Zhi-Wei Chen,Xiao Chen,Xin-Rui Sun,Fang-Li Chen,Xin-Yue Wang,Hao Wu,Cheng-Yang Yue,Xiao-Wu Lei
{"title":"Reversible Stimulus-Responsive Photoluminescence Switching in Organic Cuprous Halide Scintillators for Multifunctional Applications","authors":"Zhi-Wei Chen,Xiao Chen,Xin-Rui Sun,Fang-Li Chen,Xin-Yue Wang,Hao Wu,Cheng-Yang Yue,Xiao-Wu Lei","doi":"10.1039/d6qi01685e","DOIUrl":"https://doi.org/10.1039/d6qi01685e","url":null,"abstract":"Low-dimensional organic-inorganic cuprous halides have gained significant interest with wide potential applications in solidstate lighting, anti-counterfeiting, luminescence sensing, scintillation, etc., due to diverse coordination geometries and excellent optoelectronic properties. Nevertheless, controllable structural regulation and integrated multifunction in a structural platform remains a great challenge. Herein, two pairs of Cu(I) halide family of (MOPPZ)2Cu2X6 and (MOPPZ)2Cu4X8 (MOPPZ = 1-(2-Methoxyphenyl)piperazine, X = Br, I) were successfully synthesized in the same halide system through elaborate crystal engineering strategy. The different anionic skeletons enable these cuprous halides to display multicolor broadband light emissions arising from self-trapped excitons (STEs). Systematic studies reveal that (MOPPZ)2Cu4X8 show lower emission energies and higher luminescence efficiency than (MOPPZ)2Cu2X6, owing to stronger Cu•••Cu interactions and electron-phonon coupling, respectively. Interestingly, these halides show intriguing reversible stimulus-response phase transitions with dynamic photoluminescence (PL) switching, endowing them with significant potential for high-level anticounterfeiting and information encryption-decryption. In addition, (MOPPZ)2Cu4I8 exhibits excellent radioluminescence performance with a high light yield of 34400 photons MeV -1 , low detection limit of 470 nGy s -1 , which is attributed to the synergistic effect of high photoluminescence quantum yield (PLQY = 95.5%) and heavy atom effect. A high spatial resolution of 18 lp mm -1 in X-ray imaging was achieved on flexible (MOPPZ)2Cu4I8 screen, demonstrating significant potential in practical X-ray imaging application. This work realizes the integrated reversible stimuli-responsive PL switching and high-efficiency Xray scintillation in 0D Cu(I)-based metal halide, offering new insights for development of multifunctional optoelectronic devices.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"87 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148980717","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}
Ben Liu,Qiang Sun,Tian-Xin Xiao,Haibo Wang,Wei Zhang,Yi Li
{"title":"Lipid Droplets-Targeted Iridium(III) Complexes Synergize Type I/II Photodynamic Therapy and Glutathione Depletion to Trigger Self-amplifying Ferroptosis, Necroptosis and Immunogenic Cell Death","authors":"Ben Liu,Qiang Sun,Tian-Xin Xiao,Haibo Wang,Wei Zhang,Yi Li","doi":"10.1039/d6qi01559j","DOIUrl":"https://doi.org/10.1039/d6qi01559j","url":null,"abstract":"As the central hubs of lipid metabolism, lipid droplets (LDs) orchestrate ferroptosis, an iron-dependent cell death driven by lipid peroxidation (LPO). Despite the promising ferroptosis-induction potential, conventional photodynamic therapy (PDT) is constrained by inefficient reactive oxygen species (ROS) generation and intracellular glutathione (GSH) scavenging. Herein, we report two H2S-responsive dinuclear iridium(III) complexes, IrSS-1 and IrSS-2, engineered to simultaneously localize in LDs, generate abundant ROS via dual-type (Type I/II) PDT mechanisms and deplete GSH through disulfide bond cleavage. These synergistic actions lead to pronounced LPO accumulation and potent ferroptosis. Notably, IrSS-2-mediated PDT further triggers immunogenic cell death (ICD) by promoting calreticulin exposure, high-mobility group box 1 (HMGB1) release, and ATP secretion. Transcriptomic profiling confirms significant rewiring of ferroptosis-associated and antitumor immunity pathways. In vivo studies demonstrate robust tumor suppression with minimal systemic toxicity. Our work presents a pioneering strategy integrating LD-targeted dual-type PDT and GSH depletion to achieve self-amplifying ferroptosis and ICD. It opens a new frontier in precision medicine by merging subcellular targeting, redox control, and immune engagement in one intelligent molecular platform.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"4 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148993838","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}
