Modulating Electronic Metal-Support Interactions to Boost Visible-Light-Driven Hydrolysis of Ammonia Borane: Nickel-Platinum Nanoparticles Supported on Phosphorus-Doped Titania

Ammonia borane (AB) is a promising material for chemical H₂ storage owing to its high H₂ density (up to 19.6 wt %). However, the development of an efficient catalyst for driving H₂ evolution through AB hydrolysis remains challenging. Therefore, a visible-light-driven strategy for generating H₂ through AB hydrolysis was implemented in this study using Ni−Pt nanoparticles supported on phosphorus-doped TiO₂ (Ni-Pt/P-TiO₂) as photocatalysts. Through surface engineering, P-TiO₂ was prepared by phytic-acid-assisted phosphorization and then employed as an ideal support for immobilizing Ni−Pt nanoparticles via a facile co-reduction strategy. Under visible-light irradiation at 283 K, Ni₄₀Pt₆₀/P-TiO₂ exhibited improved recyclability and a high turnover frequency of 967.8 mol mol_Pt⁻¹ min⁻¹. Characterization experiments and density functional theory calculations indicated that the enhanced performance of Ni₄₀Pt₆₀/P-TiO₂ originated from a combination of the Ni−Pt alloying effect, the Mott–Schottky junction at the metal-semiconductor interface, and strong metal-support interactions. These findings not only underscore the benefits of utilizing multipronged effects to construct highly active AB-hydrolyzing catalysts, but also pave a path toward designing high-performance catalysts by surface engineering to modulate the electronic metal-support interactions for other visible-light-induced reactions.     

Entropic Contributions to Sodium Solvation and Solvent Stabilization upon Electrochemical Sodium Deposition from Diglyme and Propylene Carbonate Electrolytes

The formation of an appropriate solid electrolyte interphase (SEI) at the anode of a sodium battery is crucially dependent on the electrochemical stability of solvent and electrolyte at the redox potential of Na/Na⁺ in the respective system. In order to determine entropic contributions to the relative stability of the electrolyte solution, we measure the reaction entropy of Na metal deposition for diglyme (DG) and propylene carbonate (PC) based electrolyte solutions by electrochemical microcalorimetry at single electrodes. We found a large positive reaction entropy for Na⁺ deposition in DG of Δ_R 234 J mol⁻¹ K⁻¹ (c.f.: Δ_R 83 J mol⁻¹ K⁻¹), which signals substantial entropic destabilization of Na⁺ in DG by about 0.73 eV, thus increasing the stability of solvent and electrolyte relative to Na⁺ reduction. We attribute this strong entropic destabilization to a highly negative solvation entropy of Na⁺, due to the low dielectric constant and high freezing entropy of DG.     

Comproportionation of CO2 and Cellulose to Formate Using a Floating Semiconductor-Enzyme Photoreforming Catalyst

Formate production via both CO₂ reduction and cellulose oxidation in a solar-driven process is achieved by a semi-artificial biohybrid photocatalyst consisting of immobilized formate dehydrogenase on titanium dioxide (TiO₂| FDH ) producing up to 1.16±0.04 mmol_formate g ⁻¹ in 24 hours at 30 °C and 101 kPa under anaerobic conditions. Isotopic labeling experiments with ¹³C-labeled substrates support the mechanism of stoichiometric formate formation through both redox half-reactions. TiO₂| FDH was further immobilized on hollow glass microspheres to perform more practical floating photoreforming allowing vertical solar light illumination with optimal light exposure of the photocatalyst to real sunlight. Enzymatic cellulose depolymerization coupled to the floating photoreforming catalyst generates 0.36±0.04 mmol_formate per m² irradiation area after 24 hours. This work demonstrates the synergistic solar-driven valorization of solid and gaseous waste streams using a biohybrid photoreforming catalyst in aqueous solution and will thus provide inspiration for the development of future semi-artificial waste-to-chemical conversion strategies.     

