Rare Metals最新文献

{"title":"Dense homogeneous hetero-interfacial coupling between amorphous Mo–N and crystalline Mo2N for enhanced sodium-ion storage","authors":"Yao-Hui Qu,&nbsp;Zi-Juan Luo,&nbsp;Mao-Hui Yu,&nbsp;Yang Pan,&nbsp;Wen-Xiu He,&nbsp;Shu-Xiao Hu,&nbsp;Ling-Feng Zhu,&nbsp;Fan-Yan Zeng","doi":"10.1007/s12598-024-03144-3","DOIUrl":"10.1007/s12598-024-03144-3","url":null,"abstract":"<div><p>Optimizing the interfacial environments of electrodes has emerged as an effective strategy to improve their electrochemical properties. Amorphous/crystalline interfacial coupling can effectively utilize the advantages of amorphous materials to optimize the interfacial structure for efficient Na⁺ storage. Herein, the dense homologous amorphous/crystalline heterointerfaces are in situ achieved in N-doped carbon nanobundles via self-polymerization and precise nitriding (Mo–N/Mo₂N@C). The amorphous Mo–N rich in unsaturated vacancy defects provides abundant active sites with isotropic ion-transport channels, and can effectively alleviate structural stress from crystalline Mo₂N. Meanwhile, the conductive Mo₂N can facilitate effective electron transfer, augmented further by the carbon encapsulation. Theoretical calculations reveal that the dense heterointerfaces can optimize the electronic structure and shift the d-p orbital centers of Mo and N upward, thereby enhancing the adsorption and mobility of Na⁺, and ultimately improving the charge transport and storage efficiency of the electrode. The Mo–N/Mo₂N@C as an anode delivers a 46.9% increase in reversible capacity over Mo₂N@C, reaching 461.1 mAh·g^–1 at 0.1 A·g^–1, along with improved rate capability and cycling stability, underlining its practical utility. These results suggest that the homologous interfacial coupling can boost the storage properties of nitrides, providing a valuable reference for improving the properties of electrodes with low theoretical capacities.</p><h3>Graphic abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3827 - 3838"},"PeriodicalIF":9.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938543","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Enhanced strain of BiFeO3-BaTiO3 relaxor ferroelectrics ceramics: domain structure evolution induced by electric-fields and temperature","authors":"Yi-Jin Hao,&nbsp;Xiao-Qi Gao,&nbsp;Yu-Cheng Tang,&nbsp;Le-Tian Xie,&nbsp;Hao-Yu Xu,&nbsp;Xiao-Xiao Zhou,&nbsp;Jin-Hao Hu,&nbsp;Huan Liu,&nbsp;He-Zhang Li,&nbsp;Bo-Ping Zhang","doi":"10.1007/s12598-024-03139-0","DOIUrl":"10.1007/s12598-024-03139-0","url":null,"abstract":"<div><p>The study of BiFeO₃-0.3BaTiO₃ ceramics has gained significant attention due to their high Curie temperature (<i>T</i>_C ≥ 450 °C) and excellent piezoelectric properties (<i>d</i>₃₃ ≥ 200 pC·N⁻¹). These are particularly pronounced near the morphotropic phase boundary (MPB) region where coexisting rhombohedral and pseudocubic (R-PC) phases are observed. In addition, as the BaTiO₃ content increases, BiFeO₃-BaTiO₃ ceramics gradually become dominated by a single pseudocubic (PC-) phase. This shift results in a decrease in piezoelectric properties but an enhancement in strain performance. However, the underlying mechanism remains unclear. The high strain properties observed in non-MPB compositions provide a motivation for further investigation into these mechanisms. This paper presents a detailed analysis of the electric-field and temperature-induced domain structure evolution in BiFeO₃-0.4BaTiO₃, which is predominately characterized by the PC phase. Piezoresponse force microscope (PFM) observations reveal the presence of nanodomains and stripy domains associated with polar nanoregions (PNRs), as well as relaxor ferroelectrics (RFEs) and/or ferroelectrics (FEs). The RFEs exhibit a significantly better strain response than the FEs, providing direct evidence for the enhanced strain properties of RFEs. Elevated-temperature Raman spectroscopy confirms a decrease in B-O bonding and BO₆ deformation, along with an increase in structural symmetry, indicating