The development of hydrogen-bonded frameworks with both robust stability and adaptive functionality remains a significant challenge. Herein, we report a series of hydrogen-bonded ionic frameworks (HIFs) constructed via a supramolecular assembly strategy, utilizing bulky cationic Zn(II) coordination complexes and small inorganic anions. Directional charge-assisted hydrogen bonds effectively suppress close packing and yield robust architectures, with adaptive porosity under external stimuli owing to relatively weak interactions. Notably, HIF-23 exhibits a sophisticated guest-induced gate-opening effect, specifically triggered by the CO₂ with quadrupole moment. Comprehensive density functional theory (DFT) simulations and spectroscopic analyses reveal that the transition is driven by a localized conformational twisting of propane bridges and adaptive nature of the hydrogen-bonding network. The specific interaction with CO₂ enables high CO₂/CH₄ and CO₂/N₂ selectivity, complemented by a substantial high-pressure CO₂ capacity of 30.4 wt.% at 50 bar. This work underscores the potential of the HIF platform for the precision engineering of stimuli-responsive materials tailored for energy-efficient carbon capture.

Increasing the number of surface-active sites and light-harvesting capability of catalysts by regulating their electronic structures is critical for solar-driven reactions. Herein, we report an oxygen-defective rich catalyst, black In₂O_3−x nanosheets, as efficient catalysts for solar-driven CO₂ hydrogenation reaction. The efficiency of CO₂ hydrogenation can be enhanced through the combination of interband transition and active sites oxygen vacancies, coupled with exceptional photothermal conversion that rapidly elevates the catalyst surface temperature to 299 °C. Experimental results and characterization analyses reveal that the introduction of oxygen vacancies not only furnishes abundant adsorption and activation sites for CO₂ but also extends the light absorption range of In₂O_3−x and improves the photothermal conversion efficiency. Black In₂O_3−x nanosheets with oxygen-rich defects exhibit remarkable solar-driven catalytic performance in the reverse water-gas shift (RWGS) reaction, achieving a CO generation rate as high as 69.8 mmol·h⁻¹·m⁻² with a selectivity approaching 100%. This study demonstrates that structural engineering of In₂O₃ nanosheets via a mild room temperature lithium reduction strategy significantly enhances catalytic activity, a methodology promising for broader applications.

This study focuses on V₂O_3−x nanoparticles and systematically analyzes them as plasmonic solar-driven catalysts for the first time. It reveals that they exhibit the localized surface plasmon resonance (LSPR) absorption characteristics in the near-infrared regions. By integrating in-situ characterization and theoretical calculation results, the mechanism of in-situ generation of oxygen vacancies (V_o) in V₂O₃ under irradiation and subsequently transformed into catalytically active V₂O_3−x is elucidated. Furthermore, the process in which V₂O_3−x generates hot electrons and holes through plasmon damping is analyzed, as well as its excellent effects in increasing the local temperature, providing active sites, and enhancing the light absorption capacity. V₂O_3−x demonstrates excellent performance in the reverse water-gas shift (RWGS) reaction, with a CO conversion rate of 668.48 mmol·g⁻¹·h⁻¹, with a CO selectivity exceeding 99.9%, and long-term stability for 90 h, highlighting the great potential of metal oxide plasmas in solar-driven catalysis. This research provides crucial insights into enhancing the solar-chemical energy conversion efficiency by utilizing the synergistic effect of LSPR and intrinsic interband transitions.

New generation of lithium-ion batteries (LIBs) integrating solar energy conversion and storage is emerging, as they could solve the fluctuation problem in the utilization of solar energy. Photo-rechargeable lithium-ion batteries (PR-LIBs) are ideal devices for such target, in which solar energy is converted into electricity and stored in LIB. In order to achieve the high performance of PR-LIB, it is crucial to develop dual-function electrode materials that can synergistically capture solar energy and store lithium. Herein, we present photo-rechargeable lithium-ion batteries using defective black TiO₂ as photoanode prepared by lithium reduction. The photoanode exhibits excellent photo response in full solar spectrum with a capacity enhancement of 46.4% under illumination, corresponding to the energy conversion efficiency of 4.4% at the current density of 1 A·g⁻¹. When illumination is applied at 20 mA·g⁻¹, the battery capacity increases from ~ 230 in dark to ~ 349 mAh·g⁻¹ at the first cycle, and then stabilizes at 310 mAh·g⁻¹, approaching the theoretical value of 335 mAh·g⁻¹ of TiO₂ electrode material. This finding provides thoughts for breaking the capacity limitations in TiO₂ and paves the way for powering LIBs by solar illumination.

