SCIENCE CHINA Materials•2026•DOI: 10.1007/s40843-025-4046-6
The deliberate control of framework dimensionality represents a powerful yet underexplored strategy for tailoring the functionality of homochiral metal-organic frameworks (HMOFs). Herein, we report a logical dimensional evolution from 1D and 2D to 3D HMOFs, achieved by tuning the connectivity of the auxiliary ligand. Employing a planar, three-connected ligand, 2,4,6-tri(pyridin-4-yl)-1,3,5-triazine (Tpt), together with enantiopure tetracarboxylate of cyclohexane diamide linkers ((1R,2R/1S,2S)-cyclohexane-1,2-dicarbonyl bis(azanediyl)diisophthalate) (R,R/S,S-CHCAIP) and Zn2+ salts, a pair of 3D porous HMOFs (P/M-HMOF-5) was successfully constructed. The 3D framework features unique heart-shaped channels and a novel 4-(3,3,3,6)-connected topology. Structural analyses reveal trinuclear Zn3(μ3-O) clusters that, upon activation, generate open metal sites. These Lewis acid sites, synergizing with Lewis basic sites from the framework, confer efficient acid-base bifunctional heterogeneous catalysis for the synthesis of 2,3-dihydroquinazolinones in excellent yields (90%–98%). Furthermore, P/M-HMOF-5 serve as highly sensitive and enantioselective fluorescent sensors for amino acids and α-hydroxy carboxylic acids, with the highest discrimination observed for phenylalanine (KBH(D-Phe)/KBH(L-Phe) = 5.85 for M-HMOF-5). This work demonstrates how rational ligand connectivity steers dimensional evolution, enabling the integration of distinct catalytic and sensing functions within a single chiral platform, thereby providing a blueprint for the design of advanced multifunctional materials.
Environmental Chemistry•2026•DOI: 10.7524/j.issn.0254-6108.2025040401
Conventional zero-valent iron (ZVI) suffers from limited electron transfer due to its dense surface oxide layer. This study introduces a mechanochemical ball-milling strategy incorporating sodium chloride (NaCl) with ZVI to fabricate chloride-modified ZVI (Cl-ZVIbm). Using hexavalent chromium (Cr(VI)) as a model pollutant, Cl-ZVIbm exhibited a 76.5-fold enhancement in removal kinetics (0.0306 min−1 vs. 0.0004 min−1) compared to ball-milled ZVI (ZVIbm), achieving complete removal of 2 mg·L−1 Cr(VI) within 120 min. Spectroscopic characterization and density functional theory (DFT) calculations revealed dual regulation mechanisms: (1) Cl− substitution of surface hydroxyl groups alters coordination environments, enabling Cr(VI) adsorption via a bidentate binuclear configuration with adsorption energy reduced from –0.28 eV to –1.64 eV; (2) The strong electron-withdrawing effect of Cl− drives directional electron migration from the iron core to the surface, increasing surface Fe(II) content by 26.9% (67.5% vs. 53.2%) and facilitating direct electron transfer to reduce 99.5% of Cr(VI) into low-toxicity Cr(III). Notably, chloride leaching during reactions was only 0.0126 mmol·L−1, far below industrial wastewater discharge standards, confirming environmental compatibility. This work provides atomic-scale insights into chloride-mediated electronic modulation on ZVI surfaces, offering novel principles for interfacial engineering of environmental functional materials and a theoretical basis for heavy metal remediation technologies.
SCIENCE CHINA Materials•2026•DOI: 10.1007/s40843-025-3980-y
Organic solar cells (OSCs) have achieved power conversion efficiencies (PCEs) exceeding 20% in laboratory-scale devices, yet challenges persist in developing cost-effective charge-transporting materials (CTMs) that ensure high performance and long-term stability. Conventional organic CTMs such as PEDOT:PSS and PDINN suffer from thermal instability due to molecular diffusion and phase segregation. Solution-processed metal oxides (MOs) offer excellent stability and cost-effectiveness but are plagued by surface defects, particularly hydroxyl groups, which act as recombination centers and photocatalytic sites, degrading device interfaces. Here, we develop an organic-inorganic hybrid strategy to homogeneously passivate solution-processible semiconducting MOs. By first synthesizing MOs rich in surface hydroxyl groups and then introducing organic molecules, we achieve chemically homogeneous passivation that mitigates surface defects. This approach enables favorable interfacial energy level alignment, enhanced charge extraction, and tunable surface energy. Employing these passivated MOs as electron transport layers (ZnO) and hole transport layers (NiOx), we achieve a champion PCE of 20.22% for all-MO CTM-based OSCs, the highest reported to date. Scalability is demonstrated via ambient blade-coating, yielding 18.33% PCE for large-area cells (1.44 cm2) and 16.03% for modules (20.05 cm2), with material costs estimated at only 4% of organic counterparts. Furthermore, devices exhibit outstanding stability, retaining over 80% of initial PCE after 1300 h of maximum power point tracking and over 1000 h of thermal annealing at 85°C. This work establishes a new benchmark for cost-effective, high-performance organic photovoltaics.