Synergistic Modulation of π-π* and n-π* Transitions by In Situ Phenol-Like Structure Integration for Efficiently Wide-Spectrum Hydrogen Production of Ultrathin Carbon Nitride.

2D carbon nitride nanosheets, exemplified by g-C3N4, offers significant structural benefits and enhanced photocatalytic activity. Nonetheless, the quantum confinement effect prevalent in nanoscale photocatalysts would result in an enlarged bandgap, potentially restricting the spectral absorption range and impeding improvements in photocatalytic efficiency. Here, a high-performance 2D photocatalyst with an extended spectral response is achieved by incorporating a novel phenol-like structure into the conjugated framework of ultrathin g-C3N4 nanosheet. This novel strategy features targeted pyrimidine doping to create a conjugated carbon zone in heptazine structure, offering a thermodynamically favorable pathway for hydroxyl functionalization during the annealing exfoliation process. Consequently, the π-π* transition energy in the material is significantly decreased, and the active lone pair electrons in phenol-like structure induces a new n-π* transition with notably enhanced absorption from 500 to 650 nm. The optimized material shows a dramatic enhancement in photocatalytic activity, achieving ≈72 times than the activity of bulk g-C3N4, and demonstrating a measurable H2 production rate of 6.57 µmol g-1 h-1 under 650 nm light. This study represents a significant step forward in the strategic design of 2D photocatalysts, with tailored electronic structures that significantly boost light absorption and photocatalytic efficiency.

Synthesis, structure, theoretical calculation and antibacterial property of two novel Zn(II)/Ni(II) compounds based on 3, 5-dichlorosalicylaldehyde thiocarbamide ligand.

Two new compounds namely [Zn(L1)phen]31 and Ni(L1)phen(MeOH) 2 (L1 = 3, 5-dichlorosalicylaldehyde thiosemicarbazone) were synthesized by the slow evaporation method at room temperature. The structure of ligand L1 was determined using 1H NMR and 13C NMR spectra. X-ray single crystal diffraction analysis revealed that compounds 1-2 can form 3D supramolecular network structures through π···π stacking and hydrogen bonding interactions. The DFT calculation shows that the coordination of ligand and metal is in good agreement with the experimental results. Hirshfeld surface analysis revealed that H…H and Cl…H interactions were the predominant interactions in compounds 1-2. Energy framework analysis indicated that dispersion energy played a dominant role in the energy composition of compounds 1-2. The inhibitory effects of compounds 1-2 against Escherichia coli (E. coli) and Methicillin-resistant Staphylococcus aureus (MRSA) were tested using the paper disk diffusion method (1: E. coli: 18 mm, MRSA: 17 mm, 2: E. coli: 15 mm, MRSA: 16 mm). Ion releasing experiments were conducted to assess the ion release capacity of compounds 1-2 (Zn2+, 4 days, 38.33 µg/mL; Ni2+, 4 days, 29.12 µg/mL). Molecular docking demonstrated the interaction modes of compounds 1-2 with UDP-N-acetylenolpyruvoylglucosamine reductase (MurB) and dihydrofolate reductase (DHFR) in bacteria, involving hydrophobic, stacking, hydrogen bonding and halogen bonding interactions. The generation of reactive oxygen species (ROS) in bacteria under the presence of compounds 1-2 were evaluated using a fluorescent dye known as dichlorodihydrofluorescein diacetate (DCFH-DA). Potential antibacterial mechanisms of compounds 1-2 were proposed.

Zirconium Phosphate-Pillared Zeolite MCM-36 for Green Production of γ-Valerolactone from Levulinic Acid via Catalytic Transfer Hydrogenation.

γ-valerolactone (GVL), derived from biomass, is a crucial platform compound for biofuel synthesis and various industrial applications. Current methods for synthesizing GVL involve expensive catalysts and high-pressure hydrogen, prompting the search for greener alternatives. This study focuses on a novel zirconium phosphate (ZrP)-pillared zeolite MCM-36 derivative catalyst for converting levulinic acid (LA) to GVL using alcohol as a hydrogen source. The incorporation of ZrP significantly contributes to mesoporosity and greatly enhances the acidity of the catalysts. Additionally, we employed 31P MAS NMR to comprehensively investigate the influence of phosphorus species on both the acidity and the catalytic conversion of LA to GVL. By adjusting the Zr-to-P ratios, we synthesized catalysts with enhanced acidity, achieving high conversion of LA and selectivity for GVL. The catalyst exhibited high recyclability, showing only minor deactivation over the course of five cycles. Furthermore, the catalyst was successfully applied to the one-pot conversion of furfural to GVL, showcasing its versatility in biomass conversion. This study highlights the potential of the MCM-ZrP1 catalyst for sustainable biomass conversion and offers insights for future research in renewable energy technologies.