Zeolite-Encaged Pd–Mn Nanocatalysts for CO2 Hydrogenation and Formic Acid Dehydrogenation

A CO₂-mediated hydrogen storage energy cycle is a promising way to implement a hydrogen economy, but the exploration of efficient catalysts to achieve this process remains challenging. Herein, sub-nanometer Pd–Mn clusters were encaged within silicalite-1 (S-1) zeolites by a ligand-protected method under direct hydrothermal conditions. The obtained zeolite-encaged metallic nanocatalysts exhibited extraordinary catalytic activity and durability in both CO₂ hydrogenation into formate and formic acid (FA) dehydrogenation back to CO₂ and hydrogen. Thanks to the formation of ultrasmall metal clusters and the synergic effect of bimetallic components, the PdMn_0.6@S-1 catalyst afforded a formate generation rate of 2151 mol_formate mol_Pd⁻¹ h⁻¹ at 353 K, and an initial turnover frequency of 6860 mol mol_Pd⁻¹ h⁻¹ for CO-free FA decomposition at 333 K without any additive. Both values represent the top levels among state-of-the-art heterogeneous catalysts under similar conditions. This work demonstrates that zeolite-encaged metallic catalysts hold great promise to realize CO₂-mediated hydrogen energy cycles in the future that feature fast charge and release kinetics.     

Decoupling Redox Hopping and Catalysis in Metal-Organic Frameworks -based Electrocatalytic CO2 Reduction

Traditional MOF e-CRR, constructed from catalytic linkers, manifest a kinetic bottleneck during their multi-electron activation. Decoupling catalysis and charge transport can address such issues. Here, we build two MOF/e-CRR systems, CoPc@NU-1000 and TPP(Co)@NU-1000, by installing cobalt metalated phthalocyanine and tetraphenylporphyrin electrocatalysts within the redox active NU-1000 MOF. For CoPc@NU-1000, the e-CRR responsive Co^I/0 potential is close to that of NU-1000 reduction compared to the TPP(Co)@NU-1000. Efficient charge delivery, defined by a higher diffusion (D_hop=4.1×10⁻¹² cm² s⁻¹) and low charge-transport resistance ( =59.5 Ω) in CoPC@NU-1000 led FE_CO=80 %. In contrast, TPP(Co)@NU-1000 fared a poor FE_CO=24 % (D_hop=1.4×10⁻¹² cm² s⁻¹ and =91.4 Ω). For such a decoupling strategy, careful choice of the host framework is critical in pairing up with the underlying electrochemical properties of the catalysts to facilitate the charge delivery for its activation.     

Modular and Selective Arylation of Aryl Germanes (C−GeEt3) over C−Bpin,C−SiR3 and Halogens Enabled by Light‐Activated Gold Catalysis

Selective C –C couplings are powerful strategies for the rapid and programmable construction of bi‐ or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd‐catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd⁰/Pd^II catalysis) in the presence of the valuable functionalities C?BPin, C?SiMe₃, C?I, C?Br, C?Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C?Ge with aryl diazonium salts. Contrary to previous light‐/gold‐catalyzed couplings of Ar–N₂⁺, which were specialized in Ar–N₂⁺ scope, we present conditions to efficiently couple electron‐rich, electron‐poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron‐poor Ar–N₂⁺ salts are readily activated by gold under blue‐light irradiation, there is a competing dissociative deactivation pathway for excited electron‐rich Ar–N₂⁺, which requires an alternative photo‐redox approach to enable productive couplings.     

Blended Conjugated Host and Unconjugated Dopant Polymers Towards N-type All-Polymer Conductors and High-ZT Thermoelectrics

N-Type thermoelectrics typically consist of small molecule dopant+polymer host. Only a few polymer dopant+polymer host systems have been reported, and these have lower thermoelectric parameters. N-type polymers with high crystallinity and order are generally used for high-conductivity ( ) organic conductors. Few n-type polymers with only short-range lamellar stacking for high-conductivity materials have been reported. Here, we describe an n-type short-range lamellar-stacked all-polymer thermoelectric system with highest of 78 S⁻¹, power factor (PF) of 163 μW m⁻¹ K⁻², and maximum Figure of merit (ZT) of 0.53 at room temperature with a dopant/host ratio of 75 wt%. The minor effect of polymer dopant on the molecular arrangement of conjugated polymer PDPIN at high ratios, high doping capability, high Seebeck coefficient (S) absolute values relative to , and atypical decreased thermal conductivity ( ) with increased doping ratio contribute to the promising performance.     

Highly Selective Electrochemical Reduction of CO2 to Alcohols on an FeP Nanoarray

Electrochemical reduction of CO₂ into various chemicals and fuels provides an attractive pathway for environmental and energy sustainability. It is now shown that a FeP nanoarray on Ti mesh (FeP NA/TM) acts as an efficient 3D catalyst electrode for the CO₂ reduction reaction to convert CO₂ into alcohols with high selectivity. In 0.5 m KHCO₃, such FeP NA/TM is capable of achieving a high Faradaic efficiency (FE ) up to 80.2 %, with a total FE of 94.3 % at ?0.20 V vs. reversible hydrogen electrode. Density functional theory calculations reveal that the FeP(211) surface significantly promotes the adsorption and reduction of CO₂ toward CH₃OH owing to the synergistic effect of two adjacent Fe atoms, and the potential‐determining step is the hydrogenation process of *CO.     

