Lanthanide coordination polymer (Ln-CP) has emerged as a promising material for luminescent sensing applications; however, traditional single-type or dual-type emission systems often exhibit limited specificity when distinguishing analytes with similar chemical characteristics, such as phosphate species. In this work, we present the first single-component europium(III) coordination polymer, designated EuOPTD (H2OPTD = 4,4'-(5,5-dioxido-10H-phenothiazine-3,7-diyl)dibenzoic acid), which intrinsically exhibits triple-type emission originating from the ligand, excimer, and Eu3+ centers. EuOPTD demonstrates precise colorimetric pH sensing within a narrow acidic range and effectively differentiates among H2PO4-, HPO42-, and PO43- ions through distinct luminescent signatures. Moreover, EuOPTD was also employed to analyze real lake water samples for the sensing of H2PO4-, demonstrating superior sensing performance with a linear range of 309-722 mu M and a limit of detection of 86.38 mu M. This work represents a significant advancement in the development of dual-functional sensing platforms, offering improved selectivity and accuracy for simultaneous pH measurement and phosphate species differentiation.

ABSTRACT The electrocatalytic nitrate reduction reaction (eNO 3 RR) offers a sustainable strategy for both NO 3 − wastewater remediation and value‐added NH 3 production. However, its application is hindered by sluggish reaction kinetics in neutral media due to the limited availability of protons. Herein, an anionic metal–organic framework (MOF), SU‐102, is functionalized with atomically dispersed Fe sites to yield SU‐102‐Fe. This catalyst achieves a Faradaic efficiency (FE) of 96.9% and NH 3 production rate of 1.72 mg h −1 mg cat −1 at −0.7 V versus RHE, far surpassing the commercial Fe 2 O 3 and pristine SU‐102. In situ characterizations reveal that the negatively charged Zr─O units in SU‐102 create an anionic microenvironment around the Fe sites, which enriches K + •H 2 O species derived from the interfacial hydrogen‐bonding network. The facile dissociation of K + •H 2 O improves local proton supply, facilitating NO 3 − ‐to‐NH 3 conversion and accounting for the superior eNO 3 RR performance of SU‐102‐Fe.

Excessive consumption of fossil fuels has led to severe environmental and energy crises. It is urgent to develop efficient solar energy conversion technologies. Although the photothermal-photo-catalytic synergy system can achieve full-spectrum utilization, it still faces multiple limitations. These include low mass transfer efficiency, intermittent light exposure, and relatively simple functionality. To address these issues, the study designed and constructed a covalent organic framework material based on thiophene conjugated cyanide functional groups. Further, it was combined with cellulose gel and polyethylene glycol phase change material (PCM). Finally, an integrated, multifunctional bulk material, was successfully prepared (BPCEC-BCT). The system integrates photothermal conversion, phase change energy storage, photocatalysis, and thermoelectric power generation. Under a 1 kW & sdot;m- 2 light condition, the BPCEC-BCT shows impressive overall performance, with a water evaporation rate of 3.66 kg m- 2 h- 1 and a H2O2 production rate reaching 12.81 mM m-2 h- 1. The system can also simultaneously output 20 mA of current and 0.24 V of voltage. This study provides an innovative material platform and system solution for the water-energy-chemical co-production.