Elasticity, as an emerging phenomenon of crystals, endows the newfangled properties on crystals owing to the altered local crystallinity in the deformed state, and hence attracts increasing research endeavors. However, only a few molecular crystals and a limited number of one-dimensional coordination polymer crystals have exhibited such fantastic elastic response under mechanical stress. Herein, we report the first example of elastic hydrogen-bonded ionic framework (HIF) of {(CN₃H₆)₂[Ti(μ₂-O)(SO₄)₂]}_n, assembled from one-dimensional negatively charged inorganic [Ti(μ₂-O)(SO₄)₂]_n²ⁿ⁻ chains and positively charged organic guanidinium cations via hydrogen bonds and electrostatic interactions. The slender prismatic single crystal exhibits remarkable elasticity with an optimal elastic bending strain (ε) of 2.5%. Impressively, the crystals give rise to two-dimensional elasticity owing to the equivalent crystallographic planes of the exposed faces and an unusual elastic response at liquid nitrogen temperature. The in-depth crystallographic analyses reveal hydrogen bonds and electrostatic interactions between anion chains and cations function like adhesive glue and account for such specific elastic properties, owing to the flexible and dynamic attributes of hydrogen bonds as they can work in a range of distance and orientation. And the channel in HIF provides space for bending with reduced strain. Incorporating these factors into low-dimensional crystals could be a general guidance for designing elastic crystals. Elasticity ganged with other intrinsic properties of HIF materials could inspire their newfangled applications in the near future.

Polyoxometalates (POMs) with multiple redox active sites have been reported as charge sponge for lithium-ion batteries (LIBs). Herein, we for the first time introduce a polyoxovanadate (POV) ionic crystals with macrocations, [Ni(Phen)₃][ClV₁₄O₃₄]Cl (NiV₁₄, Phen = 1,10-phenanthroline), as an anode material for LIBs. The existence of macrocation [Ni(Phen)₃]²⁺ stabilizes the open tunnels inside NiV₁₄. The NiV₁₄ electrode exhibits superior rate capabilities (1083 mAh·g⁻¹ at 100 mA·g⁻¹ and 384 mAh·g⁻¹ at 2000 mA·g⁻¹) due to the rapid capacitive dominated contribution and high Li⁺ ions diffusion coefficients (3.3 × 10⁻¹² cm⁻²·s⁻¹), and it delivers a remarkable cycling stability with a Coulombic efficiency of 99.7% after 1000 cycles at 2000 mA·g⁻¹. Such performance can be attributed to the stable structure of NiV₁₄ and the highly reversible valence changes of vanadium during the charge/discharge processes, which are revealed by a combination of in situ X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS) measurements. This work not only demonstrates that NiV₁₄ with open tunnels stabilized by macrocation is a promising anode material for high performance LIBs, but also provides important references for the rational design of POMs electrode materials in advanced energy storage systems.

Polymeric carbon nitride (CN) as a metal-free photocatalyst holds great promise to produce high-value chemicals and H₂ fuel utilizing clean solar energy. However, the wider deployment of pristine CN is critically hampered by the poor charge carrier transport and high recombination. Herein, we develop a facile salt template-assisted interfacial polymerization strategy that in-situ introduces alkali ions (Na⁺, K⁺) and nitrogen defects in CN (denoted as v-CN-KNa) to simultaneously promote charge separation and transportation and steer photoexcited holes and electrons to their oxidation and reduction sites. The photocatalyst exhibits an impressive photocatalytic H₂ evolution rate of 8641.5 μmol·g⁻¹·h⁻¹ (33-fold higher than pristine CN) and also works readily in real seawater (10752.0 μmol·g⁻¹·h⁻¹) with a high apparent quantum efficiency up to 18.5% at 420 nm. In addition, we further demonstrate that the v-CN-KNa can simultaneously produce H₂ and N-benzylidenebenzylamine without using any other sacrificial reagent. In situ characterizations and DFT calculations reveal that the alkali ions notably promote charge transport, while the nitrogen defects generate abundant edge active sites, which further contribute to efficient electron excitation to trigger photoredox reactions.