Katy A Knecht,Jazmin N Garcia,Liviu M. Mirica,Sagnik Chakrabarti
{"title":"PivaloNi: A Stable, Dicationic \"Naked Nickel\" Precursor for Coordination Chemistry and Catalysis","authors":"Katy A Knecht,Jazmin N Garcia,Liviu M. Mirica,Sagnik Chakrabarti","doi":"10.1039/d6qi01758d","DOIUrl":"https://doi.org/10.1039/d6qi01758d","url":null,"abstract":"In this study, we report the isolation, characterization, and reactivity of a new dicationic Ni II compound supported by pivalonitrile ligands, with the stoichiometry [Ni(tBuCN)4(OH2)2][BF4]2, abbreviated as pivaloNi. We show that the pivalonitrile ligands are labile and can be displaced by solvent molecules like tetrahydrofuran or acetonitrile. Surprisingly, pivaloNi was found to be more stable to hydrolysis compared to the related hexakisacetonitrilenickel(II) compound. In accordance with its lability, pivaloNi can be used as an efficient Ni II precursor for coordination chemistry, as shown by a variety of ligand substitution reactions. In addition, we also show its utility as a precursor for several cross-coupling reactions, despite having no obvious transmetalation sites. This work introduces a bench-stable but labile Ni II precursor to the synthetic chemist's toolkit.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"150 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148993841","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}
Muqing Chen,Zhanxin Jiang,Lei Li,Xueyi Chang,Ziqi Hu,Yongfu Qiu,Zhiyu Cheng,Shangfeng Yang
{"title":"Cascade Radical Addition of Ce₂@I-C₈₀: Switching the Single Electron Metal-Metal Bond to Revisit Metal-Cage Interactions","authors":"Muqing Chen,Zhanxin Jiang,Lei Li,Xueyi Chang,Ziqi Hu,Yongfu Qiu,Zhiyu Cheng,Shangfeng Yang","doi":"10.1039/d6qi01781a","DOIUrl":"https://doi.org/10.1039/d6qi01781a","url":null,"abstract":"The metal-cage interaction and metal-metal bonds are two critical roles in governing the physicochemical properties of endohedral metallofullerenes (EMFs). However, the cascade modulation of the electronic structures of both the encapsulated metal cluster and the outer carbon cage through chemical functionalization remains rarely explored, despite of its great potential for revealing the evolution of metal-metal and metal-cage interactions. Herein, we report a facile radical addition reaction of Ce2@Ih-C80 with benzyl bromide. This reaction proceeds via cascade functionalization and surprisingly affords three products, rather than the typical single monoadduct: two monoadduct isomers (2a and 2b), each bearing one benzyl group, and one triadduct (3a) bearing three benzyl moieties. More importantly, the molecular structures of 2a, 2b, and 3a were unambiguously determined by single-crystal X-ray crystallography. Combining these unambiguous molecular structures with magnetic characterizations and theoretical calculations, we gain comprehensive insights into the sitedependent dynamic behaviors of metal-cage interactions and adaptive metal-metal bonds. These findings pave the way for the rational design and development of various functionalized endohedral metallofullerenes (EMFs).","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"13 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148993837","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}
Natalia Kolozsvari,Paul R Tiley,Ume-Kulsoom Shah,Sujani Imaduwa Wickrama Acharige,Daniel Harrison,James G. Cronin,Christopher J. Staples,Gareth J. S. Jenkins,Martin R Gill
