Density functional theory (DFT) computations were performed to investigate the electronic properties and Li storage capability of Ti(3)C(2), one representative MXene (M represents transition metals, X is either C or/and N) material, its fluorinated hydroxylated derivatives. The Ti(3)C(2) monolayer acts as a magnetic metal, while derived Ti(3)C(2)F(2) Ti(3)C(2)(OH)(2) in their stable conformations are semiconductors with small band gaps. adsorption forms strong Coulomb interaction...

The 1T phase of transition-metal dichalcogenides (TMDs) has been demonstrated in recent experiments to display excellent catalytic activity for hydrogen evolution reaction (HER), but the mechanism not elucidated so far. Herein, using MoS2 as prototypical TMD material, we studied HER on its basal plane from periodic density functional theory (DFT) calculations. Compared nonreactive 2H MoS2, mainly arises affinity binding H at surface S sites. Using free energy (ΔGH) descriptor, found that...

Electrocatalytic water splitting to produce H₂ plays an important role in the capture, conversion, and storage of renewable energy sources, such as solar wind power.

The bottom-up assembly of nanoparticles into diverse ordered solids is a challenge because it requires nanoparticles, which are often quasi-spherical, to have interaction anisotropy akin atoms and molecules. Typically, has been introduced by changing the shape inorganic nanoparticle core. Here, we present design, self-assembly, optical properties, total structural determination Ag29(BDT)12(TPP)4, an atomically precise tetravalent nanocluster (NC) (BDT, 1,3-benzenedithiol; TPP,...

The MoS2 monolayer is the second most studied two-dimensional material after graphene. However, covalent chemistry through S layers has not been fully explored for controlling properties of monolayer. Herein we probe potential chemical functionalization in tuning its electronic by first-principles density functional theory. We find that bonding groups (H, CH3, CF3, OCH3, NH2) anomalously strong (4–5 eV) on 1T phase (in low-coverage regimes) but very weak 2H phase. This affinity 1T-MoS2...

Abstract The theoretically predicted volcano plot for hydrogen production shows the best catalyst as one that ensures binding step is thermodynamically neutral. However, experimental realization of this concept has suffered from inherent surface heterogeneity solid catalysts. It even more challenging molecular catalysts because their complex chemical environment. Here, we report thermoneutral can be prepared by simple doping a platinum atom into molecule-like gold nanocluster. catalytic...

Copper electrocatalysts can reduce CO2 to hydrocarbons at high overpotentials. However, a mechanistic understanding of reduction on nanostructured Cu catalysts has been lacking. Herein we show that the structurally precise ligand-protected Cu-hydride nanoclusters, such as Cu32H20L12 (L is dithiophosphate ligand), offer unique selectivity for electrocatalytic low Our density functional theory (DFT) calculations predict presence negatively charged hydrides in copper cluster plays critical role...

Atomically precise, ligand-protected metal nanoclusters are of great interest for their well-defined structures, intriguing physicochemical properties, and potential applications in catalysis, biology, nanotechnology. Their structure precision provides many opportunities to correlate geometries, stability, electronic catalytic activities by closely integrating theory experiment. In this Account, we highlight recent theoretical advances from our efforts understand the metal-ligand interfaces,...

Understanding the isomerism phenomenon at nanoscale is a challenging task because of prerequisites precise composition and structural information on nanoparticles. Herein, we report ligand-induced, thermally reversible isomerization between two thiolate-protected 28-gold-atom nanoclusters, i.e. Au28(S-c-C6H11)20 (where -c-C6H11 = cyclohexyl) Au28(SPh-(t)Bu)20 -Ph-(t)Bu 4-tert-butylphenyl). The intriguing ligand effect in dictating stability Au28(SR)20 structures further investigated via...

Inspired by the intensive studies of graphene, scientists have put extraordinary efforts in exploring properties and phenomena involving noncarbon graphene‐like two‐dimensional (2D) nanomaterials, particularly those only consisting single layers or few layers. Experimentally, many 2D structures been fabricated from a large variety layered nonlayered materials. These already shown exceptional properties, which will offer new breakthroughs innovative opportunities nanomaterials science....

A novel Au19 nanocluster with a composition of [Au19(PhC≡C)9(Hdppa)3](SbF6)2 was synthesized (Hdppa = N,N-bis(diphenylphosphino)amine). Single crystal X-ray structural analysis reveals that the cluster comprises centered icosahedral Au13 core hugged by three V-shaped PhC≡C-Au-C≡C(Ph)-Au-C≡CPh motifs. Such motif is observed for first time in an alkynyl-protected gold nanocluster. The shows two main optical-absorption bands at 1.25 and 2.25 eV, confirmed time-dependent density functional...

