In this work, three dimensional (3D) self-supported Ni-FeOH@Ni-FeP needle arrays with core-shell heterojunction structure are fabricated via in situ hydroxide growth over Ni-FeP surface. The as-prepared electrodes show an outstanding oxygen evolution reaction (OER) performance, only requiring the low overpotential of 232 mV to reach 200 mA cm-2 with the Tafel slop of 40 mV dec-1. For overall water splitting, an alkaline electrolyzer with these electrodes only requires a cell voltage of 2.14 V to reach 1 A cm-2. Mechanistic investigations for such excellent electrocatalytic performances are utilized by in situ Raman spectroscopy in conjunction with density functional theory (DFT) calculations. The computation results present that Ni-FeOH@Ni-FeP attains better intrinsic conductivity and the D-band center (close to that of the ideal catalyst), thus giving superior excellent catalytic performances. Likewise, the surface Ni-FeOH layer can improve the structural stability of Ni-FeP cores and attenuate the eventual formation of irreversible FeOOH products. More importantly, the appearance of FeOOH intermediates can effectively decrease the energy barrier of NiOOH intermediates, and then rapidly accelerate the sluggish reaction dynamics, as well as further enhance the electrocatalytic activities, reversibility and cycling stability.

Chiral Plasmonic nanomaterials have gradually illustrated intriguing circularly polarized light (CPL)-dependent properties in photocatalysis due to their unique chiral optical activity. However, the connection between chiral characteristics and catalytic performance of these materials in cooperative systems is rarely reported and remains a challenge task. In this work, branched AgAuPt nanoparticles induced by L/d-cysteine (Cys) with strong and perfectly symmetric circular dichroism (CD) signals are synthesized. Chiral branched AgAuPt nanoparticles firstly exhibit superior typical electrocatalytic performance. In the photoelectrocatalytic system, chiral branched AgAuPt nanoparticles demonstrate selective catalytic water splitting performance. Specifically, chiral branched AgAuPt with related CPL irradiation exhibits enhanced acidic hydrogen evolution reaction (HER) performance. Under the continuous irradiation of related CPL, the chiral catalyst generates more heat, which further increases the catalytic activity. This contribution of heat is supported by density functional theory (DFT) calculation results. The changes in chiroptical activity during this process are recorded by variable temperature CD spectra. This work provides a novel paradigm for designing chiral catalysis systems and emphasizes the profound promise of chiral plasmonic nanomaterials as chiral catalysts.

Stabilized and metallic light elements hydrides have provided a potential route to achieve the goal of room-temperature superconductors at moderate or ambient pressures. Here, we have performed systematic DFT theoretical calculations to examine the effects of different light elements C and N atoms doped in cubic K4B8H32hydrides on the superconductivity at low pressures. As a result of various atoms substituting, we have found that metallic K4B8-xMxH32(M = C, N) hydrides are dynamically stable at 50 GPa, band structures and density of states indicate that sizeableTccorrelates with a high B-H density of states at the Fermi level. With the increasing of B atoms in K4B8-xMxH32hydrides, the density of states values at Fermi level have been improved due to the delocalized electrons in B-H bonds, which result in strong electron-phonon coupling (EPC) interaction and increase theTcfrom 19.04 to 77.07 K for KC2H8and KB2H8at 50 GPa. The NH4unit in stable K4B7NH32hydrides has weakened the EPC and led to low Tc value of 21.47 K. Our results suggest the light elements hydrides KB2H8and K4B7CH32could estimate highTcvalues at 50 GPa, and the boron hydrides would be potential candidates to design or modulate hydrides superconductors with highTcat moderate or ambient pressures.

