Conjugated microporous polymers (CMPs) provide a versatile platform for incorporating various photoactive structures into porous frameworks through the strategic design of molecular building units. This molecular engineering approach allows for precise modulation of bandgap structures and electronic configurations at the atomic level. Current research predominantly focuses on two-motif molecular designs for CMP-based photocatalysts, whereas three-motif architectures remain significantly underexplored with respect to synthetic accessibility, structure-property relationships, and the mechanistic elucidation of photocatalytic processes. Herein, we report the synthesis of a thiazolo[5,4-d]thiazole (TZ)-incorporated three-motif molecular junction CMP (CMP-TZ-BTDT) through condensation polymerization of dithiooxamide with 4,4 ',4 '',4 & tprime;-((benzo[c][1,2,5]thiadiazole-4,7-diylbis(1,4-phenylene))bis(azanetriyl))tetrabenzaldehyde (BTDT). Strategic incorporation of benzothiadiazole as a photoactive component within the CMPs framework significantly enhances visible-light absorption capacity, resulting in improved photocatalytic performance through the efficient generation and separation of photogenerated charge carriers. Systematic characterization reveals that CMP-TZ-BTDT with a three-motif molecular junction architecture, as a heterogeneous photocatalyst, has a broad substrate scope and recyclability, enabling diverse visible-light-mediated organic transformation reactions. This molecular engineering approach provides significant insights into the rational design of advanced photocatalytic CMP systems with customized optoelectronic properties.

Multifunctional coordination polymers (CPs) with stimulus responses containing viologen have been widely studied and prepared. In this work, based on a novel viologen ligand {H2BCMBPY center dot 2Cl = 1,1 '-bis [(2-carboxybipheny-4-yl)methyl]-4,4 '- bipyridinium dichloride}, 1,2,4,5-benzenetetracarboxylic acid (H4BTEC) and CdCl2 center dot 2.5H2O/ZnSO4 center dot 7H2O, three multifunctional CPs were synthesized under solvothermal conditions, named {[Cd4(BCMBPY)2(BTEC)2]center dot 4H2O}n (1), {[Zn2 center dot 2(BCMBPY)1/2 center dot 2(BTEC)1/2]center dot 2H2O}n (2a), {[Zn2(BCMBPY)(BTEC)]center dot 2H2O}n (2b). Under irradiation with a Xe lamp, three CPs exhibited distinct color changes: CP 1 turned yellowgreen, while 2a and 2b turned blue. Notably, 2b showed high photosensitivity displaying photochromic behavior within 2 s. The discoloration mechanism of three CPs were investigated via time-dependent density functional theory (TDDFT). All three CPs also undergo visible color changes under thermal treatment or ammonia vapor conditions. Furthermore, in studies on inkless erasable printing, QR code anti-counterfeiting and photochromic films, all three CPs demonstrated excellent performance, making them promising candidates for multifunctional stimulus-responsive materials. It was found that the structure and properties of CPs can be tuned by changing the metal center or solvent.

1,4,5,8-naphthalene diimide (NDI) has an electron-deficient structure and is widely used in the fields of photochemical and electrochemical chromism. In this paper, two naphthalene diimide-based coordination polymers(CPs), namely [Cd(DPNDI)(mip)]n (1a) and [Cd(DPNDI)(mip)]n (1b), were designed and synthesized by a solvothermal method using N,N-bis(4-pyridine)-1,4,5,8-naphthalenediimide (DPNDI), 5-methylisophthalic acid (H2mip) and Cd(NO3)2 & sdot;4H2O as raw materials. Both CPs 1a and 1b exhibited rapid photo/electrochromic properties and photocontrolled luminescence properties. It was found that the structure and properties of coordination polymers can be tuned by changing experimental conditions. Remarkably, both CPs 1a and 1b have high sensitivity to ammonia and various organic amines, making them excellent materials for amine detection. In addition, density functional theory (DFT) provides theoretical support for the color changing behavior and spectral simulation of CPs 1a and 1b