Atomically Precise Copper Nanoclusters for Highly Efficient Electroreduction of CO2 towards Hydrocarbons via Breaking the Coordination Symmetry of Cu Site

We propose an effective highest occupied d-orbital modulation strategy engendered by breaking the coordination symmetry of sites in the atomically precise Cu nanocluster (NC) to switch the product of CO₂ electroreduction from HCOOH/CO to higher-valued hydrocarbons. An atomically well-defined Cu₆ NC with symmetry-broken Cu−S₂N₁ active sites (named Cu₆(MBD)₆, MBD=2-mercaptobenzimidazole) was designed and synthesized by a judicious choice of ligand containing both S and N coordination atoms. Different from the previously reported high HCOOH selectivity of Cu NCs with Cu−S₃ sites, the Cu₆(MBD)₆ with Cu−S₂N₁ coordination structure shows a high Faradaic efficiency toward hydrocarbons of 65.5 % at −1.4 V versus the reversible hydrogen electrode (including 42.5 % CH₄ and 23 % C₂H₄), with the hydrocarbons partial current density of −183.4 mA cm⁻². Theoretical calculations reveal that the symmetry-broken Cu−S₂N₁ sites can rearrange the Cu 3d orbitals with as the highest occupied d-orbital, thus favoring the generation of key intermediate *COOH instead of *OCHO to favor *CO formation, followed by hydrogenation and/or C−C coupling to produce hydrocarbons. This is the first attempt to regulate the coordination mode of Cu atom in Cu NCs for hydrocarbons generation, and provides new inspiration for designing atomically precise NCs for efficient CO₂RR towards highly-valued products.     

Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles

We report a new molecular‐design principle for creating double‐gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings close to each other were designed and synthesized. NMR data revealed that the rotation of the imidazolium rings is restricted, with an activation energy as high as 63 kJ mol^?1 in DMSO‐d₆ solution (DFT prediction for a model compound in the vacuum: 90–100 kJ mol^?1). Due to the restricted rotation, the amphiphiles feature “double” atropisomeric axes in their ionic segments and form three stable atropisomers: meso, R, and S. These isomers co‐organize into ‐type bicontinuous cubic liquid‐crystalline mesophases through nanosegregation of the ionic and non‐ionic parts. Considering the intrinsic characteristic of ‐type bicontinuous cubic structures that they are composed of intertwined right‐ and left‐handed single gyroids, we propose that the simultaneous presence of both R‐ and S‐atropisomers is an important contributor to the formation of double‐gyroid structures.     

An Artificial Single Molecular Channel Showing High Chloride Transport Selectivity and pH-Responsive Conductance

Inspired by the unique structure and function of the natural chloride channel (ClC) selectivity filter, we present herein the design of a ClC-type single channel molecule. This channel displays high ion transport activity with half-maximal effective concentration, EC₅₀, of 0.10 μM, or 0.075 mol % (channel molecule to lipid ratio), as determined by fluorescent analysis using lucigenin-encapsulated vesicles. Planar bilayer lipid membrane conductance measurements indicated an excellent Cl⁻/K⁺ selectivity with a permeability ratio P /P up to 12.31, which is comparable with the chloride selectivity of natural ClC proteins. Moreover, high anion/anion selectivity (P /P =66.21) and pH-dependent conductance and ion selectivity of the channel molecule were revealed. The ClC-like transport behavior is contributed by the cooperation of hydrogen bonding and anion–π interactions in the central macrocyclic skeleton, and by the existence of pH-responsive terminal phenylalanine residues.     

Hole and Electron Doping of the 4d Transition‐Metal Oxyhydride LaSr3NiRuO4H4

Hole or electron doping of phases prepared by topochemical reactions (e.g. anion deintercalation or anion‐exchange) is extremely challenging as these low‐temperature conversion reactions are typically very sensitive to the electron counts of precursor phases. Herein we report the successful hole and electron doping of the transition‐metal oxyhydride LaSr₃NiRuO₄H₄ by first preparing precursors in the range La_xSr_4?xNiRuO₈ 0.5<x<1.4 and then converting into the corresponding La_xSr_4?xNiRuO₄H₄ phases. This is particularly noteworthy as the (Ni/Ru)H₂ sheets in the La_xSr_4?xNiRuO₄H₄ phases are structurally analogous to the CuO₂ sheets in cuprate superconductors and hole doping (Ni^1+/2+, Ru²⁺) or electron doping (Ni²⁺, Ru^1+/2+) yields materials with partial occupancy in Ni/Ru –H 1s bands which are analogous to the partially occupied Cu –O 2p bands present in the CuO₂ sheets of doped superconducting cuprates.     