Bio-oil derived from biomass fast pyrolysis can be upgraded to gasoline and diesel alternatives by catalytic hydrodeoxygenation (HDO). Here, the novel nitrogen-doped carbon-alumina hybrid supported cobalt (Co/NCAn, n = 1, 2.5, 5) catalyst is established by a coagulation bath technique. The optimized Co/NCA2.5 catalyst presented 100 % conversion of guaiacol, high selectivity to cyclohexane (93.6 %), and extremely high deoxygenation degree (97.3 %), respectively. Therein, the formation of cyclohexanol was facilitated by stronger binding energy and greater charge transfer between Co and NC which was unraveled by density functional theory calculations. In addition, the appropriate amount of Lewis acid sites enhanced the cleavage of the C-O bond in cyclohexanol, finally resulting in a remarkable selectivity for cyclohexane. Finally, the Co/NCA2.5 catalyst also exhibited excellent selectivity (93.1 %) for high heating value hydrocarbon fuel in crude bio-oil HDO. This work provides a theoretical basis on N dopants collaborating alumina hybrid catalysts for efficient HDO reaction.

Developing high electroactivity ruthenium (Ru)-based electrocatalysts for pH-universal hydrogen evolution reaction (HER) is challenging due to the strong bonding strengths of key Ru─H/Ru─OH intermediates and sluggish water dissociation rates on active Ru sites. Herein, a semi-ionic F-modified N-doped porous carbon implanted with ruthenium nanoclusters (Ru/FNPC) is introduced by a hydrogel sealing-pyrolying-etching strategy toward highly efficient pH-universal hydrogen generation. Benefiting from the synergistic effects between Ru nanoclusters (Ru NCs) and hierarchically F, N-codoped porous carbon support, such synthesized catalyst displays exceptional HER reactivity and durability at all pH levels. The optimal 8Ru/FNPC affords ultralow overpotentials of 17.8, 71.2, and 53.8 mV at the current density of 10 mA cm-2 in alkaline, neutral, and acidic media, respectively. Density functional theory (DFT) calculations elucidate that the F-doped substrate to support Ru NCs weakens the adsorption energies of H and OH on Ru sites and reduces the energy barriers of elementary steps for HER, thus enhancing the intrinsic activity of Ru sites and accelerating the HER kinetics. This work provides new perspectives for the design of advanced electrocatalysts by porous carbon substrate implanted with ultrafine metal NCs for energy conversion applications.

Covalent organic frameworks (COFs) have emerged as promising renewable electrode materials for LIBs and gained significant attention, but their capacity has been limited by the densely packed 2D layer structures, low active site availability, and poor electronic conductivity. Combining COFs with high-conductivity MXenes is an effective strategy to enhance their electrochemical performance. Nevertheless, simply gluing them without conformal growth and covalent linkage restricts the number of redox-active sites and the structural stability of the composite. Therefore, in this study, a covalently assembled 3D COF on Ti3C2 MXenes (Ti3C2@COF) is synthesized and serves as an ultralong cycling electrode material for LIBs. Due to the covalent bonding between the COF and Ti3C2, the Ti3C2@COF composite exhibits excellent stability, good conductivity, and a unique 3D cavity structure that enables stable Li+ storage and rapid ion transport. As a result, the Ti3C2-supported 3D COF nanosheets deliver a high specific capacity of 490 mAh g-1 at 0.1 A g-1, along with an ultralong cyclability of 10,000 cycles at 1 A g-1. This work may inspire a wide range of 3D COF designs for high-performance electrode materials.

We herein describe the first example of ligand-controlled, copper-catalyzed regiodivergent asymmetric difunctionalization of terminal alkynes through a cascade hydroboration and hydroallylation process. The catalytic system, consisting of (R)-DTBM-Segphos and CuBr, could efficiently achieve asymmetric 1,1-difunctionalization of aryl terminal alkynes, while ligand switching to (S,S)-Ph-BPE could result in asymmetric 1,2-difunctionalization exclusively. In addition, alkyl substituted terminal alkynes, especially industrially relevant acetylene and propyne, were also valid feedstocks for asymmetric 1,1-difunctionalization. This protocol is characterized by good functional group tolerance, a broad scope of substrates (> 150 examples), and mild reaction conditions. We also showcase the value of this method in the late-stage functionalization of complicated bioactive molecules and simplifying the synthetic routes toward the key intermediacy of natural product (bruguierol A). Mechanistic studies combined with DFT calculations provide insight into the mechanism and origins of this ligand-controlled regio- and stereoselectivity.