Metamaterials possess the powerful capability to manipulate electromagnetic waves and have found extensive applications in some areas such as negative refractive index, optical cloaking, and high absorption. In particular, research on the perfect solar absorbers has attracted significant attention. Here, a simple metamaterial solar absorber is designed, which consists of a Ti substrate, a Si3N4 dielectric layer, a periodically patterned layer made up of Ti-TiN-Si3N4. The research results indicate that the average absorption of the designed absorber reaches 98.9% within the wavelength span of 280-3800 nm, and the overall absorption remains above 94%. Ultra-wideband perfect absorption of the proposed absorber is achieved through the coupled effect of localized surface plasmon resonance (LSPR), propagating surface plasmon resonance (PSPR), magnetic resonance (MR) and cavity resonance (CR). Moreover, both polarization and large-angle incidence have a significant advantage of insensitivity on the absorber. In solar thermal systems, it achieves a total solar absorptivity of 98.8%, with only a 1.2% loss. Moreover, the thermal radiation efficiency reaches 99.0% when the temperature reaches as high as 1500 K, the efficiency of photothermal conversion is 93.2% when the temperature reaches up to 1000 K. Based on the above-mentioned results, the absorber holds excellent application prospects in related fields of solar energy. And its outstanding absorption performance can be fully utilized for driving innovation and development, thereby meeting the continuous growth of clean and renewable energy.

Uncovering the structural-functional relationship between entropy-driven phase structures and lattice distortion/points defect-induced dielectric polarization has always been a long-standing challenge in electromagnetic (EM) wave absorption field. In this work, a strategy of entropy-driven phase engineering was proposed to regulate the evolution of EM spectra of carbon confined alloy composites. With increasing alloy entropy, the phase structure evolves from a single FCC phase to an FCC+BCC dual-phase structure, accompanied by lattice distortion and point defects. These entropy-induced effects effectively enhance electron scattering, moderately suppress excessive electrical conductivity, and weaken the skin effect, thereby significantly improving impedance matching. Moreover, abundant dual-phase interfaces and lattice defects generate strong interfacial polarization and dipole polarization, which further boost dielectric loss. Importantly, polarization-dominant medium-entropy FeCoNiCu@C has been obtained by balancing the contribution between dielectric loss and impedance matching, as well as polarization loss and conduction loss, which realizes a broad effective absorption bandwidth (EAB) of 5.8 GHz at 1.8 mm and a minimum reflection loss (RL) of -42.19 dB at 3.85 mm. This work demonstrates that entropy-driven phase engineering accompanied by lattice distortion and point defects provides an effective strategy to synergistically regulate the evolution of EM spectra, thus achieving high-efficiency EM wave absorption performance.

The catalytic activation and reduction of N2 for ammonia synthesis have attracted substantial research interest due to their pivotal role in sustainable nitrogen utilization. Herein, density functional theory (DFT) is employed to systematically investigate the adsorption and reduction of N2 on planar four-metal-atom clusters (M2Cu2, M = Sc, Y, Ti, Zr, Hf, Sn, Pd, Pt, Ag, Au, Zn, Ga) supported by two-dimensional substrate C5N2H2. In the twelve catalysts, four metal atoms exhibit two unique coordination modes with the substrate: 31-type (each M coordinates to three N atoms; each Cu to one N atom) and 22-type (each M and Cu both coordinate to two N atoms), with the 31-type ones having a higher symmetry. All these catalysts can form stable structures, and generally the 31-type ones have more negative formation energies and binding energies of metal atoms on the substrate. The 31-type catalysts adsorb N2 more strongly, with the Zr2Cu2@C5N2H2 catalyst showing the highest adsorption energy of -1.39 eV. The M metal dominates N2 adsorption in the 31-type catalysts, while Cu also plays a prominent role in 22-type ones. By evaluating N2 and H adsorption energies, three 31-type catalysts (Zr, Y, and Hf) were selected for further protonation pathway analysis. The Zr2Cu2@C5N2H2 catalyst exhibits optimal performance for the nitrogen reduction reaction (NRR) with the lowest rate-determining step energy barrier of 0.84 eV (*NH2NH3 -> *NH3NH3) across both enzymatic and consecutive mechanisms. Notably, a pronounced Metal-site Charge Transfer Effect (MCTE) is observed, where substantial electron gain by the active metal atoms correlates with elevated energy barriers in each hydrogenation step. These findings demonstrate that planar fourmetal-atom cluster catalysts M2Cu2@C5N2H2, with unique coordination environments, particularly the 31-type ones, provide an effective strategy for boosting N2 activation and NRR performance.