the formation of RFEs and/or PNRs. The phase diagram shows the Burns temperature (<i>T</i>_B), dielectric maxima temperature (<i>T</i>_m) and freezing temperature (<i>T</i>_f) evaluated from the dielectric spectra; the temperature-induced evolution of domain structures; and the sequential quasi-dielectric states: PNRs, RFEs and FEs. The evolution of the domain structure, including the morphology and ratio of FEs, RFEs and PNRs, induced by either electric-fields or temperature strongly affects the strain properties of RFEs. A superior piezoelectric coefficient of <i>d</i>₃₃^* = 533 pm·V⁻¹ at 40 kV·cm⁻¹ and a large electric strain of <i>S</i>_uni = 0.285% are obtained. These results further validate that domain modulation can effectively enhance the strain properties of BiFeO₃-BaTiO₃ ceramics, which makes them promising candidates for actuator applications.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 4","pages":"2661 - 2671"},"PeriodicalIF":9.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143786456","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of BiVO4/CdS Z-type heterojunction for sunlight-driven degradation of quinolone antibiotics","authors":"Wen-Wen Chen,&nbsp;Fang-Fang Huang,&nbsp;Qing-Yun Qu,&nbsp;Lei Li,&nbsp;Jian-Feng Jia,&nbsp;Ding-Sheng Wang,&nbsp;Ya-Dong Li","doi":"10.1007/s12598-024-03174-x","DOIUrl":"10.1007/s12598-024-03174-x","url":null,"abstract":"<div><p>Antibiotics are crucial medications for preventing and treating bacterial infections. However, due to their inherent resistance to degradation, they are also a major component of water pollutants. Semiconductor photocatalysis is considered to be an important green technology for sewage treatment. In this study, BiVO₄/CdS Z-type heterojunction was synthesized and applied in the photocatalytic degradation of tetracycline hydrochloride (TCH). The Z-type heterojunction not only facilitates the separation of photogenerated charges, but also preserves photogenerated electrons with strong reduction capability and photogenerated holes with high oxidation capability. Following visible light irradiation for 90 min, the efficiency of BiVO₄/CdS photocatalytic degradation of TCH reached 93.1%. Moreover, BiVO₄/CdS demonstrates notable degradation efficacy toward other quinolone antibiotics. Free radical trapping experiments and EPR test results suggest that superoxide radicals, hydroxyl radicals, photogenerated electrons, and holes serve as the primary active species in the photocatalytic degradation process of tetracycline hydrochloride. This study offers valuable insights into the development of Z-type heterojunction photocatalysts for the efficient degradation of tetracycline hydrochloride.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3970 - 3980"},"PeriodicalIF":9.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938540","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Exceptional degradation of organic pollutant through piezoelectric photocatalysis and peroxymonosulfate activation in the designed Bi4O5Br2/BCZT S-scheme heterojunction","authors":"Feng Huang,&nbsp;Wen-Lin Wang,&nbsp;Gang Li,&nbsp;Muhammad Humayun,&nbsp;Qian Yu,&nbsp;Yan Wang,&nbsp;Chun-Dong Wang,&nbsp;Jing Wang","doi":"10.1007/s12598-024-03203-9","DOIUrl":"10.1007/s12598-024-03203-9","url":null,"abstract":"<div><p>Peroxymonosulfate (PMS) is commonly used in advanced oxidation processes to degrade organic pollutants in wastewater. In this work, to obtain better PMS activation efficiency, Bi₄O₅Br₂/BCZT (BBT) piezoelectric photocatalyst was designed. Abundant active radicals produced by BBT under visible light irradiation and ultrasonic vibration were used to activate PMS, thereby achieving rapid degradation of high concentration pollutants. With the introduction of BCZT, the catalyst has a strong internal electric field and three-dimensional lamellar structure, which promotes the separation and transfer of electrons and holes. It is worth noting that under optimal reaction conditions, the degradation rate of ARB reached 93% by BBT15 within 10 min. The catalytic experiment combined with the piezoelectric performance test results revealed the key role of piezoelectric photocatalytic reaction in PMS activation. This provides an important prospect for PMS to effectively deal with the degradation of high concentrations of organic pollutants.