The exceptional stability of thiolate-protected Au25 clusters, [Au25(SR)18](-), arises from the closure superatomic electron shells, leading to a noble-gas-like 8-electron configuration (1S(2)1P(6)). Here we present that replacing core Au atom with Pd or Pt results in stable [MAu24(SR)18](0) clusters (M = Pd, Pt) having 6-electron (1S(2)1P(4)). Voltammetric studies [PdAu24(SR)18](0) and [PtAu24(SR)18](0) reveal highest occupied molecular orbital-lowest unoccupied orbital (HOMO-LUMO) gaps...

As a fundamental step of water splitting and stepping stone toward exploring other multielectron transfer processes, the electrocatalytic hydrogen evolution reaction (HER) is an ideal model for both understanding electrocatalyst design. Here, we review fundamentals recent developments theoretical insights into HER, covering mechanistic aspects, key activity descriptors, local environment considerations, advances beyond computational electrode. Although it experimentally challenging to...

We report the fabrication of homoleptic alkynyl-protected Ag15 (C≡C-t Bu)12+ (abbreviated as ) nanocluster and its electrocatalytic properties toward CO2 reduction reaction. Crystal structure analysis reveals that possesses a body-centered-cubic (BCC) with an Ag@Ag8 @Ag6 metal core configuration. Interestingly, we found can adsorb in air spontaneously self-assembled into one-dimensional linear material during crystal growth process. Furthermore, convert CO faradaic efficiency ca. 95.0 % at...

Abstract Bioelectronics are powerful tools for monitoring and stimulating biological biochemical processes, with applications ranging from neural interface simulation to biosensing. The increasing demand bioelectronics has greatly promoted the development of new nanomaterials as detection platforms. Recently, owing their ultrathin structures excellent physicochemical properties, emerging two‐dimensional (2D) materials have become one most researched areas in fields biosensors. In this timely...

While atomically monodisperse nanostructured materials are highly desirable to unravel the size- and structure-catalysis relationships, their controlled synthesis atomic-level structure determination pose challenges. Particularly, copper-containing precise alloy nanoclusters potential catalyst candidates for electrochemical CO2 reduction reaction (eCO2RR) due high abundance tunable catalytic activity of copper. Herein, we report total an alkynyl-protected 21-atom AgCu nanocluster...

Electrochemically converting NO3- compounds into ammonia represents a sustainable route to remove industrial pollutants in wastewater and produce valuable chemicals. Bimetallic nanomaterials usually exhibit better catalytic performance than the monometallic counterparts, yet unveiling reaction mechanism is extremely challenging. Herein, we report an atomically precise [Ag30Pd4 (C6H9)26](BPh4)2 (Ag30Pd4) nanocluster as model catalyst toward electrochemical reduction (eNO3-RR) elucidate...

Unraveling the atomistic synergistic effects of nanoalloys on electrocatalytic CO2 reduction reaction (eCO2RR), especially in presence copper, is paramount importance. However, this endeavor encounters significant challenges due to lack crystallographically determined atomic-level structure appropriate monometallic and bimetallic analogues. Herein, we report a one-pot synthesis characterization AuCu nanoalloy cluster catalyst, [Au15Cu4(DPPM)6Cl4(C≡CR)1]2+ (denoted as Au15Cu4). Single-crystal...

Atomically precise metal nanoclusters (NCs) have emerged as an intriguing class of model catalysts for electrochemical CO2 reduction reactions (CO2RR). However, the interplay between interface environment (e.g., potential, cation concentration) and electron–proton transfer (ET/PT) kinetics─particularly in alkynyl-protected NCs─remains poorly understood. Here, we combined first-principles simulations experiments to investigate role potential effect on CO2RR performance a prototype...

Using ligand-protected Au 25 nanoclusters as a prototype model, we demonstrated that hydrophilic ligands enhance the hydrogen evolution reaction while hydrophobic improve efficiency of CO 2 electroreduction to CO.

Nitrogen-doped yellowish rutile titania was prepared by a mechanochemical method. The samples were high-energy ball milling of P-25 powder with various amounts hexamethylenetetramine (HMT) under different conditions at around room temperature. effects the reaction on phase composition, particle size, specific surface area, amount nitrogen-doping, microstructure and photocatalysis nitrogen monoxide destruction investigated in detail. high mechanical energy accelerated transformation from...

Anatase, brookite and rutile type nitrogen-doped titania nanocrystals (TiO2−xNy) which are beige in color were successfully prepared by a 'Homogeneous Precipitation–Solvothermal Process' (HPSP) TiCl3–hexamethylenetetramine (C6H12N4) aqueous alcohol solutions. The phase composition, crystallinity, microstructure, specific surface area, nitrogen doping amount photocatalytic activity of powders greatly changed depending on pH, temperature the treatment alcohols. TiO2−xNy showed excellent...