With the continuous development of agriculture and industry,nitrate(NO3-)pollution in water bodies worldwide remains a serious issue,characterized by decentralized distribution across multiple sites.The electrocatalytic nitrate reduction reaction(eNO3RR)technology enables the reduction of NO3-waste into ammonia(NH3)—a substance useful to humans—under ambient temperature and pressure.However,under near-neutral pH conditions that mimic actual aquatic environments,eNO3RR faces multiple bottlenecks,including limited proton supply,competition from hydrogen evolution side reactions,risks of nitrite(NO2-)accumulation,and insufficient catalyst lifespan.Metal-organic framework(MOF)materials,which have at-tracted significant attention recently,hold tremendous potential.Their tunable porous structures and well-defined active sites are conducive to improving NO3-reduction efficiency and selectivity.Remarkable progress has been made in this field:ad-vanced MOF-based materials have achieved an NH3 Faraday efficiency(FE)of nearly 99％,suppressed NO2-accumulation,and pushed the NH3 yield to＞23000 μg·h-1·mgcat-1.By constructing conductive composite structures and employing derivat-ization strategies,MOF-based materials can maintain a FE of＞90％and remain stable for over 10 h at industrial-level current densities(＞950 mA·cm-2).This review focuses on MOF-based electrocatalysts and systematically analyzes the mechanism of neutral eNO3RR.Leveraging the atomic-level designability of MOFs,strategies such as single-atom/cluster regulation,multi-metal synergy,conductive composites,and derivatization can precisely overcome the bottlenecks of proton supply,hydrogen evolution competition,and stability in neutral eNO3RR,enabling efficient conversion of pollutants to NH3.Nevertheless,sev-eral challenges remain before this goal is fully achieved:the dynamic identification of active centers during catalysis is not sufficiently clear and accurate,long-term stability in real water bodies needs verification,and issues such as large-scale syn-thesis urgently require solutions.

Ligands with high sulfur densities hold immense promises for constructing coordination materials with superior electronic and catalytic properties; however, the synthetic challenges associated with their solubility and stability have left this area largely unexplored. Addressing this gap, we designed a novel octakis(methylthio)functionalized ligand, dimethyl 2,2 ',3,3 ',5,5 ',6,6 '-octakis(methylthio)-[1,1 '-biphenyl]-4,4 '-dicarboxylate (SDA), and successfully incorporated it into a cuprous cyanide framework. Solvothermal reaction of SDA with CuCN yielded [Cu-19(CN)(19)(SDA)(2)(DMF)(2)]center dot 2DMF (1), an unprecedented compound featuring two-dimensional coordination layers. Structurally, the architecture is defined by inorganic cuprous cyanide chains woven together by Cu-4(SDA) nodes and reinforced by Cu center dot center dot center dot Cu interactions. This unique assembly endows the compound with intense photoluminescence at 550 nm upon excitation at 400 nm. Combined experimental spectroscopy and theoretical calculations reveal that this emission stems from a rare metal-ligand-to-ligand charge transfer (MLLCT) mechanism, where electron transfer occurs from the copper-cyanide-dominated highest occupied crystal orbital to the lowest unoccupied orbital localized on the organic ligand. These findings demonstrate the potential of sulfur-dense ligands to access novel electronic states and to form stable functional frameworks.

Open-shell radicals, susceptible to quenching by self-coupling, have found numerous practical applications in materials science and the medical field due to their high reactivity and rich photophysical and electronic properties. Porous and highly customisable crystalline frameworks, such as metal-organic frameworks (MOFs) and covalent organic frameworks (COFs), are ideal platforms for hosting radicals while suppressing their self-coupled annihilation. Yet, current strategies for introducing persistent radicals into these frameworks involve the benzannulation of sterically bulky alkyne-rich motifs and post-synthetic addition to alkyne moieties, which in turn compromise the porosity and crystallinity of the frameworks. Herein, a simple backfolded alkyne-rich diamine-terminated linker was designed and allowed to form a stable 2D COF, BF-COF. Upon facile thermocyclisation, radical-rich BF-COF-300 was obtained with retained crystallinity and porosity as well as far intense and wider light absorption than the primitive BF-COF. These also feature BF-COF-300 as a better candidate than BF-COF in both photothermal conversion and photocatalytic thioether oxidation.