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3981 - 3994"},"PeriodicalIF":9.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938542","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Relationship of grain size to the physicochemical properties and osteogenesis in magnesium–zinc–calcium alloys for bone implants","authors":"Shu-Quan Zhang,&nbsp;Jiang-Tao Feng,&nbsp;Zhi-Gang Cui,&nbsp;Ai-Min Zhang,&nbsp;Chao-Kun Tang,&nbsp;Ran Pang,&nbsp;Xing-Long Zhang,&nbsp;Chen-Guang Li,&nbsp;Feng-Xin Zhou,&nbsp;Feng Xue,&nbsp;Hao Wang,&nbsp;Jing-Yu Zhang,&nbsp;Qing-Hong Song,&nbsp;Min-Fang Chen,&nbsp;Bin Yao,&nbsp;Shao-Yuan Lyu,&nbsp;Bao-Shan Xu","doi":"10.1007/s12598-024-03160-3","DOIUrl":"10.1007/s12598-024-03160-3","url":null,"abstract":"<p>Magnesium–zinc–calcium alloy has emerged as a key focus in the field of medical degradable materials due to its excellent biodegradability and osteoconductive properties. Grain size is crucial for the physicochemical and biological properties of Mg–Zn–Ca alloy, but it has not been clearly elucidated yet. In this research, Mg-1Zn-0.2Ca-1.0MgO with different grain sizes were prepared to investigate the effect of grain size on the physicochemical properties, corrosion resistance, and osteogenesis. The results indicate that grain refinement improves the mechanical properties and enhances the corrosion resistance of the alloy. The bone surface area to bone volume ratio, bone surface area to tissue volume ratio, and bone volume fraction of the 0.6–0.8 μm group show significantly better performance compared to the 2–3 μm group and 5–6 μm group, indicating that grain refinement can promote the osseointegration between alloy and natural bone. This may be achieved by enhancing the metabolic intensity of alanine, aspartate, glutamate, serine, and glycine around the implant. This work illustrates the effect of grain size on the osseointegration of bone implants and provides a reference for optimizing the properties of bone implant alloys.</p>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"4191 - 4207"},"PeriodicalIF":9.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938262","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Zn3V3O8 nanorods with outstanding electrochemical kinetics as novel anode for aqueous ammonium-ion batteries","authors":"Xiao-Yu Wen,&nbsp;Wei Li,&nbsp;Han Chen,&nbsp;Wei Zhou,&nbsp;Kai-Xiong Xiang","doi":"10.1007/s12598-024-03227-1","DOIUrl":"10.1007/s12598-024-03227-1","url":null,"abstract":"<div><p>Aqueous ammonium-ion batteries (AAIBs) showed great potential in large-scale energy storage systems due to their low-cost, ultrafast kinetics, plentiful resources, inherent security and environmental friendliness. Herein, the well-dispersed Zn₃V₃O₈ nanorods and agglomerated MnV₂O₄ nanoparticles were prepared and firstly used as anodes for AAIBs. The ultrafast reaction kinetics and NH₄⁺ diffusion kinetics of Zn₃V₃O₈ were confirmed by systematically contrasting with MnV₂O₄. Specifically, Zn₃V₃O₈ delivered perfect cyclic performances with 82.6% capacity retention after 500 cycles. When coupled with the β-MnO₂ cathode, the β-MnO₂//Zn₃V₃O₈ full batteries submitted a maximum energy density of 86 Wh·kg⁻¹ and a maximum power density of 677 W·kg⁻¹. The phase transformation from Zn₃V₃O₈ to Zn₃(OH)₂V₂O₇·2H₂O during the first charge process and the reversible building/breaking behaviors of hydrogen bonds during the NH₄⁺ insertion/extraction processes were discussed by ex situ technology analyses. Thus, the fresh perceptions on the phase transformation laws and the hydrogen bonds evolution mechanisms could enrich the fundamental understanding of the NH₄⁺ storage mechanism, and promote the development of the practical applications for Zn₃V₃O₈ in aqueous ammonium-ion batteries.