Low-silica Cu-CHA Zeolite Enriched with Al Pairs Transcribed from Silicoaluminophosphate Seed: Synthesis and Ammonia Selective Catalytic Reduction Performance.

Cu-exchanged low-silica CHA zeolites (Si/Al≤4) synthesized without organic templates are promising candidate catalysts for ammonia selective catalytic reduction of nitrogen oxides (NH3 -SCR), but their practical application is restricted due to the low hydrothermal stability. Here, inspired by the transcription from duplex DNA to RNA, we synthesized Al pairs enriched low-silica CHA zeolite (CHA-SPAEI, Si/Al=3.7) by using silicoaluminophosphate (SAPO) featured by strict alternation of -Al-O-P(Si)-O-Al-O- tetrahedra as seed. The proportion of Al pairs in CHA-SPAEI is 78 %, which is much higher than that in the conventional low-silica CHA (CHA-LS, 52 %). After hydrothermal ageing at 800 °C for 6 h, Cu-exchanged CHA-SPAEI shows NO conversion above 90 % within 225-500 °C under a gas hourly space velocity of 200,000 h-1 , which is much better than that of Cu-exchanged CHA-LS. The spatial close proximity of Al pairs in CHA-SPAEI is confirmed by the 27 Al double-quantum single-quantum two-dimensional NMR analyses. The strict -P(Si)-O-Al-O-P(Si)-O- sequence in the fragments from the dissolution of SAPO seed promotes the Al pairs with the -Al-O-Si-O-Al-O- sequence via a transcription process. The utilization of aluminophosphate-based zeolites as seeds opens up a new avenue for the regulation of the Al distribution in zeolites.

Evolution of Stabilized 1T-MoS2 by Atomic-Interface Engineering of 2H-MoS2 /Fe-Nx towards Enhanced Sodium Ion Storage.

Metallic conductive 1T phase molybdenum sulfide (MoS2 ) has been identified as promising anode for sodium ion (Na+ ) batteries, but its metastable feature makes it difficult to obtain and its restacking during the charge/discharge processing result in part capacity reversibility. Herein, a synergetic effect of atomic-interface engineering is employed for constructing 2H-MoS2 layers assembled on single atomically dispersed Fe-N-C (SA Fe-N-C) anode material that boosts its reversible capacity. The work-function-driven-electron transfer occurs from SA Fe-N-C to 2H-MoS2 via the Fe-S bonds, which enhances the adsorption of Na+ by 2H-MoS2 , and lays the foundation for the sodiation process. A phase transfer from 2H to 1T/2H MoS2 with the ferromagnetic spin-polarization of SA Fe-N-C occurs during the sodiation/desodiation process, which significantly enhances the Na+ storage kinetics, and thus the 1T/2H MoS2 /SA Fe-N-C display a high electronic conductivity and a fast Na+ diffusion rate.

Porous Copper-Loaded Zeolites for High-Efficiency Capture of Iodine from Spent Fuel Reprocessing Off-Gas.

Capturing volatile radionuclide iodine produced in the nuclear industry is a crucial environmental issue. In previous studies, the principal efficient adsorbent for iodine capture was silver-containing zeolite. As silver-containing zeolites are expensive, alternate copper-loaded porous zeolites, including CuCl loaded NaY reduced by H2 (denoted as H2CuY) and CO (denoted as COCuY), were studied for iodine adsorption at moderate temperatures. The current work also discusses the influence of copper valency on iodine adsorption. Due to the copper sites and nanosized pore structure, H2CuY and COCuY showed high iodine adsorption capacities of 450 and 219 mg/g, respectively. The iodine adsorption capacity of H2CuY was higher than that of silver-loaded zeolites. Moreover, H2CuY and COCuY adsorbed volatile iodine through a chemical mechanism involving the copper sites of different valencies, and the Cu0 was more effective in adsorbing iodine than Cu+. These copper-loaded zeolites with strong chemical interactions with iodine and high iodine adsorption capacities provided the possibility for iodine adsorption application in the nuclear industry.