Solar-driven photocatalytic synthesis of hydrogen peroxide (H2O2) offers a sustainable alternative to the energy-intensive anthraquinone process. Donor-acceptor (D-A) covalent organic frameworks (COFs) are highly promising photocatalysts for this transformation; however, the precise correlation between electronic conjugation, D-A pairing, and catalytic efficiency remains poorly understood. Here, we systematically investigate the threshold of conjugation enhancement on photocatalytic H2O2 production by designing D-A COFs with varying degrees of π-conjugation. Using benzotrithiophene (BTT) as the electron donor, we integrated acceptor units featuring alkyne and extended-ring motifs (yielding TATAB-BTT and TATAP-BTT). We reveal a distinct structure-activity relationship: moderate conjugation (TATAB-BTT) optimizes energy-level matching and maximizes charge separation, achieving an outstanding H2O2 production rate of 1610.8 µmol g-1 h-1, outperforming the less-conjugated literature example, TAPB-BTT (557.0 µmol g-1 h-1). Conversely, excessive conjugation (TATAP-BTT) induces a structural mismatch that shifts the electronic configuration from D-A to D-D, severely trapping excitons and diminishing performance (780.0 µmol g-1 h-1. These findings demonstrate that an optimal conjugation threshold is critical for sustaining D-A charge-transfer dynamics, providing a fundamental molecular design principle for next-generation polymeric photocatalysts.

Dual-atom catalysts (DACs) provide great potential for boosted photoreduction of diluted CO2, while the significance of inert sites in DACs is still overlooked. Herein, by loading extra Zn atoms into conducive metal-organic frameworks (CMOFs), we elaborately construct a well-defined DACs with a NiZn & horbar;O4 configuration to decipher the critical role of inert Zn sites in DACs. Under visible light irradiation in pure CO2, the NiZn & horbar;O4 DACs with the optimal Zn/Ni ratio exert a boosted CO generation rate of 20.17 mu mol h-1 with a selectivity of 97%, which is significantly higher than that of the pristine Ni & horbar;O4 single atom catalysts (SACs) and most documented systems. Additionally, in diluted CO2, the activity difference between them increases, and the CO selectivity of Ni & horbar;O4 SACs drops from 95% to 88%, while it remains nearly constant (94%) in the NiZn & horbar;O4 DAC-based system. Experiments combined with theoretical analysis demonstrate that the inert Zn sites enhance the electronic density of the coupled Ni sites, which accelerates electron transfer, promotes reduction kinetics, and lowers the energy barrier for the generation of *COOH key intermediate. This work highlights the intrinsic role of inert sites, paving new avenues for designing effective DACs for various applications.

Deciphering heterometallic synergy in the oxygen evolution reaction (OER) remains a challenge due to the structural complexity of traditional catalysts. We report a series of fluorinated metal–organic frameworks, M‐dfdmt (M = Fe, Co, Ni), featuring a “mercapto‐carboxyl” (mercarb) coordination motif that marries electrical conductivity with catalytic site accessibility. Within this architecture, soft thiolate groups establish deep M–S orbital hybridization for continuous charge transport, while labile [MO6] units serve as primary active sites. While homoleptic Ni‐dfdmt exhibits high intrinsic conductivity (7.34 × 10−4 S cm−1), the heterometallic NiFe‐dfdmt achieves superior OER activity. Theoretical charge population analyses, corroborated by X‐ray photoelectron spectroscopic binding energy shifts, reveal that coupling Ni and Fe induces a directed electron density shift and establishes local electric‐field gradients between heterometallic centers, which optimizes the electronic environment for intermediate adsorption. Kinetic studies, including a reaction order of 1.04 with respect to OH−, further support a lattice oxygen mechanism (LOM). By isolating heterometallic crosstalk within a crystallographically precise lattice, this work clarifies how electronically rewired coordination environments can modulate intermediate binding and facilitate charge transfer in molecularly defined electrocatalysts.

A benzothiophene-based COF (BDT-COF) is designed and grown in situ on a glass fiber (GF) separator. Leveraging the imine-thiophene bidentate coordination toward Zn2+, BDT-COF achieves a uniform Zn2+ flux, improved ion migration kinetics, and efficient desolvation of hydrated Zn2+, thus boosting the reversibility of the Zn anode in aqueous zinc-ion rechargeable batteries. Consequently, the symmetric cell with the BDT-COF@GF separator achieves a stable stripping/plating process over 1000 h at 3 mA cm-2/1 mAh cm-2 and the asymmetric cell can cycle stably for more than 1100 cycles at 10 mA cm-2/1 mAh cm- 2. The Zn|BDT-COF@GF|MnO2 cell exhibits impressive cycling performance with a capacity retention of 89.2% after 1000 cycles.