{"title":"Design and evaluation of mismatch-selective Ru(qdppz) complexes with unexpected mitochondrial activity","authors":"Natalia Kolozsvari,Paul R Tiley,Ume-Kulsoom Shah,Sujani Imaduwa Wickrama Acharige,Daniel Harrison,James G. Cronin,Christopher J. Staples,Gareth J. S. Jenkins,Martin R Gill","doi":"10.1039/d6qi01113f","DOIUrl":"https://doi.org/10.1039/d6qi01113f","url":null,"abstract":"Small molecules that bind DNA mismatches have been proposed as potential tools by which to achieve preferential activity in MMR-deficient cancer cells. Here, we describe the synthesis of a series of DNA binding ruthenium(II) polypyridyl complexes (RPCs) containing the extended anthraquinone intercalating ligand qdppz (qdppz = naphtho[2,3-a]dipyrido[3,2-h:2‘,3‘-f]phenazine-5,18-dione) and methylated ancillary ligands. A modified ethidium bromide displacement assay indicated all complexes possess enhanced affinities for CC mismatch-containing duplexes over well-matched, with [Ru(5,5’ dmbpy)2(qdppz)]2+ (5,5’ dmbpy = 5,5'-dimethyl-2,2'-bipyridine) showing the broadest mismatch selectivity of the series. Mismatch binding was further supported by a novel quenching assay that exploits the previously unreported ability of Ru(qdppz) complexes to quench Cyanine 5.5-labelled DNA. In MTT assays using MMR-deficient DLD-1 and MMR-proficient DLD-1+Chr2 colorectal adenocarcinoma cells, [Ru(5,5′-dmbpy)2(qdppz)]2+ was the most active complex and exhibited lower IC50 values than cisplatin in both cell lines. However, the limited DNA damage observed was consistent with the absence of MMR-dependent selectivity, suggesting a mismatch-independent mechanism of cytotoxicity. Live-cell bioenergetics instead revealed an unexpected impact of [Ru(5,5’ dmbpy)2(qdppz)]2+ on mitochondrial respiration, including a decrease in basal respiration, ATP production, maximal respiration, and spare respiratory capacity. ICP-MS analysis of isolated mitochondria confirmed mitochondrial localisation and displacement of a mitochondrial DNA dye is consistent with mtDNA as a target. Combined with the absence of a cytotoxic response, this work provides a distinct biological activity for a substitutionally inert RPC that binds DNA by intercalation.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148993843","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}
Zhuoqi Wang,Xiaoming Liu,Ranran Zhang,Keke Li,Bo Wang,Lulu Xu,Xiaolei Li,Shuo Tao
{"title":"Constructing hierarchical aluminophosphate-based zeotypes via a neutral phosphorus-compensated dissolution-recrystallization strategy","authors":"Zhuoqi Wang,Xiaoming Liu,Ranran Zhang,Keke Li,Bo Wang,Lulu Xu,Xiaolei Li,Shuo Tao","doi":"10.1039/d6qi01717g","DOIUrl":"https://doi.org/10.1039/d6qi01717g","url":null,"abstract":"The post-synthetic construction of hierarchical porosity is pivotal for mitigating mass transfer limitations in zeolites, yet its application to aluminophosphate zeotypes is restricted by inherent framework instability. Unlike robust aluminosilicates, their Al-O-P linkages are susceptible to rapid structural collapse during conventional alkaline etching due to preferential phosphorus leaching and fatal stoichiometric imbalance. Herein, we resolve this dilemma via a neutral phosphorus-compensated dissolution-recrystallization strategy. By employing neutral triethyl phosphate (TEP) as a buffered phosphorus reservoir, this protocol decouples alkalinity maintenance from chemical nutrient supply. TEP’s slow hydrolysis kinetically matches the framework dissolution rate, facilitating immediate in-situ recrystallization of dissolved species into ordered frameworks. Using nanosized AlPO4-11 as a model, we demonstrate its transformation into single-crystalline hollow architectures with restored Al/P stoichiometry and high solid yields (>70%). The universality of this constructive remodeling mechanism is verified across AEL, AFI, AEI, and CHA topologies. Crucially, the resulting hierarchical SAPO-34 catalyst exhibits superior performance in the methanol-to-olefins (MTO) reaction, achieving a 2.7-fold lifetime extension with 86% light olefin selectivity. This enhanced stability stems from alleviating confinement-induced coking within the 8-membered ring cages, establishing a generalized paradigm for the structural engineering of chemically labile porous materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"1 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148980724","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}
