Inorganic Chemistry Frontiers最新文献

{"title":"Quenching Quantum Tunnelling of the Magnetization Utilizing 4d-4f Exchange Interactions in Butterfly-shaped {RuIII2LnIII2} (Ln = Gd, Tb, Dy, Ho, and Er) Single-Molecule Magnets","authors":"Imon J. Dutta, Vignesh Kasi, Deepanshu Chauhan, Keith S. Murray, Stuart K. Langley, Maheswaran Shanmugam, Kuduva R. Vignesh","doi":"10.1039/d5qi01665g","DOIUrl":"https://doi.org/10.1039/d5qi01665g","url":null,"abstract":"The performance of Single-Molecule Magnets (SMMs) can be enhanced by reducing quantum tunneling of magnetization (QTM), which can be achieved with the aid of strong magnetic exchange interactions and strong magnetic anisotropy. When 4d ions are mixed with 4f ions, the strong spin-orbit coupling and moderate ligand-field strength of 4d elements complement the highly anisotropic 4f ions, and the combined effect decreases the transverse anisotropy and stabilizes the magnetic easy axis, both of which are essential for lowering QTM. Despite their synthetic challenges, the unique electronic properties of Ru-4f systems make them promising candidates for designing advanced single-molecule magnets. Here, we report the synthesis, magnetic, and theoretical studies of five tetranuclear \"butterfly-shaped\" complexes of formulae [RuIII2LnIII2(OMe)2(o-tol)4(mdea)2(NO3)2] (Ln = Gd (1-Gd), Tb (2-Tb), Dy (3-Dy), Ho (4-Ho), mdeaH2 = N-methyldiethanolamine) and [RuIII2ErIII2(OMe)2(o-tol)6(mdea)2]•2MeOH (5-Er). Complexes 2-Tb, 4-Ho, and 5-Er are the first reported examples of 4d-4f complexes using these LnIII ions. DC magnetic susceptibility studies revealed an antiferromagnetic exchange interaction between the LnIII and RuIII metal ions in all complexes. Among the complexes reported, 3-Dy and 4-Ho show out-of-phase susceptibility signals in the absence of an external magnetic field, while the remaining complexes exhibit field-induced slow relaxation of magnetization. These observations were attributed to the presence of an ideal crystal field combined with the strong exchange interaction exerted between the RuIII and LnIII ions in the complexes. Importantly, the 4-Ho is the first non-dysprosium Ru-Ln polynuclear complex to show zero-field SMM behavior. Detailed ab initio CASSCF+RASSI-SO+SINGLE_ANISO+POLY_ANISO and Density Functional Theory (DFT) calculations reveal that the magnitude of exchange interaction increases in the following order: 1-Gd (−1.3 cm -1 ) < 2-Tb (−1.6 cm -1 ) < 3-Dy (−2.7 cm-1) < 4-Ho (−2.8 cm-1) < 5-Er (−4.0 cm-1). The larger single-ion anisotropy of the DyIII ions in 3-Dy leads to the largest barrier of 101 cm-1 (146 K), which increases further to 111 cm-1 (158.7 K) when considering the exchange-coupled model, with the strong Ru⋯Ln exchange further quenching QTM effects. These results highlight the importance of strong magnetic exchange between 4d-4f (RuIII⋯LnIII) ions in enhancing the SMM behavior of 4d-4f complexes.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"123 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229249","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Mn2+-doping and Vacancy Engineering Induce Phase Transition with Ultrahigh Dielectric Switching Ratio in Lead Chloride Hybrids","authors":"Wei Ye, Gang Chen, Dongsheng Shao, Jia-Yi Zhang, Yueqi Shen, Xiaozu Wang, Weihua Ning, Zhengfang Tian, Xiaoming Ren","doi":"10.1039/d5qi01839k","DOIUrl":"https://doi.org/10.1039/d5qi01839k","url":null,"abstract":"Lead halide hybrids are promising switchable dielectric materials owing to their structural tunability, which enables thermotropic phase transitions. However, achieving large dielectric contrasts remains a significant challenge. Here, we demonstrate a strategy to markedly enhance the dielectric switching ratio (DSR) by engineering a phase-transition compound with elevated ionic conduction in the high-temperature phase via vacancy-enabled ionic transport. Using [C<small>₅</small>H<small>₁₂</small>N]<small>₂</small>PbCl<small>₄</small> (C<small>₅</small>H<small>₁₂</small>N<small>⁺</small> = piperidinium) as a model, we synthesized a series of [C<small>₅</small>H<small>₁₂</small>N]<small>_2-2x</small>Pb<small>_1-x</small>Mn<small>_x</small>Cl<small>_4-2x</small> (x = 0.01–0.15) via solvent-free mechanochemistry. Mn<small>²⁺</small>-doping introduces charge-compensating C<small>₅</small>H<small>₁₂</small>N<small>⁺</small> and Cl⁻ vacancies into the lattice, triggering a structural phase transition. As anticipated, the doped hybrids exhibit substantially improved DSR, with the x = 0.15 composition reaching an ultrahigh value of ~10<small>³</small>-surpassing most reported dielectric switching materials. This enhancement is attributed to a grain boundary-induced barrier layer mechanism within the ion-conducting system. Our results establish vacancy-enabled ionic transport as a viable strategy for designing high-performance dielectric switching materials within soft halide frameworks.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"27 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145229101","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In-situ Electrodeposition of Pt into a Trimetallic MOFs Composite Electrode and Its Application in Water Splitting","authors":"Yukou Du, Tianpeng Liu, Xin Wang, Jie Li, Mengyun Hu, Jun Yu, Shudi Yu, Zhengying Wu","doi":"10.1039/d5qi01505g","DOIUrl":"https://doi.org/10.1039/d5qi01505g","url":null,"abstract":"High current density and low cost are key considerations in the design of new electrolytic water catalytic materials. Herein, ternary metal-organic frameworks (MOFs) arrays with a coral-like nanostructure are constructed via solvothermal growth and in situ electrochemical deposition methods. The excellent gas transfer capability of self-supported electrodes and the synergistic effect between transition metals contribute to the stable operation of the composite electrodes at high current densities. The results demonstrate that FeNiCo/NF and FeNiCoPt/NF exhibit remarkable OER (262 mV@100 mA cm-2) and HER performance (218 mV@100 mA cm-2). The two-electrode system (FeNiCo/NF || FeNiCoPt/NF) only requires a terminal voltage of 1.70 V to drive the overall water splitting reaction to a current density of 100 mA cm-2, with electrochemical stability maintained for over 100 h.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"69 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209926","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Dual-functional Zr(IV)-based Metal-organic Gel via a Cage-to-Gel Strategy: Nerve Agent Simulant Degradation and Blister Agent Simulant Adsorptive Sensing","authors":"Lai-Yi Li, Bao-Ying Guo, Liang-Hua Wu, Zai-Kun Yan, Songliang Cai, Jun Fan, Yu-Wei Zhang, Wei-Guang Zhang, Sheng-Run Zheng","doi":"10.1039/d5qi01321f","DOIUrl":"https://doi.org/10.1039/d5qi01321f","url":null,"abstract":"The adsorption, degradation, and sensing of chemical warfare agents are highly important. In this work, a new Zr(IV)-based metal‒organic gel (MOG) was designed and synthesized, which demonstrated dual-functional performance in the degradation of nerve agent simulants and the adsorptive sensing of blister agent simulants. Zr(IV)-based MOG, namely, Zr-MOG-taBDC (H2taBDC = 2-(1H-1,2,4-triazol-1-yl) terephthalic acid), was synthesized through the thermal transformation of a tetrahedral Zr(IV)-based metal-organic cage, {[Cp3Zr3(μ3-O)(μ2-OH)3]4(taBDC)6}·(Cl-)4 (Zr-MOC-taBDC), in a mixed acetonitrile/water solvent system, bypassing the need for tedious anion exchange and high-boiling solvents. The resulting MOG exhibited hierarchical porosity and high stability across a wide pH range (1–11). Catalytic tests revealed that Zr-MOG-taBDC achieved 95.4% degradation efficiency for the nerve agent simulant diethyl phenylphosphonate (DEPPT), with a half-life of 49.5 minutes, outperforming its crystalline MOC precursor. Additionally, the gel demonstrated a high adsorption capacity (0.6 g/g) for the mustard gas simulant 2-chloroethyl ethyl sulfide (CEES), enabling real-time detection via a quartz crystal microbalance (QCM) with a linear response range up to 100 ppm. Mechanistic studies indicated that degradation proceeds via P‒S bond cleavage catalyzed by Zr‒OH‒H₂O Lewis acid‒base sites, whereas adsorption involves reversible physical and irreversible chemical interactions with triazole groups and Zr‒oxo clusters. This work highlights the potential of Zr-MOGs as multifunctional materials for chemical warfare agent mitigation and sensing.