The development of environmentally sustainable solar fuels through the carbon dioxide reduction reaction (CO2RR) is a crucial advancement towards achieving a carbon-neutral society. However, the sluggish reaction kinetics of CO2RR present practical obstacles in fully realizing its potential. This work demonstrates the introduction of functional groups (such as -OH, -F) proximity to the catalytic site can significantly enhance the photocatalytic CO2RR performance of trinuclear metal-organic framework (MOF) catalysts. Experimental results indicate that the Fe2NiTPTB-OH exhibits the highest CO2-to-CO conversion efficiency, achieving a rate of 63.5 mmol g- 1 h- 1 and a product selectivity of 98.4 %, outperforming its counterparts. The superior performance of Fe2NiTPTB-OH benefits from the favorable formation of *COOH intermediates, as confirmed by in-situ FT-IR spectroscopy. Theoretical analyses reveal that dual sites of metal centers and functional groups in MOFs synergistically stabilize the key intermediate *COOH, with Fe2NiTPTB-OH exhibiting optimal adsorption energy and hydrogen bond interactions with *COOH. Furthermore, free energy calculations indicate that Fe2NiTPTB-OH exhibits a low energy barrier for the conversion of CO2-to-CO. This work offers a novel and promising strategy to facilitate the conversion of CO2 into CO by optimizing the secondary coordination sphere of the catalytic site to promote photocatalytic activity.

Addressing heavy-metal pollution and anthropogenic CO2 emissions simultaneously represents a formidable challenge. Herein, we report a closed-loop "waste-to-wealth" strategy that couples Pb2+ remediation with electrocatalytic CO2 upgrading using SU-102, a stable metal-organic framework (MOF) constructed from biomass-derived ellagic acid. SU-102 exhibits an exceptional intrinsic affinity for sequestering Pb2+ directly from highly acidic simulated industrial wastewater. Rather than generating hazardous secondary waste, this targeted cation-exchange process seamlessly transforms the pollutant-loaded matrix into SU-102-Pb, a structurally precise electrocatalyst with Pb2+ uniformly tethered to oxygen-rich nodes. These captured Pb ions act as isolated catalytic centres for CO2 reduction, delivering a state-of-the-art HCOO- faradaic efficiency of 96.5% at -0.98 V vs. reversible hydrogen electrode (RHE) and maintaining >80% selectivity across a broad 600 mV window. In situ spectroscopy mechanistically validates that these rationally engineered sites drive the reaction exclusively via a favorable *OCHO intermediate pathway. Scalable to the gram level using actual wastewater matrices, SU-102-Pb represents one of the highest-performing Pb-based MOF electrocatalysts reported to date. This work provides a compelling, sustainable blueprint for valorising toxic environmental pollutants into high-value functional materials for clean energy conversion.

Sulfur-containing PTZ-COF and oxygen-substituted PXZ-COF were synthesized for photocatalytic H2O2 production. PXZ-COF demonstrated superior catalytic performance, attributed to a unique dipole polarization enhancement mechanism arising from high electronegativity of the oxygen heteroatom combined with an optimal π-conjugated system. This work presents a novel microenvironment engineering strategy for advanced COF photocatalysts.

Aqueous Zn-ion batteries provide an alternative solution to grid energy storage, but their development has been hindered by dendrite formation and parasitic reactions on Zn anodes. Artificial protective layers hold great potential for alleviating these issues, in which the coordination between zincophilic sites and Zn2+ plays a crucial role. However, the coordination mode, a key descriptor of interactions, is largely overlooked. Herein, we present a strategy to govern Zn2+ diffusion and deposition behavior by changing its coordination mode in the metal-organic framework (MOF) protective layer by installing bidentate dihydroxyanthraquinone (AQOH) and monodentate anthraquinone (AQ) groups onto UiO-66 to afford UiOAQOH and UiO-AQ. Thanks to the superior chelating ability of the adjacent dual oxygen sites, the bidentate coordination is demonstrated to enable UiO-AQOH as a powerful ion-trapper to modulate Zn2+ more effectively than UiO-AQ. Specifically, this coordination mode expedites the desolvation of hydrated Zn2+ by kicking off more coordinated water than monodentate coordination, thereby suppressing waterinduced side reactions. Meanwhile, it contributes to improving Zn2+ transport kinetics and guiding the diffusion of captured Zn2+ along the target-distributed sites in nanochannels, ensuring a homogeneous Zn deposition. Notably, the assembled Zn||MnO2 full cell achieves an impressive ultra-long cycle life of 10,000 cycles at 3 A g-1, surpassing most reported cases. This work provides new insights into designing advanced Zn anodes for high-performing aqueous batteries. (c) 2026 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights are reserved, including those for text and data mining, AI training, and similar technologies.