Multivariate Synergistic Flexible Metal-Organic Frameworks with Superproton Conductivity for Direct Methanol Fuel Cells.

Improving proton conductivity and fabricating viable metal-organic frameworks (MOFs) based proton exchange membranes (PEMs) are central issues exploiting electrolyte MOFs. We aim to design multivariate flexibility synergistic strategy to achieve Flexible MOFs (FMOFs) with high conductivity at a wide range of humidity. In situ powder X-ray diffraction (PXRD) and temperature-dependent Fourier transform infrared spectra (FT-IR) prove the synergistic self-adaption between dynamic torsion of alkyl sulfonic acid and dynamic breathing of FMOF, forming a continuous hydrogen-bonding networks to maintain high conductivity. Based on the convincing proton conductivity, we construct a series of long-term durable MOF-based PEMs that serve as a bridge between MOF and fuel cell. Consequently, the membrane electrode assembly (MEA) of the flexible PMNS1-40 exhibits a maximum single-cell power density of 34.76 mW cm-2 and hopefully opens doors to evaluate the practical application of proton-conducting MOFs in direct methanol fuel cells.

High-Silica CHA Zeolite Membrane with Ultra-High Selectivity and Irradiation Stability for Krypton/Xenon Separation.

Capture and storage of the long-lived 85 Kr is an efficient approach to mitigate the emission of volatile radionuclides from the spent nuclear fuel reprocessing facilities. However, it is challenging to separate krypton (Kr) from xenon (Xe) because of the chemical inertness and similar physical properties. Herein we prepared high-silica CHA zeolite membranes with ultra-high selectivity and irradiation stability for Kr/Xe separation. The suitable aperture size and rigid framework endures the membrane a strong size-exclusion effect. The ultrahigh selectivity of 51-152 together with the Kr permeance of 0.7-1.3×10-8  mol m-2 s-1 Pa-1 of high-silica CHA zeolite membranes far surpass the state-of-the-art polymeric membranes. The membrane is among the most stable polycrystalline membranes for separation of humid Kr/Xe mixtures. Together with the excellent irradiation stability, high-silica CHA zeolite membranes pave the way to separate radioactive Kr from Xe for a notable reduction of the volatile nuclear waste storage volume.

Electron Beam Irradiation-Induced Formation of Defect-Rich Zeolites under Ambient Condition within Minutes.

Zeolites are a well-known family of microporous aluminosilicate crystals with a wide range of applications. Their industrial synthetic method under hydrothermal condition requires elevated temperature and long crystallization time and is therefore quite energy-consuming. Herein, we utilize high-energy electron beam irradiation generated by an industrial accelerator as a distinct type of energy source to activate the formation reaction of Na-A zeolite. The initial efforts afford an attractive reaction process that can be achieved under ambient conditions and completed within minutes with almost quantitative yield, leading to notable energy saving of one order of magnitude compared to the hydrothermal reaction. More importantly, electron beam irradiation simultaneously exhibits an etching effect during the formation of zeolite generating a series of crystal defects and additional pore windows that can be controlled by irradiation dose. These observations give rise to significantly enhanced surface area and heavy metal removal capabilities in comparison with Na-A zeolite synthesized hydrothermally. Finally, we show that this method can be applied to many other types of zeolites.

Synthesis and Post-Synthesis Transformation of Germanosilicate Zeolites.

Zeolites are one of the most important heterogeneous catalysts, with a high number of large-scale industrial applications. While the synthesis of new zeolites remain rather limited, introduction of germanium has substantially increased our ability to not only direct the synthesis of zeolites but also to convert them into new materials post-synthetically. The smaller Ge-O-Ge angles (vs. Si-O-Si) and lability of the Ge-O bonds in aqueous solutions account for this behaviour. This Minireview discusses critical aspects of germanosilicate synthesis and their post-synthesis transformations to porous materials.

A Layered Cationic Aluminum Oxyhydroxide as a Highly Efficient and Selective Trap for Heavy Metal Oxyanions.