A novel propellane-nanoring hybrid, TPPTI-[9]CMP, was synthesized by triply combining [9]cyclo-meta-phenylene ([9]CMP) with triperyleno[3,3,3]propellane triimides (TPPTI). This structure features two [9]CMP subunits, which necessarily fill the voids of TPPTI and promote assembly of the hybrid to form a porous superstructure held together by attractive dispersion between the [9]CMP subunits of neighboring molecules. In the structure, three large spatial cavities are formed, which allow efficient binding of up to three C60 within a single hybrid. Transient absorption spectroscopy revealed that TPPTI-[9]CMP and C60 interact with each other to form a stable complex and produce long-lived triplet states. Notably, the hybrid can adsorb ethane (C2H6) with very excellent selectivity over ethylene (C2H4), leading to a highly selective C2H6/C2H4 separation.

One dimensional metal silicate composites have attracted a considerable interest across diverse applications due to their high specific surface area and exceptional unique structure. However, rare works have been developed for their inherent functionalization. To address this issue, we systematically explored the co-condensation growth mechanism of amino-functionalized silica micro/nanotubes using MoO3@APTES microcables as templates. Followed by coated with SiO2 layer under stober condition, the APTES@SiO2 micro/nanotubes can be easily obtained. After treated by hydrothermal reaction in the presence of transition metal ions, the amine functioned metal silicate microtubes were finally harvested. The experimental results revealed that APTES layer could not only retain the tubular structure, but also can enhance the adsorption capacity for organic pollutants. As a concept of application, the APTES@magnesium silicates micro/nanotubes with a diameter of approximately 750 nm, featuring high amino group densities and mesoporous magnesium silicates, exhibited an exceptional maximum adsorption capacity of 555.96 mg g-1 for methylene blue(MB), underscoring their potential for the removal of organic pollutants. More importantly, these APTES@nickel/copper silicate micro/nanotubes were utilized as self-sacrifical template for loading Ni/Cu NPs owing to reduction ability of APTES under the N2

Nickel-cobalt layered double hydroxides (NiCo-LDHs), as potential electrode materials for supercapacitors, have unique layered structures and high theoretical specific capacitance. Unfortunately, NiCo-LDHs often suffer from inherent low electrical conductivity and their unsatisfactory cyclic stability, hindering their practical applications. In this study, three-dimensional porous spherical structural NiCoZn-LDH/GN composites were constructed with small-sized graphene nanosheets (GN) as substrates by a facile hydrothermal strategy. GN can act as mechanical supports to prevent aggregation of NiCoZn-LDH nanosheets. The as-fabricated Ni1Co2Zn1-LDH/GN composite has a high specific capacitance of 2838 F g-1 at 1 A g-1, which is much higher than those of GN (21 F g-1) and NiCo-LDH (1979 F g-1). This is because the surface functional groups of the small-sized GN contribute to the initial nucleation of NiCo-LDH, which ensures the efficient combination of NiCo-LDH and GN, thus enhancing the electron transport rate of Ni1Co2Zn1-LDH/GN. Moreover, compared to NiCo-LDH, Zn doping induces the NiCoZn-LDH/GN composite a more open three-dimensional structure, facilitating mass transfer and improving the charge transport behavior. An asymmetric supercapacitor (Ni1Co2Zn1-LDH/GN//AC) was assembled using Ni1Co2Zn1-LDH/GN as a positive electrode and AC as a negative electrode, with an energy density of 61.1 Wh kg-1 at 800 W kg-1. Therefore, this study provides a new approach for obtaining highperformance NiCo-LDH-based supercapacitor electrodes through the introduction of GN and Zn doping.