This study explores a novel approach to enhance proton (H+) conduction in covalent organic frameworks (COFs), key to advancing proton exchange membrane fuel cells (PEMFCs). Traditional strategies to improve H+ conductivity involve increasing carrier concentration or optimizing conduction pathways, but these approaches are often applied separately. Here, azole-induced tautomerization is proposed as a combined strategy that both boosts H+ carrier density and improves conduction via active ordering within COF pores. Specifically, loading imidazole into the pristine thiourea-bridged COF (COF-S) transformed it from an insulator into a highly conductive material, boosting its H+ conductivity by 5 orders of magnitude and yielding the proton-conducting COF-S-T. Spectroscopic analyses reveal greater tautomerization in COF-S-T than in other analogues reported in this work, with solid-state pulsed-field gradient nuclear magnetic resonance (PFG-NMR) indicating a more ordered arrangement of H+ carriers. Complementary density functional theory (DFT) and molecular dynamics (MD) simulations provide insight into the mechanisms, demonstrating how azole-induced tautomerization promotes H+ conduction at both microscopic and dynamic levels. This work introduces an unprecedented way for manipulating guest molecules to achieve active ordering of H+ carriers, thereby significantly advancing the development of high-performance COFs for fuel cell applications.

Soft/hard carbon nanosheets are promising anodes for potassium-ion batteries, of which the key challenge is to improve their sluggish diffusion kinetics and severe volume variation. Herein, N/P/S co-doped soft/hard carbon nanosheets (NPSNs) were fabricated for the first time from coal tar pitch and rapeseed cake by a green salt-template-assisted strategy. The as-fabricated NPSN3–1 features enlarged interlayer spacing (0.38 nm) and abundant defect sites. Consequently, the NPSN3–1 anode delivers a capacity of 395.2 mAh g−1 at 0.1C and retains 121.1 mAh g−1 at 20C, respectively, maintaining 143.2 mAh g−1 with a capacity retention of 84.8% after 1000 cycles at 5C. This work provides a green salt-template-assisted strategy to develop high-performance N/P/S co-doped carbon nanosheet anodes for potassium-ion batteries.

Controlling the network topology in crystalline materials is a key challenge in crystal engineering. While masked synthesis has facilitated the growth of single-crystal thiol-metal-organic frameworks (S-MOFs), achieving precise control over complex features, such as interpenetration, remains difficult. We show that the metal precursor's hydration level acts as a crucial switch that guides the framework topology. Simply replacing hydrated zinc acetate (Zn(OAc)2 & centerdot;2H2O) with anhydrous Zn(OAc)2 results in a significant topological change from a three-fold (Zn-HTT-3F) to a six-fold interpenetrated framework (Zn-HTT-6F), based on [ZnS4] nodes and hexathioltriphenylene linkers. Single-crystal analysis uncovers a hierarchical "intertwining of sub-nets" packing mode in Zn-HTT-6F, highlighting precursor engineering as an effective strategy for controlling network topologies.