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3881 - 3892"},"PeriodicalIF":9.6,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938538","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Single-atom rhodium mimicking the oxidase and peroxidase for NADH cascade oxidation","authors":"Hong-Jin Xue,&nbsp;Meng Zhang,&nbsp;Yong-Qing Li,&nbsp;Chao-Ran Liu,&nbsp;Xin-Yu Ma,&nbsp;Qin-Bin He,&nbsp;Yin-Chuan Wang,&nbsp;Jin-Xing Chen,&nbsp;Jian-Feng Qiu","doi":"10.1007/s12598-024-03221-7","DOIUrl":"10.1007/s12598-024-03221-7","url":null,"abstract":"<div><p>Constructing high-performance nanozymes for specific biomolecules is crucial but challenging for practical applications and fundamental research. Herein, through the examination of the catalytic reaction paths of natural nicotinamide adenine dinucleotide (NADH) oxidase (NOX), a novel and efficient single-atom rhodium catalyst (Rh₁/NC) was developed to mimic NOX. The Rh₁/NC demonstrated the ability to catalyze the dehydrogenation of NADH and transfer electrons to O₂ to generate H₂O₂ through the typical two-electron pathway. Furthermore, our findings revealed that Rh₁/NC exhibits the ability to catalyze the conversion of produced H₂O₂ into OH under mildly acidic conditions. This process amplifies the oxidation of NADH, showcasing NADH peroxidase-like activity (NPx-like). As a paradigm, this unique dual enzyme-like property of Rh₁/NC with a positive feedback effect holds significance in disrupting cancer cellular homeostasis. Rh₁/NC can effectively consume NADH via cascade biocatalytic reactions within cancer cells, further triggering the elevation of reactive oxygen species (ROS), leading to impaired oxidative phosphorylation and decreased mitochondrial membrane potential, thus damaging the adenosine triphosphate (ATP) synthesis. The resulting 'domino effect' interferes with the energy metabolism homeostasis of cancer cells, ultimately promoting cell apoptosis. This study provides potential guidance for the rational design of materials with greater capabilities.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"4025 - 4037"},"PeriodicalIF":9.6,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938517","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multi-interface engineering of FeS2/C/MoS2 with core–shell structure for superior microwave absorption performance","authors":"Pan-Pan Zhou,&nbsp;Cheng-Yao Hu,&nbsp;Shi-Lin Yuan,&nbsp;Jian-Cheng Zhao,&nbsp;Ya-Wei Kuang,&nbsp;Han Gu,&nbsp;Yu-Shen Liu,&nbsp;Li-Xi Wang,&nbsp;Qi-Tu Zhang","doi":"10.1007/s12598-025-03264-4","DOIUrl":"10.1007/s12598-025-03264-4","url":null,"abstract":"<div><p>Heterojunction and morphology control assume a significant part in adjusting the intrinsic electromagnetic properties of absorbers to acquire outstanding microwave absorption (MA) performance, but this still faces huge challenges. Herein, FeS₂/C/MoS₂ composite with core–shell structure was successfully designed and prepared via a multi-interface engineering. MoS₂ nanosheets with 1T and 2H phases are coated on the outside of FeS₂/C to form a porous interconnected structure that can optimize the impedance matching characteristics and strengthen the interfacial polarization loss capacity. Remarkably, as-fabricated FCM-3 harvests a broad effective absorption bandwidth (EAB) of 5.12 GHz and a minimum reflection loss (RL_min) value of −45.1 dB. Meanwhile, FCM-3 can accomplish a greatest radar cross section (RCS) reduction value of 18.52 dB m² when the detection angle is 0°. Thus, the convenient computer simulation technology (CST) simulations and encouraging accomplishments provide a novel avenue for the further development of efficient and lightweight MA materials.