ConspectusThe introduction of a five-membered ring into hexagon-fused networks typically induces strain that causes positive Gaussian curvature, leading to bowl-shaped polycyclic aromatic hydrocarbons (PAHs), often referred to as buckybowls or π-bowls. The interest in buckybowls is derived from their intriguing properties including, but not limited to, pyramidalized sp2 carbon atoms, low-lying lowest unoccupied molecular orbital (LUMO), surface charge stabilization, and bowl-to-bowl inversion. In recent years, investigations into the functionalization of buckybowls, as well as the structural aspects related to properties, have made significant progress. Indeed, the functionalization of buckybowls is a major route to increase structural diversity and fine-tune their properties. In particular, the fusion of aromatic rings to buckybowl rims (π-extension of buckybowls) has established a particularly promising synthetic strategy to access a wide range of buckybowl-based nanostructures with unique topologies and properties. A major obstacle, however, is the limited number of appropriate buckybowls, which could be suggested as potential frameworks for further functionalization. Moreover, buckybowls have been typically synthesized by ring-closing reactions, but many of these procedures suffer from the occurrence of considerable strain and lead to an undesired rearrangement. As a result, the development of buckybowl-based nanocarbons with desirable properties is still in its infancy due to the limited structural diversity, functionalization, and scalability.This Account describes our recent progress in the synthesis of buckybowls and buckybowl-based nanocarbons. In our study, diindeno[4,3,2,1-fghi:4',3',2',1'-opqr]perylene (DIP), pyracyleno[6,5,4,3,2,1-pqrstuv]pentaphene (PP), tetracyclopenta[cd,fg,jk,mn]pyrene (TPP), and corannulene are employed as basic structural units, which exhibit a bowl-shaped geometry and offer an ideal platform for functionalization. General bottom-up approaches have been used to access buckybowl derivatives functionalized with peripheral alkynyl and aryl groups. These substituent groups significantly influence solubility, energy levels, and crystal packing, all of which impact their performance. These buckybowls are ultimately converted into π-extended nanocarbons with wide-ranging structural diversity, including doubly curved, rippled, and chiral nanocarbons. Chiral buckybowl-based nanocarbons, where chirality is introduced from quasi-[8]circulene moieties, have high enantiomerization barriers, enabling the separation of the enantiomers. Notably, the rippled nanocarbon containing 10 aromatic rings directly fused to the TPP core exhibits attractive electronic, magnetic, and mechanical properties, which can be further functionalized through the use of well-established chemistry, opening up many possibilities to access unusual carbon allotropes.The assembly with fullerenes is an important application for buckybowls and buckybowl-based nanocarbons. Depending on the peripheral substituent, the binding constant of buckybowls with fullerenes can be tuned. Moreover, buckybowl-based nanocarbons significantly increase the ability to bind fullerenes, resulting in the formation of highly ordered host-guest systems. These features make the nanocarbons excellent molecules for device applications. As expected, these buckybowl-based nanocarbons can function as organic semiconductors for organic field-effect transistors (OFETs), which have mobilities up to 2.30 cm2 V-1 s-1. The host-guest complexes exhibit highly efficient ambipolar characteristics with nearly balanced mobilities on the order of 10-1 cm2 V-1 s-1. In addition, some buckybowl-based nanocarbons show promising applications in photothermal materials with over 90% photothermal conversion efficiency.

Na4Fe3(PO4)2P2O7 (NFPP) has garnered significant attention as a promising cathode material for practical sodium-ion batteries, owing to its high structural stability and low cost. However, the susceptibility to form inactive maricite-NaFePO4 during synthesis and poor intrinsic electronic conductivity limit the high Na-storage performance in NFPP. A self-sacrificing and clean-exit strategy was developed to synthesize phase-pure NFPP. The formation mechanism was elucidated through molecular dynamics simulations, UV-Vis, Raman and XRD: an amorphous precursor from complex coordination ensures homogeneous elemental mixing, creating a kinetically and thermodynamically favorable environment for crystallization. Crucially, oxalic acid serves only as a coordinating agent and is fully volatilized, mitigating the high carbon content issue associated with conventional synthesis methods using citric acid. Consequently, the phase-pure NFPP/OA composite exhibits a high reversible capacity of 110.8 mAh g-1 at 0.1C, outstanding rate capability (101.5 mAh g-1 at 10C), and exceptional cycling stability (99.75 % retention after 2000 cycles). Furthermore, The Na+ storage mechanism and electrochemical kinetics were systematically investigated via in-situ XRD and EIS-DRT analysis. These results provide new insights into the research on mixed polyanion-type cathode materials and offer valuable guidance for their practical application.

