanism in electrocatalytic urea synthesis.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 11","pages":" 1521-1528"},"PeriodicalIF":2.6,"publicationDate":"2025-02-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143602088","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":"Synthesis, characterization, and green to orange luminescence properties of copper(i) complexes with 3-bdppmapy ligand-containing phenanthroline and its derivatives†","authors":"Wen-Long Mou, Si-Jie Fan, Ying-Long Wang, Guo Wang, Fu-Zhen Hu, Gui-Xiong Guo, Hong-Liang Han, Xiu-Lan Xin, Jian-Ming Liu, Yu-Ping Yang, Zhong-Feng Li and Qiong-Hua Jin","doi":"10.1039/D4CE01324G","DOIUrl":"https://doi.org/10.1039/D4CE01324G","url":null,"abstract":"<p >This paper presents the successful synthesis of eight Cu(<small>I</small>) complexes <strong>1–8</strong>, [Cu(phen)(3-bdppmapy)]BF<small>₄</small>·CH<small>₃</small>OH (<strong>1</strong>), [Cu(phen)(3-bdppmapy)]ClO<small>₄</small>·CH<small>₃</small>OH (<strong>2</strong>), [Cu(phen)(3-bdppmapy)]I (<strong>3</strong>), [Cu(phen)(3-bdppmapy)]CF<small>₃</small>SO<small>₃</small> (<strong>4</strong>), [Cu(2,3-<em>f</em>)(3-bdppmapy)]BF<small>₄</small>·CH<small>₃</small>OH (<strong>5</strong>), [Cu(2,3-<em>f</em>)(3-bdppmapy)]ClO<small>₄</small>·CH<small>₃</small>OH (<strong>6</strong>), [Cu(2,3-<em>f</em>)(3-bdppmapy)]I·2CH<small>₃</small>OH (<strong>7</strong>), and [Cu(2,3-<em>f</em>)(3-bdppmapy)]CF<small>₃</small>SO<small>₃</small>·CH<small>₃</small>OH (<strong>8</strong>) (3-bdppmapy<img><em>N</em>,<em>N</em>-bis[(diphenylphosphino)methyl]-3-pyridinamine; phen<img>1,10-phenanthroline; 2,3-<em>f</em><img>pyrazino[2,3-<em>f</em>][1,10]phenanthroline) exhibiting luminescence properties ranging from green to orange emission. Comprehensive characterization and analysis of their structural and photophysical properties were conducted. The results demonstrate that complexes <strong>1–4</strong> and <strong>5–8</strong> possess the same nitrogen ligand, respectively. However, a notable distinction is observed in their fluorescent luminescence position, with complexes <strong>1–4</strong> exhibiting a pronounced blue-shift relative to complexes <strong>5–8</strong>. Further structural analysis demonstrated that the phosphine ligands in complexes <strong>5–8</strong> exhibited markedly disparate spatial configurations and photophysical properties compared to previously studied complexes. This finding demonstrates that the luminescence properties of the complexes can be effectively modulated by the structure of the micromodules. Finally, all the complexes were tested using terahertz time-domain spectroscopy, and the results exhibited a clear regularity, supporting our understanding of the relationship between the structure and photophysical properties of the complexes.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 14","pages":" 2086-2100"},"PeriodicalIF":2.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143740541","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":"Polytypism phenomenon in GaN nanocrystals grown on a van der Waals surface","authors":"Y. E. Maidebura, V. G. Mansurov, T. V. Malin, I. A. Aleksandrov, K. S. Zhuravlev and B. Pecz","doi":"10.1039/D4CE01154F","DOIUrl":"https://doi.org/10.1039/D4CE01154F","url":null,"abstract":"<p >The polytypism phenomenon in the growth of nanostructures reveals new properties and opportunities for bandgap engineering by enabling controlled formation of different phases of the same material with distinct crystalline and electronic structures. In the case of III-nitrides, the occurrence of polytypism is unlikely and has not been experimentally observed to date. Here, we report the discovery of polytypism in GaN nanocrystals (NCs) grown <em>via</em> the vapor–liquid–solid mechanism on the surface of a van der Waals graphene-like SiN structure. Through a detailed analysis of the diffraction patterns, we have established the formation of three structures during the growth of NCs, namely zinc-blende with the (111) plane, the 6H polytype and wurtzite with the non-polar (10−10) plane. As shown by transmission electron microscopy data, the crystal structures form within the volume of a single NC. The formation of zinc-blende and wurtzite phases is explained within the framework of classical nucleation theory, while the 6H polytype nucleates at the boundary between these phases. Calculations indicate the possibility of growing NCs with either pure zinc-blende or wurtzite structures. In essence, this study introduces a new degree of freedom in the growth and application of GaN-based nanostructures grown <em>via</em> the vapor–liquid–solid method.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 15","pages":" 2109-2118"},"PeriodicalIF":2.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143786418","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":"UiO66-NH2@In2O3 heterostructures for improved photocatalytic CO2 reduction†","authors":"Bolin Ma, Guanghui Chen, Lingling Zhou, Chengyang Ni, Xinyu Sun, Lei Zhang, Xinguo Xi, Lanqin Tang and Yong Zhou","doi":"10.1039/D5CE00106D","DOIUrl":"https://doi.org/10.1039/D5CE00106D","url":null,"abstract":"<p >The development of highly efficient photocatalysts for CO<small>₂</small> reduction remains a critical challenge in achieving sustainable energy conversion. In this study, we report the synthesis of a UiO66-NH<small>₂</small>@In<small>₂</small>O<small>₃</small>, integrating UiO66-NH<small>₂</small> metal organic frameworks (MOFs) with indium oxide (In<small>₂</small>O<small>₃</small>) nanoparticles, forming a robust heterostructure. Characterization results demonstrated that calcination at 250 °C for 4 hours yielded a heterostructure with indium uniformly incorporated, as confirmed by XRD, SEM, TEM and ICP-OES analyses. XPS studies revealed significant electronic interactions between UiO66-NH<small>₂</small> and In<small>₂</small>O<small>₃</small>, including shifts in binding energies of indium and zirconium, indicative of chemical bonding. This heterostructure facilitated enhanced charge separation and transfer, as evidenced by photocurrent measurements, leading to superior photocatalytic CO<small>₂</small> reduction performance. Under light irradiation, UiO66-NH<small>₂</small>@In<small>₂</small>O<small>₃</small> achieved a CO production rate of 83.68 μmol g<small>⁻¹</small> during the first hour and a cumulative yield of 485.08 μmol g<small>⁻¹</small> after 7 hours, significantly outperforming pristine UiO66-NH<small>₂</small> and In<small>₂</small>O<small>₃</small>. The superior activity is attributed to the large surface area of UiO66-NH<small>₂</small>, facilitating CO<small>₂</small> adsorption, and the heterojunction formation with In<small>₂</small>O<small>₃</small>, enhancing charge carrier dynamics. These findings highlight the synergistic effects of UiO66-NH<small>₂</small> and In<small>₂</small>O<small>₃</small>, providing insights into the design of advanced photocatalysts for environmental and energy applications.</p>","PeriodicalId":70,"journal":{"name":"CrystEngComm","volume":" 12","pages":" 1781-1788"},"PeriodicalIF":2.6,"publicationDate":"2025-02-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143632285","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}