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"20 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209901","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Tetranuclear Zn(II) Based Host-Guest MOF Resistant to Thermal Quenching","authors":"Xiao-Gang Yang, Xin-Ya Zhang, Zhao-Tong Yang, Xin-Ci Wu, Jia-Chen Liu, Xiao-Tian Wei, Huarui Wang, Lufang Ma","doi":"10.1039/d5qi01707f","DOIUrl":"https://doi.org/10.1039/d5qi01707f","url":null,"abstract":"The development of phosphor-converted white-light-emitting diodes applied in the fields of solid-state lighting and displaying has attracted increasing interests due to their high efficiency, small size, and low operating voltage. However, one important issue that cannot be ignored is the so-called thermal quenching: heat (∼150 °C) generated by the operated inner diode chips usually cause the emission losses of the outer phosphors. Herein, One new tetranuclear Zn(II) based host-guest MOF was isolated by in situ encapsulation of acridine chromophore. Crystallographic information for the relative position and arrangement of the guests, multiple interactions between the host and guest, guest and guest and density functional (DFT) calculations were well studided. The host-guest MOF phosphor shows bright yellow emission and long lifetime of 29.15 ns at room temperature. It exhibits thermal quenching of 9.08% at 150 °C, lower than several reported inorganic phosphor (28~50%). The successful fabrication of phosphor-converted white-light-emitting diode by direct integration of the yellow emission MOF with blue InGaN chip enables it promising phosphor applied in solid-state lighting.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"32 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209902","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Charge Compensation via Tetravalent Doping for High-Efficiency Mn 2+ -Activated Inorganic Double Perovskites toward High-Resolution X-Ray Imaging","authors":"Gaoyuan Xing, Endian Cui, Xiangyang Yuan, Bing Wang, Jiucun Chen, Yanan Zhao, Jianfeng Tang, Jing Liu","doi":"10.1039/d5qi01582k","DOIUrl":"https://doi.org/10.1039/d5qi01582k","url":null,"abstract":"In recent years, lead-free halide double perovskites nanocrystals (NCs) have emerged as compelling scintillator candidates due to their high effective atomic number, ultrafast scintillation decay kinetics, eco-friendly composition, and bandgap tunability, which are essential for high-temporal-resolution radiation detection. While nanostructured scintillators achieve exceptional optical uniformity, their nanocrystalline forms inherently exhibit inherent limitations in light emission intensity and overall scintillation efficiency. A critical limitation in X-ray flat-panel minidetectors remains the absence of novel engineering approaches to amplify radioluminescence capabilities. Herein, we engineered a charge compensation strategy in Cs 2 AgInCl 6 double perovskite NCs through co-doping tetravalent ions with Mn 2+ emissive centers to stabilize the heterovalent substitution of In 3+ sites by Mn 2+ . The co-doping of Zr 4+ or Ce 4+ enhanced Mn 2+ -activated emission, and induced sequential improvements in photoluminescence lifetime and quantum yield for CAIC:Mn 2+ , CAIC:Mn 2+ , Zr 4+ and CAIC:Mn 2+ , Ce 4+ . XPS analysis confirmed 1.46-fold (CAIC:Mn 2+ , Zr 4+ ) and 1.59-fold (CAIC:Mn 2+ , Ce 4+ ) increases in effective Mn 2+ /Mn 4+ doping concentration relative to CAIC:Mn 2+ . The Ce 4+ effectively suppressed Mn 2+ oxidation to higher valence states, enhancing the Mn 2+ /Mn 4+ ratio by 3.4 times. The CAIC:Mn 2+ , Ce 4+ @PDMS scintillator film demonstrated a superior light yield of 16,807 photons MeV -1 , spatial resolution of 7.7 lp mm -1 , and detection limit of 619.2 nGy air s -1 .","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"18 