Antibiotic drugs are biotoxic and difficult to degrade, causing irreversible effects on aquatic environment and human health. The photoelectrocatalytic (PEC) process is regarded as a promising strategy for simultaneously addressing environmental pollution and the energy crisis. Herein, a plum tree-type composite semiconductor photoanode MnOx@Co/NC-x with core-shell heterostructures was constructed to evaluate the PEC activity for sulfamethoxazole (SMX). The synergistic effects of Co nanoparticles, a high content of graphitic N, an open framework, and interfacial structures played a decisive role in improving the PEC activity of the MnOx@Co/NC-x system. The engineered micro-nano structure significantly improved the specific surface area and conductivity of electrode materials, and promoted the diffusion of electrolyte. Among them, MnOx@Co/NC-500 photoanode exhibited the best performance (reached 98.92% in 50 min), cyclic stability and repeatability. The results showed that it was feasible to construct a high-performance heterostructural interface for pollutant treatment based on micro-nano structure regulation and valence band matching.

In recent years, halide perovskites have made great progress due to their excellent optoelectronic properties. Taking advantage of the excellent elemental tunability of perovskites, a novel perovskite is designed as DAPPb2I6, where DAP indicates NH3(CH2)5 NH32+ The geometry, stability, electronic structure, and optical properties of DAPPb2I6 are investigated based on first principles calculations. Doping effects are taken into account by replacing I by Br. The ab initio molecular dynamics (AIMD) simulations show that these materials have high thermodynamic stability at room temperature. All DAPPb2(I1-xBrx)6 have indirect bandgaps with the calculated values of 2.22-2.72 eV, indicating that introducing of DAP increase the bandgap remarkably. The conduction bands are mainly contributed by Pb atoms, followed by halogen atoms, while the valence band part is mainly contributed by halogen atoms. These materials have high remarkable light absorption capacity with light absorption coefficients up to 4.5 x 105 cm-1 with wavelengths in the range of 200-450 nm. Doping of Br can increase the bandgap values and the cause blue-shift of the light adsorption. The newly designed DAPPb2(I1-xBrx)6 may serve as a promising wide bandgap perovskite material.

Wide-bandgap perovskite solar cells (PSCs) continue to encounter challenges in long-term stability and open-circuit voltage (VOC) deficits, thereby constraining the performance and stability of all-perovskite tandem solar cells (TSCs). Constructing 3D/2D perovskite heterojunctions represents a promising avenue for performance enhancement; nonetheless, notable shortcomings still persist in carrier transport efficiency and thermal-stability at the 3D/2D heterojunction interface. Herein, a newly designed cross-linked polymer is meticulously deposited onto the surface of 3D perovskite, of which freely distributed carbonyl group (C═O) and N/O atoms effectively saturate surface defects and alleviate tensile strains. The improvement of surface properties induces the generation of gradient energy levels, effectively minimizes the recombination loss caused by the accumulation of minority carriers at the 3D/2D interface. More interestingly, the cross-linked polymer skeleton employs a strong physical barrier to effectively halt the migration of volatile A-site cations across the 3D/2D interface under thermal stress, maximizing the heterostructure's stability. The resultant wide-bandgap PSCs and all-perovskite TSCs achieve a champion power conversion efficiency (PCE) of 20.23% and 28.26% (certified 27.29%), accompanied by exceptional thermal-stability. This work underscores the vast potential of 3D/2D heterojunction design, offering valuable insights for the advancement of wide-bandgap PSCs and all-perovskite TSCs.