Incorporating two organic ligands with different functionalities into a titanium-oxo cluster entity simultaneously can endow the material with their respective properties and provide synergistic performance enhancement, which is of great significance for enriching the structure and properties of titanium-oxo clusters (TOCs). However, the synthesis of such TOCs is highly challenging. In this work, we successfully synthesized a TBC4A-functionalized TOC, [Ti2(TBC4A)2(MeO)2] (Ti2; MeOH = methanol, TBC4A = tert-butylcalix[4]arene). By adjusting the solvent system, we successfully introduced 1,10-phenanthroline (Phen) and prepared TBC4A and Phen co-protected [Ti2(TBC4A)2(Phen)2] (Ti2-Phen). Moreover, when Phen was replaced with bulky 4,7-diphenyl-1,10-phenanthroline (Bphen), [Ti2(TBC4A)2(Bphen)2] (Ti2-Bphen), which is isostructural with Ti2-Phen, was obtained, demonstrating the generality of the synthetic method. Remarkably, Ti2-Phen demonstrates good stability and stronger light absorption, as well as superior photoelectric performance compared to Ti2. Density functional theory (DFT) calculations reveal that there exists ligand-to-core charge transfer (LCCT) in Ti2, while an unusual ligand-to-ligand charge transfer (LLCT) is present in Ti2-Phen, accompanied by partial LCCT. Therefore, the superior light absorption and photoelectric properties of Ti2-Phen are attributed to the existence of the unusual LLCT phenomenon. This study not only deeply explores the influence of Phen on the performance of the material but also provides a reference for the preparation of materials with excellent photoelectric performance.

Urea electrosynthesis from co-electrolysis of NO3 - and CO2 (UENC) offers a promising technology for achieving sustainable and efficient urea production. Herein, a diatomic alloy catalyst (CuPd1Rh1-DAA), with mutually isolated Pd and Rh atoms alloyed on Cu substrate, is theoretically designed and experimentally confirmed to be a highly active and selective UENC catalyst. Combining theoretical computations and operando spectroscopic characterizations reveals the synergistic effect of Pd1-Cu and Rh1-Cu active sites to promote the UENC via a tandem catalysis mechanism, where Pd1-Cu site triggers the early C-N coupling and promotes *CO2NO2-to-*CO2NH steps, while Rh1-Cu site facilitates the subsequent protonation step of *CO2NH2 to *COOHNH2 toward the urea formation. Impressively, CuPd1Rh1-DAA assembled in a flow cell presents the highest urea Faradaic efficiency of 72.1% and urea yield rate of 53.2 mmol h-1 gcat -1 at -0.5 V versus RHE, representing nearly the highest performance among all reported UENC catalysts.

Hydrogen energy has attracted a lot of interest from researchers as a sustainable and renewable energy source, but there are some technical challenges related to its storage. Hydride materials demonstrate the ability to store hydrogen adequately and safely. In the current study, we have investigated the structural and optoelectronic properties of the XCuH3 (where X = Li, Na and K) perovskite-type hydride using LDA and GGA formalisms for hydrogen storage application. Electronic properties such as band structure, density of states reveal the metallic character of the studied XCuH3 hydrides. Various optical parameters such as the complex dielectric function, refractive index, extinction coefficient, absorption coefficient, reflectivity, optical conductivity, energy loss function, and joint density of states have been computed and compared. The gravimetric hydrogen storage capacity for LiCuH3, NaCuH3 and KCuH3 are found to be 4.11, 3.37 and 2.86 wt%, respectively. The computed values of the gravimetric ratio manifest that XCuH3 hydrides are potential candidates for hydrogen storage applications. These calculations are made for the first time for XCuH3 hydrides and will be inspirational in the future for comparison and for hydrogen storage purposes.