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209927","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Multiple relaxor phases driven excellent energy storage performance in Na 0.5 Bi 0.5 TiO 3 -based ceramics via dual-site ion-pair structure design","authors":"Pan Gao, Hanjun Wang, Chang Liu, Wenjing Geng, Yun Ling, Yubo Li, Hongyan Wan, Jing Zhang, Haijuan Li","doi":"10.1039/d5qi01577d","DOIUrl":"https://doi.org/10.1039/d5qi01577d","url":null,"abstract":"Dielectric ceramics have attracted extensive attention for high-power energy storage applications due to their fast charge-discharge capabilities and high-power density. Bi 0.5 Na 0.5 TiO 3 (BNT)-based lead-free ceramics are notable for their high saturation polarization and moderate breakdown electric field (E b ), but they still suffer from low breakdown field, large hysteresis losses and insufficient efficiency. Here, we propose a strategy of dual-site ion-pair engineering by introducing Ba(Sr 0.5 W 0.5 )O 3 (BSW) into the BNT matrix. In this design, Ba²⁺-Ba²⁺ pairs at the A-site and Sr²⁺-W⁶⁺ pairs at the B-site induce local lattice distortion and generate strong random fields, which effectively promote the formation of multiple relaxor phases with polymorphic nanodomains. The features of electrical properties and phase-field simulations indicate that BSW doping facilitates a more composition disorder and disruption of long-range FE and AFE orders, integrating the short-range ordered antiferroelectric (AFE) nanodomains with highly disordered relaxor ferroelectric (RFE) to reduce the electric field-induced AFE-FE phase transition barrier. Additionally, the incorporation of BSW refines the grain size and increases microstructural homogeneity, enhancing the breakdown strength and delaying the polarization saturation. Accordingly, the 0.90BNT-0.10BSW ceramic exhibited an outstanding energy storage performance with high W rec of 6.57 J/cm³ and an η of 72% under an electric field of 450 kV/cm. In addition, the ceramic synchronously possesses excellent transient discharge rate t 0.9 of 90 ns and a high-power density P D of 121.9MW/cm 3 . This work suggests that the dual-site ionpair engineering is an effective approach for regulating structure-property relationships in BNT-based ceramics and provides a viable pathway for the development of highperformance lead-free dielectric materials for advanced energy storage applications.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"10 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209900","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In situ synthesis of bioorthogonally catalyzed drugs based on hydrogen-bonded organic frameworks for cancer therapy","authors":"Yan Wang, Luwen Zhang, Jiarui Qiao, Xianhao Wei, Tingyan Jiang, Junhe Ou, Maolin Pang","doi":"10.1039/d5qi01690h","DOIUrl":"https://doi.org/10.1039/d5qi01690h","url":null,"abstract":"As one of the most representative bioorthogonal reactions, the copper(<small>I</small>)-catalyzed azide–alkyne cycloaddition (CuAAC) reaction has attracted considerable attention in biomedical applications, attributed to its high efficiency and selectivity for the <em>in situ</em> synthesis of drugs within tumor cells. However, effectively achieving tumor-targeted drug activation through the CuAAC reaction still remains a major challenge, and an efficient delivery system is also needed for the prodrugs to avoid the rapid metabolism within biological environments. In this study, the inactive prodrug precursors were encapsulated within hydrogen-bonded organic framework (HOF) nanoparticles, and then selectively activated in the tumor microenvironment <em>via</em> an intracellular CuAAC reaction. The <em>in situ</em> formed drugs could effectively kill the cancer cells and suppress tumor growth. This strategy enables precise, <em>in situ</em> synthesis of active drug molecules within cancer cells, thereby achieving targeted therapeutic activation while minimizing off-target toxicity to normal tissues and cells.