Subnanometer Bimetallic Platinum–Zinc Clusters in Zeolites for Propane Dehydrogenation

Propane dehydrogenation (PDH) has great potential to meet the increasing global demand for propylene, but the widely used Pt-based catalysts usually suffer from short-term stability and unsatisfactory propylene selectivity. Herein, we develop a ligand-protected direct hydrogen reduction method for encapsulating subnanometer bimetallic Pt–Zn clusters inside silicalite-1 (S-1) zeolite. The introduction of Zn species significantly improved the stability of the Pt clusters and gave a superhigh propylene selectivity of 99.3 % with a weight hourly space velocity (WHSV) of 3.6–54 h⁻¹ and specific activity of propylene formation of 65.5 mol g_Pt⁻¹ h⁻¹ (WHSV=108 h⁻¹) at 550 °C. Moreover, no obvious deactivation was observed over PtZn4@S-1-H catalyst even after 13000 min on stream (WHSV=3.6 h⁻¹), affording an extremely low deactivation constant of 0.001 h⁻¹, which is 200 times lower than that of the PtZn4/Al₂O₃ counterpart under the same conditions. We also show that the introduction of Cs⁺ ions into the zeolite can improve the regeneration stability of catalysts, and the catalytic activity kept unchanged after four continuous cycles.     

17O Hyperfine Spectroscopy Reveals Hydration Structure of Nitroxide Radicals in Aqueous Solutions

The hydration structure of nitroxide radicals in aqueous solutions is elucidated by advanced ¹⁷O hyperfine (hf) spectroscopy with support of quantum chemical calculations and MD simulations. A piperidine and a pyrrolidine-based nitroxide radical are compared and show clear differences in the preferred directionality of H-bond formation. We demonstrate that these scenarios are best represented in ¹⁷O hf spectra, where in-plane coordination over -type H-bonding leads to little spin density transfer on the water oxygen and small hf couplings, whereas -type perpendicular coordination generates much larger hf couplings. Quantitative analysis of the spectra based on MD simulations and DFT predicted hf parameters is consistent with a distribution of close solvating water molecules, in which directionality is influenced by subtle steric effects of the ring and the methyl group substituents.     

Quantum Nuclear Delocalization and its Rovibrational Fingerprints

Quantum mechanics dictates that nuclei must undergo some delocalization. In this work, emergence of quantum nuclear delocalization and its rovibrational fingerprints are discussed for the case of the van der Waals complex . The equilibrium structure of is planar and T-shaped, one He atom solvating the quasi-linear He−H⁺−He core. The dynamical structure of , in all of its bound states, is fundamentally different. As revealed by spatial distribution functions and nuclear densities, during the vibrations of the molecule the solvating He is not restricted to be in the plane defined by the instantaneously bent chomophore, but freely orbits the central proton, forming a three-dimensional torus around the chromophore. This quantum delocalization is observed for all vibrational states, the type of vibrational excitation being reflected in the topology of the nodal surfaces in the nuclear densities, showing, for example, that intramolecular bending involves excitation along the circumference of the torus.     

A Rare Low‐Spin CoIV Bis(β‐silyldiamide) with High Thermal Stability: Steric Enforcement of a Doublet Configuration

Attempted preparation of a chelated Co^II β‐silylamide resulted in the unprecedented disproportionation to Co⁰ and a spirocyclic cobalt(IV) bis(β‐silyldiamide): [Co[(N^tBu)₂SiMe₂]₂] ( 1 ). Compound 1 exhibited a room‐temperature magnetic moment of 1.8 B.M. and a solid‐state axial EPR spectrum diagnostic of a rare S= configuration for tetrahedral Co^IV. Ab initio semicanonical coupled‐cluster calculations (DLPNO‐CCSD(T)) revealed the doublet state was clearly preferred (?27 kcal mol^?1) over higher spin configurations only for the bulky tert‐butyl‐substituted analogue. Unlike other Co^IV complexes, 1 had remarkable thermal stability, and was demonstrated to form a stable self‐limiting monolayer in preliminary atomic layer deposition (ALD) surface saturation experiments. The ease of synthesis and high stability make 1 an attractive starting point to investigate otherwise inaccessible Co^IV intermediates and for synthesizing new materials.