Aqueous zinc-ion batteries (AZIBs) have emerged as a promising candidate for next-generation energy storage technologies due to their inherent safety, environmental compatibility, and cost-effectiveness. However, the propensity for concomitant hydrogen evolution reaction (HER), corrosion, and zinc dendrite formation at the zinc anode significantly impede their widespread adoption. To overcome the limitations, we propose using a trace-amount low-cost additive, dihydroxyacetone (C3H6O3) with 20 mM, to improve the reversibility of zinc plating/stripping for high-performance AZIBs. C3H6O3 with high zinc adsorption ability not only can reconstruct the Zn2+ solvation sheath, reducing the H2O activity in the solvation sheath but exhibits strong affinity on the zinc surface, inhibiting corrosion and regulating ion flux for uniform Zn2+ plating, which effectively improve the stability of zinc anode. Therefore, the Zn||Cu cell achieves a high Coulombic efficiency of >99 % at 1 mA cm-2, and the Zn||Zn symmetric cell demonstrates high cycling stability, exceeding 1600 h at a current density of 1 mA cm-2 while maintaining a low overpotential, and sustaining operation for 220 h at a high current density of 10 mA cm-2. This study elucidates the mechanistic underpinnings of the influence of a new additive on the zinc anode interface, offering a viable pathway toward high-performance aqueous zinc-ion batteries.

Ruthenium has regards as a potential electrocatalyst candidate towards hydrogen evolution reaction (HER) to substitute platinum and its surface property regulation is vital for increasing catalytic activity to realize the wide industrialization. Herein, we report a simple and facile method to regulate the metallic surface of Ru nano-particles through high temperature calcination without particle overgrowth. The nanopores in Ketjenblack EC600JD are employed as nanoreactors with Ru precursor ultrasonicated and impregnated and the subsize Ru nanoparticles embedded in porous carbon with highly metallic surface are obtained by high temperature annealing. The as-prepared Ru@KB-900 electrocatalyst shows excellent catalytic activity for HER with the overpotentials reached 9.9 mV and 28 mV at the current density of 10 mA cm-2 and the mass activities of 7404 A gRu-1 outperformed that of commercial Pt/C catalyst in the corresponding conditions. Furthermore, it also delivers a very good life-span performance at the overpotential of 50 mV over 48 h. The high HER activity is ascribed to the highly metallic surface of active site tuned by calcination temperature and the efficient exposure of active sites for the ultrasmall particle size. This study provides a simple and effective method for designing highly active sites with efficient exposure. and 478 A gRu-1 at the overpotential of 50 mV, in acidic and alkaline electrolytes, respectively, which

A photocatalyst-tuned, Ni-catalyzed system enables switchable C-C or C-N coupling of aryl halides with formamide, directly synthesizing unprotected benzamides or N-arylformamides. Selectivity is governed by PC/base pairs. Benzophenone/K2HPO4 affords C-C-coupled benzamides, while thioxanthone TXO/NaHCO3 yields C-N-coupled N-arylformamides. This atom-economical method exhibits a broad scope and excellent regioselectivity, providing a sustainable platform for synthesizing unprotected benzamides and N-arylformamides as valuable building blocks in organic synthesis.

This work presents the first recyclable multi layer films with an impedance optimization design, created via simulation screening, that consists of films ordered and arranged to enhance the absorption bandwidth from 0 GHz to 2.17 GHz. The results presented here provide valuable insights into the design and construction of high-efficiency microwave absorption films by environmentally friendly and sustainable technological means.

Compared to organic-inorganic hybrid perovskite solar cells (PSCs), all inorganic CsPbBr3 perovskite solar cells have higher stability but lower efficiency. Owing to the low solid solubility of CsBr in methyl alcohol, an incomplete first-step reaction with PbBr2 reaction takes place at room temperature. As a result, a large amount of CsPb2Br5 is generated in the final CsPbBr3 film, which deteriorates the performance of CsPbBr3 PSCs. Along these lines, in this work, CsCl was added to increase the reaction between CsBr and PbBr2 in the first step and high-quality CsPbBr3 films were prepared without CsPb2Br5. Our analysis demonstrated that at the optimal CsCl concentration of 6% in CsBr solution, the CsPbBr3 perovskite solar cells exhibited a power conversion efficiency of 7.33%. The best device retained 98.57% of the power conversion efficiency (PCE) after storing it for 30 days under ambient air condition.