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"48 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145203194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Excitation Energy Funnelling in NIR-Emissive [YbPrYb] Heterometallic Complexes","authors":"Guillem Aromi, Laura Abad Galan, Olivier Maury, Yannick Guyot, Olivier Roubeau, David Aguilà, Annika Sickinger, Diamantoula Maniaki, Salauat Kiraev, Leoní A Barrios","doi":"10.1039/d5qi01585e","DOIUrl":"https://doi.org/10.1039/d5qi01585e","url":null,"abstract":"Energy transfer (ET) among different lanthanide ions is a promising avenue to access up-and down-conversion processes, as has been demonstrated on various solid-state materials. It is far less common to observe these phenomena on discrete species containing different lanthanide ions on predetermined locations of their molecular structure. The advantages are many, such as the ability to investigate these phenomena with ultimate atomic control, even in solution. A site-selective molecular scaffold combining ligands H₂LA and H₂LB has been developed to enable the targeted positioning of lanthanide ions based on differences in ionic radius. This architecture allows a Pr³⁺ ion to be stabilised in the central coordination cavity, while smaller Yb³⁺ ions preferentially occupy peripheral sites, giving rise to a [YbPrYb] topology within a discrete heterometallic complex. The resulting compound, [Yb₂Pr(LA)₂(LB)₂(H₂O)₂(py)]NO 3 , has been structurally characterised and used to investigate intramolecular ET between Pr³⁺ and Yb³⁺ ions. Two structural analogues, [YbLaYb] and [LuPrLu], were employed as luminescence controls to independently probe the donor and acceptor roles of each metal ion. Photophysical studies in solution and in the solid state revealed two distinct ET processes: a highly efficient Pr³⁺ → Yb³⁺ transfer, resulting in near-infrared (NIR) emission at 980 nm, and a competitive Yb³⁺ → Pr³⁺ back-transfer, leading to non-radiative deactivation.Lifetime analyses confirmed that both transfer pathways occur with near-quantitative efficiency. These findings represent the first evidence of bidirectional Pr³⁺ ⇄ Yb³⁺ energy transfer within a molecular complex and highlight the power of ligand architecture in enabling and modulating the lanthanide photophysical behaviour.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"23 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209928","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Construction of Carbon Nanotube-Supported CuO-Fe3O4 Dual-Site Catalysts for Ambient Electrosynthesis of Ammonia","authors":"Shun Zhang, Shengbo Zhang, Jiafang Liu, Zhixian Mao, Yunxia Zhang, Guozhong Wang, Huajie Yin, Haimin Zhang","doi":"10.1039/d5qi01543j","DOIUrl":"https://doi.org/10.1039/d5qi01543j","url":null,"abstract":"Electrocatalytic nitrate (NO3⁻) reduction reaction (NitRR) to ammonia (NH3) is considered a sustainable and environmentally friendly approach for synthesizing ammonia. However, the electrocatalyst encounters challenges related to the limited distribution of NO3⁻ and insufficient active hydrogen on the catalyst surface, which result from the high concentration of NO3⁻ and the difficulty of water splitting under ambient conditions. Here, by introducing Cu and Fe oxides onto carbon nanotube substrates (CuO-Fe3O4/CNT), a CuO-Fe3O4 dual-site synergistic catalytic mechanism is proposed to promote the adsorption and conversion of NO 3 ⁻ at CuO site and accelerate water splitting at Fe3O4 site, thereby significantly enhancing the performance of nitrate reduction reactions. The as-synthesized CuO-Fe3O4/CNT exhibits good activity for NitRR, achieving an NH3 yield rate of 39.2 ± 3.5 mg h-1 mg cat.-1 and a Faradaic efficiency of 90.5 ± 2.2% at -0.8 V (vs. RHE). Furthermore, different in-situ characterizations were employed to identify intermediates in the electrocatalytic NitRR process, confirming CuO-Fe3O4/CNT as a promising catalyst for NH3 electrosynthesis.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"9 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2025-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145195393","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}