Cationic framework materials, especially pure inorganic cationic frameworks that can efficiently and selectively capture harmful heavy metal oxyanions from aqueous solution are highly desired yet scarcely reported. Herein, we report the discovery of a 2D cationic aluminum oxyhydroxide, JU-111, which sets a new benchmark for heavy metal oxyanion sorbents, especially for CrVI . Its structure was solved based on 3D electron diffraction tomography data. JU-111 shows fast sorption kinetics (ca. 20 min), high capture capacity (105.4 mg g-1 ), and broad working pH range (3-10) toward CrVI oxyanions. Unlike layered double hydroxides (LDHs), which are poorly selective in the presence of CO3 2- , JU-111 retains excellent selectivity for CrVI even under a large excess of CO3 2- . These superior features coupled with the ultra-low cost and environmentally benign nature make JU-111 a promising candidate for toxic metal oxyanion remediation as well as other potential applications.

Effects of substituents on luminescent efficiency of stable triaryl methyl radicals.

A series of perchlorotriphenyl methyl (PTM) and tris(2,4,6-trichlorophenyl)methyl (TTM) radical derivatives were synthesized. The factors affecting the photoluminescence quantum yields (PLQYs) of π-radicals were studied systematically for the first time through comparing the photophysical properties of the synthesized PTM and TTM radicals. The room-temperature PLQY of a PTM radical derivative achieves to be 56.6%, which is the highest value among the organic near-infrared materials with peak wavelength over 650 nm. The photostabilities of the radicals was significantly enhanced via incorporation of substituent groups. The molecular rigidity, electron donating ability of the donor and dihedral angle between D-A system were found to be the potential factors to affect the luminescent efficiency of the open-shell molecules.

Thermoresponsive Polyoxometalate/Ionic Liquid Supramolecular Gel Electrolytes for Supercapacitors: Fabrication, Structure, and Heteropolyanion Structure Effect.

We report the fabrication, structure, and heteropolyanion structure effect of polyoxometalate (POM)/ionic liquid (IL) supramolecular gels. These supramolecular gels exhibit ordered structures, as a result of their excellent reversible self-assembly, and they show various physicochemical properties, determined by the heteropolyanion structure effect of POM anions. Specifically, the formation of POM/IL supramolecular gels results in a highly ordered layer-shape structure, which has been calculated using X-ray powder diffraction patterns and proven by transmission electron microscopy images for the first time. When these POM/IL supramolecular gels are heated, they become viscous liquid sols, with melting isotropic drops and even flowerlike structures on microscopic scales, while it undergoes a reversible gel-sol phase transformation from gel to sol. The heteropolyanion structure effect in these two IL gels, [TBTP]5PW10V2O40 and [TBTP]8P2W16V2O62, on their physicochemical properties is demonstrated. The POM structures have a strong structure effect on the physicochemical properties. As the size of heteropolyanions increases, there is a significant improvement in the conductivity, thermal performance, and oxidizability, with a lower phase inversion temperature, which means that the Dawson-type compound, [TBTP]8P2W16V2O62, has a higher conductivity, lower melting point, stronger oxidizability, and better thermal performance than the Keggin-type compound, [TBTP]5PW10V2O40, under the same conditions.

Spatial separation of the hydrogen evolution center from semiconductors using a freestanding silica-sphere-supported Pt composite.

Spatial separation of the reduction center (photosystem I) and oxidation center (photosystem II) is an obvious characteristic of natural photosynthesis. Enlightened by this natural process, a simple material based on silica-sphere-supported Pt nanoparticles (SSP) was designed as a freestanding hydrogen evolution center for semiconductor photocatalysts. In situ photoluminescence characterization showed that the radiation recombination of electron-hole pairs in semiconductors (i.e. TiO2 and CdS) was well suppressed due to the presence of SSP. And the quenching efficiency increases with the hydrogen evolution rate of photocatalysts. These results indicated that SSP could effectively trap electrons from the photoexcited semiconductors during collision between SSP and semiconductor, and then complete the hydrogen evolution reaction over the Pt nanoparticles. Detailed investigation also showed that the performance of SSP was influenced by several factors, including the particle size of the silica sphere and the physical and chemical states of Pt nanoparticles. Besides, it was demonstrated that the loaded metal was not limited to Pt. Pd, Ni and Au can also be used as active sites in this freestanding cocatalyst strategy.