Daniel Brüx,Ben Ebel,Johannes Bartusel,Irmgard Kalf,Christoph Hennig,Florian Kleemiss
{"title":"Following the Spin-Transition in Iron(II) Complexes by Crystallographic Disorder Modelling","authors":"Daniel Brüx,Ben Ebel,Johannes Bartusel,Irmgard Kalf,Christoph Hennig,Florian Kleemiss","doi":"10.1039/d6qi01319h","DOIUrl":"https://doi.org/10.1039/d6qi01319h","url":null,"abstract":"Spin crossover in iron(II) complexes refers to the switch between a low-spin M = 1 and a high-spin M = 5 state, producing pronounced magnetic, optical and structural changes. Single-crystal X-ray diffraction directly monitors the accompanying crystallographic modifications. Here we show that Hirshfeld Atom Refinement (HAR), which employs ab-initio electron-density-derived atomic form factors, allows quantitative modelling of co-existing LS and HS isomers as crystallographic disorder. Applying this method to four representative iron(II) SCO complexes -[Fe(phen)₂(SCN)₂], [Fe(pic)₃]Cl₂•EtOH, [Fe(PM-Bia)₂(NCS)₂] and [Fe(tpa)(SCN)₂]₂•MeOH -we refined temperature-dependent site-occupancy factors that correspond to the HS fraction. High-resolution data (in-house and synchrotron) reveal abrupt or gradual changes of the HS and LS-fractions. Reproducibility measurements across different crystals yield uncertainties ≤0.5 %, and the choice of hybrid DFT functional influences the occupancies only marginally. Even a two-step transition, observable for [Fe(tpa)(SCN)₂]₂•MeOH, is accurately described using a simple disorder model. Consequently, HAR-based disorder refinement provides a robust, quantitative crystallographic tool for probing spin-state superpositions in SCO materials.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"52 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148980725","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}
Zilong Chen,Wenxia Xu,Suping Li,Guohui Qin,Lei Wang,Jianping Lai
{"title":"Precise Atomic/Molecular Design and Functional Regulation of Dynamic Cross-Scale Electrocatalytic Interfaces","authors":"Zilong Chen,Wenxia Xu,Suping Li,Guohui Qin,Lei Wang,Jianping Lai","doi":"10.1039/d6qi01545j","DOIUrl":"https://doi.org/10.1039/d6qi01545j","url":null,"abstract":"T Electrocatalytic modulation at atomic/molecular scale on catalyst-electrolyte interfaces is the key bottleneck limiting the efficiency and industrialization of electrocatalysis. Static characterization and single-scale research fail to capture dynamic interfacial evolution and crossscale coupling, restricting catalytic interface optimization and performance breakthroughs. This review systematically summarizes four core advances in dynamic cross-scale interface regulation: controllable microstructural reconstruction of catalysts, mesoscopic optimization of electrolyte interfacial microenvironment, multi-scale stabilization of catalytic interfaces, and integrated macroscopic characterization/computational technologies, alongside their underlying working mechanisms. Cross-scale research bridges micro, meso and macro dimensions to enable full analysis of dynamic interfacial behaviors and full-chain collaborative regulation, which provides systematic theoretical guidance for the atomic-precise design of high-efficiency electrocatalysts.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"19 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148980723","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":"Sc III -Ce III heterometallic bismuthotungstate with triple-modal colorimetric-photothermal-smartphone sensing capability toward thiosulfate","authors":"Zhigang Tang,Jiaxin Li,Dan Wang,Lijuan Chen,Junwei Zhao","doi":"10.1039/d6qi01767c","DOIUrl":"https://doi.org/10.1039/d6qi01767c","url":null,"abstract":"Rapid and accurate detection of thiosulfate (S2O32−) is highly imperative for ecological protection, food quality supervision and human health monitoring. However, its