Jian Li

In situ ligand dimerization enables redox-active conductive Zn-TAPT with extended π-conjugation, high conductivity, and durable sodium-ion storage.

Stable silica-based extra-large-pore (ELP) zeolites are highly desirable for processing bulky molecules but remain exceedingly challenging to synthesize directly. Here, we report JU-87, a stable, fully connected pure-silica ELP zeolite formed through a 3D-to-3D topotactic condensation of an interrupted 24-membered-ring zeolite precursor (JU-86). The calcination-induced full condensation of the SiO–···HOSi defects in JU-86 yields JU-87, which features one-dimensional 18-membered-ring channels (max. dimension: 17.36 Å) lined with pocket-like cavities and contains abundant, unprecedented, highly strained three-membered-ring units. Owing to its spacious channels, JU-87 can accommodate bulky dye molecules, demonstrating its potential for the adsorption and catalytic upgrading of large substrates.

Sodium‐ion batteries (SIBs) are promising for low‐temperature applications compared with commercial lithium‐ion batteries, because of the weaker solvation and higher conductivity of Na ⁺ in electrolytes. However, the large size of Na ⁺ leads to slow ionic transport and sluggish reaction kinetics in the electrodes, which is more severe after the lattice shrinks under low temperatures. Herein, a conjugated coordination polymer (CCP) is reported as a cathode for low‐temperature SIBs, by using naphthazarin (DHNQ) as the ligands and Ni ²⁺ as the metal centers. Benefiting from the π‐d conjugation, the Ni‐DHNQ exhibits a high electrical conductivity of 69.7 mS/m and maintains both structural integrity and efficient electron and ion transport even at −40°C. These characteristics collectively enhance the reaction kinetics and cycling stability. The Ni‐DHNQ cathode enables ultrafast charging to 52% state‐of‐charge (SOC) in 90 s and exhibits an ultralow capacity decay rate of 0.0028% per cycle over 5000 cycles. When paired with an organic anode, the pouch full‐cell could reach 87% of its SOC even at −40°C, far higher than the commercial lithium‐ion batteries (12%) and reported alkali‐metal‐ion batteries. This work demonstrates the promise of CCPs for high‐performance sustainable energy storage under extreme conditions.

With significant advances in alkane dehydrogenation in recent years, the direct CO2 hydrogenation to light alkanes (ethane, propane, and butanes) over an oxide/zeolite (OXZEO) composite catalyst offers a pathway for light olefin production. Nevertheless, the existing CO2-to-alkanes conversion often relies on the strong acid sites in zeolite micropores for olefin hydrogenation, which tends to cause side reactions and coking. Herein, we discovered the Ni-doping on a CdZrOx catalyst not only enhanced the density of oxygen vacancy for efficient CO2 activation but also promoted the H2 dissociation and spillover capacity. When combined with SAPO-34 aluminophosphate with medium acidity, the NiCdZrOx(0.05)/SAPO-34(0.075) bifunctional system converted CO2 and H2 directly into light alkanes (C20–C40) with an alkane-in-hydrocarbons selectivity of 81% and CO2 conversion of 40% at 350 °C and 4 MPa, maintaining its stability for 100 h. In situ X-ray photoelectron spectroscopy (XPS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) analysis and density functional theory (DFT) calculations attributed the robust catalytic performance to a tailored reaction pathway: CO2 and H2 were efficiently activated on NiCdZrOx(0.05) to form a methanol intermediate, which then migrated to the moderately acidic SAPO-34 aluminophosphate and underwent a controlled methanol-to-olefins (MTO) reaction. The generation of active hydrogen species due to the strong hydrogen spillover effect of NiCdZrOx(0.05) drove the secondary hydrogenation of light olefins into corresponding alkanes. Moreover, the hydrogen spillover also effectively minimized the coke deposition in SAPO-34 micropores, thereby significantly promoting the catalytic activity and stability of CO2 hydrogenation to light alkanes.

Conductive metal-organic frameworks (c-MOFs) are promising functional materials, yet their atomic-level clarity remains obscured by the limited size of available single crystals (typically <10 μm). We demonstrate that the kinetic mismatch between redox-coordination processes and crystal growth is the underlying obstacle, and propose a general strategy to reduce this mismatch by balancing the ligand acid-base equilibrium to control the redox-coordination kinetics. This kinetic aligning strategy enables the growth of single crystals up to over 1 mm in seven c-MOFs, and reveals three new crystal structures with distinct electronic properties. Single-crystal devices demonstrate record-high intrinsic electron-proton dual conductivity among porous MOFs. This work establishes both a fundamental framework and a practical strategy for growing c-MOF single crystals and designing materials that integrate electronic and protonic transport.

The physical properties of van der Waals materials are highly dependent on their stacking sequences. However, constructing layered materials with specific compositions and desired stackings is challenging. Here we show that a solvent-directed strategy enables targeted stacking in van der Waals metal-organic frameworks, an emerging class of van der Waals materials. By leveraging the tunable metastable states of conjugated ligands through various solvents, and stabilizing these states via metal-ligand coordination, we enable the inheritance of stacking patterns from ligands to van der Waals metal-organic frameworks. Notably, this strategy enables the controlled manipulation of stacking sequences and divergent charge transport regimes in two-dimensional and three-dimensional van der Waals metal-organic framework single crystals, yielding an electrical conductivity of 1,792 S cm^-1. These results provide a versatile approach for designing layered materials with programmable stackings and tailored electronic properties.

Stable extra-large-pore zeolites are highly desirable for catalysis and molecular separation, but most remain microporous, limiting their effectiveness for bulky substrates. Among the few extra-large-pore zeolites that exhibit mesoporosity, the pores typically form as elongated, noncircular pore apertures. We report that NJU120-6, a stable silicate zeolite with an intrinsic cylindrical mesoporous system, has the currently largest 36-ring windows with a free diameter of 25.71 angstroms by 19.12 angstroms. NJU120-6 exhibits the lowest framework density of 9.39 silicon atoms per cubic nanometer and a pore volume of 0.66 cubic centimeters per gram. It remains stable up to 1173 kelvin and can incorporate aluminum and titanium, enabling superior performance in catalytic cracking and in liquid-phase alkene oxidation of bulky molecules, respectively.

The stacking modes in two-dimensional conductive metal-organic frameworks (2D c-MOFs) serve as a pivotal design parameter for precisely controlling charge transport pathways, thereby directly regulating carrier mobility and anisotropic transport. Precise control over the stacking modes of atomically precise single-crystal structures of 2D c-MOFs through the bottom-up synthesis remains a major challenge. The reason lies in the dominant role of coordination bonds during 2D c-MOF synthesis, where the weak van der Waals interactions between ligands are often overridden and fail to be expressed in the final MOF architecture. Moreover, most 2D c-MOFs can only be obtained as nanocrystalline powders, making it difficult to obtain precise structural information. Here, we report a new strategy for achieving controllable stacking and enhanced crystallinity in 2D c-MOFs through the asymmetrical electrostatic potential modulation of ligands. By strategically substituting fluorine atoms into the hexahydroxytriphenylene (HHTP) ligands, we modulated the intrinsic charge distribution, enabling the synthesis of two HHTP derivatives with different packing modes. The c-MOF crystals synthesized through this approach exhibit distinct stacking modes and tunable electrical properties. Through the systematic modulation of ligand stacking configurations, this work elucidates fundamental structure-property correlations in 2D c-MOFs, providing a rational design strategy for tailoring 2D c-MOF materials with optimized performance characteristics.