Steering the O2 photoactivation for boosting the generation of reactive oxygen species (ROSs) with moderate oxidant strength is crucial for fine organic synthesis, while it remains a huge challenge. Herein, by constructing a pair of metal-organic frameworks (MOFs) with isomeric linkers, i.e., Ni-TTPz-α and Ni-TTPz-β, we demonstrate the first achievement in modulating the chromophore linker torsional angle in MOFs for the precise regulation of ROSs generation. Ni-TTPz-α is equipped with a coplanar conjugated α-thiophene linker, while Ni-TTPz-β features misalignment between the bithiophene and pyrazole moieties due to the zigzag configuration of the β-linker. As a result, Ni-TTPz-α significantly boosts the production of superoxide radicals (O2•-) under visible light in air, whereas Ni-TTPz-β exclusively generates singlet oxygen (1O2) with much lower performance. The boosted generation of O2•- empowers Ni-TTPz-α to efficiently drive the oxidative coupling of benzylamine to imine, achieving a 99% yield within 12 h, which is significantly boosted than that of Ni-TTPz-β (48%). Experiments and theoretical calculations jointly confirm that planar α-thiophene features an angle-induced restricted twist effect that facilitates efficient electron transfer from the thiophene sulfur to the pyrazole unit and, ultimately, to the metal center, thereby driving single-electron oxygen reduction to produce O2•-.

Metal-organic frameworks (MOFs) are premier platforms for photocatalytic hydrogen evolution (PHER), yet navigating their multidimensional parameter space typically relies on inefficient trial-and-error approach. While machine learning (ML) can accelerate discovery, it is often hindered by ″black-box″ predictions that lack mechanistic transparency and experimental validation. Herein, we establish an interpretable ML-to-experimental framework for rational MOF engineering. By training a CatBoost model on a curated database and employing SHapley Additive Explanations (SHAP), we deconstructed the hierarchical influence of ligand motifs on catalytic activity. This revealed the cooperative effect of hydroxyl and amino dual functionalization, which optimizes the electronic landscape through balanced bandgap dynamics and hard-soft acid-base (HSAB) matching. Guided by these insights, we synthesized benzophenanthrene-based mixed-ligand MOFs. The champion catalyst achieved a peak HER rate of 73.7 mmol g-1 h-1─without external photosensitizers or cocatalysts─exhibiting a 4.18% deviation from algorithmic predictions and a 15.8% enhancement over the top of the data set. This work develops a high-performance photocatalytic system and provides a generalizable, interpretable paradigm for data-driven discovery of advanced energy materials.

Plasmonic metal-organic frameworks (MOFs) integrate the exceptional light harvesting capability of plasmonic nanostructures with unparalleled active-site designability of MOFs, offering a promising avenue for constructing advanced antenna-reactor catalysts for chemical conversions. However, conventional synthetic strategies typically require the use of surfactants or polymeric stabilizers to prevent aggregation of plasmonic metals, impeding interfacial charge transfer and thus compromising the synergy between plasmonic effects and catalytic processes. Herein, we report a ligand-induced self-reduction strategy to fabricate a plasmonic MOF-based antenna-reactor catalyst (Au NP/HTHATN-Ni) through the spontaneous reduction of HAuCl4 by the redox-active bipyridine moieties and NiS4 entities embedded within a two-dimensional conjugated HTHATN-Ni framework. In this architecture, atomically defined NiS4 motifs function as reactors for nitrite electroreduction to ammonia, while the Au nanoparticles (Au NPs) serve as the plasmonic antennas for accelerating the reaction kinetics and enhancing product selectivity during nonradiative decay processes. The intimate interfacial contact between the Au NPs and HTHATN-Ni enables efficient hot-electron injection into NiS4 active sites, while the ordered two-dimensional porous framework facilitates rapid mass transport of reactants and intermediates. As a result, the Faradaic efficiency toward NH3 is nearly doubled, accompanied by a 15% suppression of the Faradaic efficiency toward competitive hydrogen evolution. Combined experimental investigations and density functional theory calculations reveal that plasmon-induced hot electrons lower the energy barriers for key hydrogenation and deoxygenation steps (*NO2-* *NO, *NO-* *NOH and *NH2-* *NH3), while strengthening *H adsorption to inhibit parasitic H2 generation. This work provides a general interfacial engineering strategy to construct plasmonic MOF-based antenna-reactor catalysts for distributed green ammonia synthesis from environmentally hazardous nitrogen oxyanions via efficient light-electricity synergy.