practical sensing implementation still suffers from an inherent trade-off between analytical sensitivity and operational simplicity. Herein, we successfully fabricated the first ScIII–CeIII heterometallic bismuthotungstate H11Na14(NH4)8[Ce3(H2O)8Sc6(H2O)6W9O30(B-β-BiW9O33)6]∙78H2O (1) via a facile stepwise assembly strategy. Structural analysis reveals that the polyanion of 1 is constructed from six [B-β-BiW9O33]9– building blocks and an 18-nuclear ScIII–CeIII–WVI trimetallic [Ce3(H2O)8 Sc6(H2O)6W9O30]21+ core. Leveraging the unique multimetallic synergistic effect, 1 displays favorable peroxidase-like activity, which enables the efficient decomposition of H2O2 into hydroxyl radicals (·OH) and further oxidizes colorless 3,3',5,5'-tetramethylbenzidine (TMB) into blue oxidized TMB. Based on the mechanism that S2O32− scavenges ·OH to inhibit the oxidation of TMB, which causes the blue color to fade, we constructed a novel 1-based triple- modal colorimetric-photothermal-smartphone sensing platform for S2O32− detection. This platform demonstrates a linear response to S2O32− in the range of 0.05–60 μM, with corresponding detection limits of 0.0081±0.0006 μM (colorimetric), 0.0086±0.0008 μM (photothermal) and 0.0075±0.0005 μM (smartphone). Moreover, it displays outstanding selectivity, operational stability, and anti-interference capability. Satisfactory recoveries (93.5%–108.2%) in real environmental and food samples further validate its robustness and practical applicability. This work not only reports the first ScIII–CeIII heterometallic bismuthotungstate, but also establishes an unprecedented polyoxometalate-based triple-modal sensing strategy for S2O32– detection.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"21 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973498","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}
Yating Wu,Chuanzhen Feng,Kaiwen Bo,Shicheng Xu,Jiangli Zhang,Yao Li,Danhong Li,Huijuan Zhang,Yu Wang
{"title":"A site-decoupled photothermal relay for efficient nitrate-toammonia electroreduction","authors":"Yating Wu,Chuanzhen Feng,Kaiwen Bo,Shicheng Xu,Jiangli Zhang,Yao Li,Danhong Li,Huijuan Zhang,Yu Wang","doi":"10.1039/d6qi01599a","DOIUrl":"https://doi.org/10.1039/d6qi01599a","url":null,"abstract":"Electrocatalytic nitrate reduction (NO3RR) offers a sustainable route for nitrate remediation and green ammonia synthesis, but two kinetic barriers limit performance: the mismatch between NO3 -deoxygenation and NO2 -hydrogenation, and nonelectron-transfer steps that applied potential alone cannot regulate. Herein, we report a facile in-situ partial phosphorization strategy to construct an intimately contacted CoP-CoO heterostructure, in which a single CoP phase bears two functions: acting as the *NO2 hydrogenation site, and serving as the near-infrared (NIR) photothermal transducer. A spatially decoupled adsorption relay (SDAR) mechanism is established, wherein CoO preferentially deoxygenates NO3 -and the resulting *NO2 is thermodynamically relayed to adjacent CoP sites for hydrogenation. The intimate heterointerface drives electron transfer from CoO to CoP, facilitating intermediate relay. The NIR irradiation is concurrently converted into localized surface heat (~23°C rise, versus only ~2°C in the bulk electrolyte), accelerating the potential-insensitive steps and lowering interfacial charge-transfer resistance. The optimized CoP-CoO-10 achieves an NH3 Faradaic efficiency of 93.9% and a yield rate of 111.6 μmol h -1 cm -2 at -0.3 V vs. RHE under NIR irradiation, a 1.6-fold enhancement over dark conditions. This work establishes a design principle in which a single active phase concurrently governs intermediate selectivity and localized thermal input.This strategy is generalizable to other multi-step electrocatalytic systems facing similar kinetic constraints.","PeriodicalId":79,"journal":{"name":"Inorganic Chemistry Frontiers","volume":"54 1","pages":""},"PeriodicalIF":7.0,"publicationDate":"2026-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148973502","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}