</p><h3>Graphical abstract</h3><div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"4095 - 4106"},"PeriodicalIF":9.6,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938518","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Integration of interface engineering and La doping to boost two-electron oxygen reduction to hydrogen peroxide over La2Sn2O7@La-doped ZnSnO3 heterostructures","authors":"Yan-Yan Sun,&nbsp;Kun Li,&nbsp;Muhammad Arif,&nbsp;Lei Han,&nbsp;Amjad Nisar,&nbsp;Ting Zhu","doi":"10.1007/s12598-024-03224-4","DOIUrl":"10.1007/s12598-024-03224-4","url":null,"abstract":"<div><p>Perovskite oxides have shown great potential application in fuel cells due to the unique crystal structures and tunable composition as well as effective capability toward the oxygen reduction reaction (ORR), whereas the investigation on the electrocatalytic performance of perovskite oxides toward the two-electron ORR to H₂O₂ production remains very limited. Herein, a facile synthetic method has been developed to prepare La₂Sn₂O₇@La-doped ZnSnO₃ heterostructures comprising of amorphous La₂Sn₂O₇ and crystalline La-doped ZnSnO₃. The optimal La₂Sn₂O₇@La-doped ZnSnO₃ heterostructures catalyst exhibits a significantly improved two-electron ORR performance to H₂O₂ production with onset potential of 0.77 V and large current density of 2.51 mA·cm⁻² at 0.1 V compared to ZnSnO₃ (0.75 V, 1.80 mA·cm⁻², 0.11 mA) as well as maintains high H₂O₂ selectivity of 80%, which has been theoretically demonstrated to be contributed to the synergistic effect of amorphous La₂Sn₂O₇ and crystalline La-doped ZnSnO₃. Moreover, high H₂O₂ yield rate of 2.9 mM·h⁻¹ at 0.1 V can be achieved with a superior turnover frequency (TOF) of 3.31 × 10⁻² s⁻¹ compared to the ZnSnO₃ catalyst (2.10 × 10⁻² s⁻¹). This work reveals the great potential of perovskite oxide as promising candidates for the environmentally friendly synthesis of hydrogen peroxide.</p><h3>Graphical abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div><div><p>Perovskite oxide-based La-doped ZnSnO₃ (La₂Sn₂O₇@La-doped ZnSnO₃) heterostructures were prepared as a high-efficient electrocatalyst, delivering a high H₂O₂ yield rate of 2.9 mmol·L⁻¹·h⁻¹ at 0.1 V.\u0000</p></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"3934 - 3942"},"PeriodicalIF":9.6,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Additive-free oxidation of isochromans with molecular oxygen synergistically catalyzed by mixed-addendum polyoxometalate-based coordination polymers","authors":"Zou-Guang Han,&nbsp;Ling-Ling Dai,&nbsp;Hong-Rui Tian,&nbsp;Xiang-Yu Ren,&nbsp;Jie Lian,&nbsp;Bao-Kuan Chen,&nbsp;Yan-Feng Bi","doi":"10.1007/s12598-024-03120-x","DOIUrl":"10.1007/s12598-024-03120-x","url":null,"abstract":"<div><p>Attaining the selective oxidation of isochroman into isochromanone in a molecular oxygen (O₂) environment without any additives, via a heterogeneous oxidation process, is highly desirable and challenging work. Herein, we prepare two mixed-addendum polyoxometalate-based coordination polymers of the general formula [H_<i>x</i>M_1-<i>x</i>(<i>i</i>-Pr-Im)₄][H₂N(CH₃)₂]₄[HPMo₈V₆O₄₂] (M = Co 1, Ni, 2; <i>i</i>-Pr-Im = 1-isopropyl-1H-imidazole). Needing no additives, they can catalyze the selective oxidation of isochroman to isochromanone with O₂ as an oxidant, with yields of 91.5% (1) and 46.8% (2), respectively. Mechanistic studies indicate that the excellent performance of catalyst 1 is attributed to the synergistic operation of [Co(<i>i</i>-Pr-Im)₄)] complex and PMo₈V₆ unit, and that the catalytic reaction is a radical pathway involving superoxide radicals. Additionally, the catalyst 1 can be recycled and reused at least four times with uncompromised performance. These results provide fundamental guidelines for designing efficient and multi-site heterogeneous catalysts for the selective oxidation of benzyl C(sp³)-H bonds by activating O₂.</p><h3>Graphical Abstract</h3>\u0000<div><figure><div><div><picture><source><img></source></picture></div></div></figure></div></div>","PeriodicalId":749,"journal":{"name":"Rare Metals","volume":"44 6","pages":"4003 - 4013"},"PeriodicalIF":9.6,"publicationDate":"2025-02-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143938231","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}