Keggin-type polyoxometalate-based ionic liquid gels.

A series of reversible phase transformation ammonium- and phosphonium-based polyoxometalate ionic liquid (POM-IL) gels were synthesized and studied with a focus on the correlation between their physicochemical properties and their chemical structure. The products were successfully characterized by IR, UV, XRD and TG-DTA, and their ionic conductivities were measured. The Keggin-type heteropolyanion clusters decorated with long alkyl chains demonstrated a tendency to exhibit a gel state at room temperature, while all the gels transformed into liquids after heating and then recovered after cooling. With a decrease in the alkyl chain length, a significant improvement in the thermal stability and conductivity of the ammonium-based POM-IL gels can be achieved. Moreover, compared with the corresponding ammonium compound, phosphonium-based POM-IL gel was found to be more stable at high temperature and exhibited better conductivity.

Correction: The invertible electrochemical properties and thermal response of a series of gel-type ionic liquids based on polyoxometalates.

Correction for 'The invertible electrochemical properties and thermal response of a series of gel-type ionic liquids based on polyoxometalates' by Xuefei Wu et al., Phys. Chem. Chem. Phys., 2014, 16, 24598-24603.

The invertible electrochemical properties and thermal response of a series of gel-type ionic liquids based on polyoxometalates.

A series of vanadium-substituted Dawson-structure POM-type ionic liquids, [TEAPS]7P2W17VO62 and [TEAPS]9P2W15V3O62, bearing sulfo-group grafted ammonium (TEAPS) cations and Dawson-type polyoxoanions have been formed which are reversible-thermal-response type gels. These gel-type compounds exhibit a phase transition from a quasi-solid gel phase to an isotropic sol phase. What's more, this series of hybrid compounds can undergo reversible electrochemical reactions in dimethyl formamide (DMF) owing to the reduction of the vanadium in POM anions as a simple anion, which is unlikely to happen in water solution because of water protonation.

Strong Electronic Metal-Support Interactions Enable the Increased Spin State of Co-N4 Active Sites and Performance for Acidic Oxygen Reduction Reaction.

Nonprecious metal catalysts, particularly M-N-C catalysts, are widely recognized as promising contenders for the oxygen reduction reaction (ORR). However, a notable performance gap persists between M-N-C catalysts and Pt-based catalysts under acidic conditions. In this study, hybrid catalysts comprising single Co atoms and ultralow concentrations of Pt3Co intermetallic nanoparticles (NPs) are introduced to enhance ORR performance. Under acidic conditions, these hybrid catalysts demonstrate ORR efficiency with a half-wave potential of 0.895 V, negligible decay even after 80 000 cycles, and a high maximum power density of 1.34 W cm-2 in fuel cells. This performance surpasses those of Co-N-C and Pt/Co-N-C catalysts. Both experimental findings and theoretical computations suggest that the heightened ORR activity stems from an increase in the spin density of Co sites induced by noble metal NPs, facilitating the activation of O-O bonds via side-on overlapping and enabling a transition in the reaction pathway from associative to dissociative processes. This research offers a promising avenue for the systematic design of M-N-C cathodes with an enhanced performance for acidic fuel cells.

High-efficiency encapsulation of Pt nanoparticles into the channel of carbon nanotubes as an enhanced electrocatalyst for methanol oxidation.

Pt-based nanostructures serving as anode catalysts for the methanol oxidation reaction (MOR) have been widely studied for many years. Nevertheless, challenging issues such as poor reaction kinetics and the short-term stability of the MOR are the main drawbacks of such catalysts and limit their applications. Herein, we have developed a facile approach to encapsulate Pt nanoparticles (NPs) inside the nanochannels of porous carbon nanotubes (CNTs; Pt-in-CNTs) as a new enhanced electrocatalytic material. The as-prepared CNTs offer simultaneously ordered diffusion channels for ions and a confinement effect for the NPs, which both facilitate the promotion of catalytic kinetics and avoid the Ostwald ripening of Pt NPs, thus leading to high activity and durable cycle life as an anode catalyst for MOR. This work provides a new approach for enhancing the stability and activity by optimizing the structure of the catalyst, and the Pt-in-CNTs represent the most durable catalysts ever reported for MOR.