Theoretical Insights into the Efficient Reduction of Nitrate to Ammonia on Crystalline Carbon Nitride.

The nitrate reduction reaction (NORR) has emerged as a promising approach for wastewater treatment and ammonia (NH) synthesis. Poly(triazine imide)/LiCl (PTI/LiCl), a highly crystalline carbon nitride with a well-defined structure, has shown significant potential in this field. In this study, the electronic properties and catalytic performance of PTI/LiCl for NORR were investigated through theoretical calculations.

Regulation of electron density in Pt nanoparticles via bimetallic metal-organic frameworks for enhancing photothermal catalysis of toluene decomposition.

Volatile Organic Compounds (VOCs) are omnipresent in the sphere of human industrial, harboring latent adverse consequences for health and the ecological system. The photothermal catalytic oxidation of VOCs is an advanced integrated technology that harnesses the combined effects of light and heat energy to enhance the efficiency of VOCs degradation. Herein, a bimetallic Metal-Organic Framework (MOF) was synthesized with the incorporation of Ce into the UiO-66-NH(Zr) (i.

A 3D Robust and Microporous B←N Framework with 8-connected Sandwich Nodes for Efficient Separation of Hexane Isomers.

Recently B←N organic frameworks (BNFs) have gained substantial attention owing to their unique dative bond energy, which imparts them with specialized functionalities across a broad spectrum of applications. Despite previous reports on BNFs with permanent porosity, research endeavors towards three-dimensional (3D) BNFs with similar properties are scarce, with no report of robust 3D BNFs featuring permanent porosity to date. Herein, electrostatic complementary strategy is proposed to construct the first example of 3D robust and microporous BNF, BNF-100, featuring a reo topology with 8-connected sandwich nodes assembled via dative B←N bonds.

Regulating electron transfer and orbital interaction within metalloporphyrin-MOFs for highly sensitive NO sensing.

The understanding of electron transfer pathways and orbital interactions between analytes and adsorption sites in gas-sensitive studies, especially at the atomic level, is currently limited. Herein, we have designed eight isoreticular catechol-metalloporphyrin scaffolds, FeTCP-M and InTCP-M (TCP = 5,10,15,20-tetrakis-catechol-porphyrin, M = Fe, Co, Ni and Zn) with adjustable charge transfer schemes in the coordination microenvironment and precise tuning of orbital interactions between analytes and adsorption sites, which can be used as models for exploring the influence of these factors on gas sensing. Our experimental findings indicate that the sensitivity and selectivity can be modulated using the type of metals in the metal-catechol chains (which regulate the electron transfer routes) and the metalloporphyrin rings (which fine-tune the orbital interactions between analytes and adsorption sites).

Synergistic effect between transition metal single atom and SnS toward deep CO reduction.

The electrochemical reduction of CO is an efficient channel to facilitate energy conversion, but the rapid design and rational screening of high-performance catalysts remain a great challenge. In this work, we investigated the relationships between the configuration, energy, and electronic properties of SnS loaded with transition metal single atom (TM@SnS) and analyzed the mechanism of CO activation and reduction by using density functional theory. The "charge transfer bridge" promoted the adsorption of CO on TM@SnS, thus enhancing the binding of HCOOH∗ to the catalyst for further hydrogenation and reduction to high-value CH.

Reveal long-lived hot electrons in 2D indium selenide and ferroelectric-regulated carrier dynamics of InSe/α-In2Se3/InSe heterostructure.

As typical representatives of group III chalcogenides, InSe, α-In2Se3, and β'-In2Se3 have drawn considerable interest in the domain of photoelectrochemistry. However, the microscopic mechanisms of carrier dynamics in these systems remain largely unexplored. In this work, we first reveal that hot electrons in the three systems have different cooling rate stages and long-lived hot electrons, through the utilization of density functional theory calculations and nonadiabatic molecular dynamics simulations.

Self-driven electrochemical system using solvent-regulated structural diversity of cadmium(II) metal-organic frameworks.

Optimizing friction materials based on molecular diversity in a molecular framework system is an effective method to improve the output performance of triboelectric nanogenerators (TENGs). In this study, three cadmium(II) metal-organic frameworks (Cd-MOFs) with different cavities were synthesized solvothermally by the assembly of cadmium nitrate (Cd(NO)·4HO), 4',4'''-carbonylbis(([1,1'-biphenyl]-3,5-dicarboxylic acid)) (HCBBD), and trans-1,2-bis(4-pyridyl)ethylene (4,4'-bpe) via a solvent-regulated strategy. The topology and porosity of Cd-MOFs could be controlled effectively by the solvent constituents and were demonstrated to be closely related to their triboelectric behaviors.

Two-dimensional correlation infrared spectroscopy study on vanadoborate anionic skeleton regulated by countercations.

Two novel vanadoborate compounds, [Cu(en)][Li(HO)][Li(HO)][VBO(OH)(HO)]·33.5HO (1) and (Hen)[Li(HO)][VBO(OH)(HO)]·14HO (2), were synthesized via hydrothermal synthesis under identical conditions except for temperature. Structural analysis revealed that although both contain [VBO] cluster anion, the different countercations potentially lead to variations in the [VBO] cluster anion skeletons.

Multistate structures in a hydrogen-bonded polycatenation non-covalent organic framework with diverse resistive switching behaviors.

The inherent structural flexibility and reversibility of non-covalent organic frameworks have enabled them to exhibit switchable multistate structures under external stimuli, providing great potential in the field of resistive switching (RS), but not well explored yet. Herein, we report the 0D+1D hydrogen-bonded polycatenation non-covalent organic framework (HOF-FJU-52), exhibiting diverse and reversible RS behaviors with the high performance. Triggered by the external stimulus of electrical field E at room temperature, HOF-FJU-52 has excellent resistive random-access memory (RRAM) behaviors, comparable to the state-of-the-art materials.

Theoretical Insight into the Special Synergy of Bimetallic Site in Co/MoC Catalyst to Promote N -to-NH Conversion.

The catalytic mechanisms of nitrogen reduction reaction (NRR) on the pristine and Co/α-MoC(001) surfaces were explored by density functional theory calculations. The results show that the preferred pathway is that a direct N≡N cleavage occurs first, followed by continuous hydrogenations. The production of second NH molecule is identified as the rate-limiting step on both systems with kinetic barriers of 1.

First-principles study of CO2 hydrogenation on Cd-doped ZrO2: Insights into the heterolytic dissociation of H2.

Cd-doped ZrO2 catalyst has been found to have high selectivity and activity for CO2 hydrogenation to methanol. In this work, density functional theory calculations were carried out to investigate the microscopic mechanism of the reaction. The results show that Cd doping effectively promotes the generation of oxygen vacancies, which significantly activate the CO2 with stable adsorption configurations.

Computational screening of high activity and selectivity of CO reduction transition metal single-atom catalysts on triazine-based graphite carbon nitride.

Single-atom catalysts (SACs) are emerging as promising catalysts in the field of the electrocatalytic CO reduction reaction (CORR). Herein, a series of 3d to 5d transition metal atoms supported on triazine-based graphite carbon nitride (TM@TGCN) as a CO reduction catalyst are studied density functional theory computations. Eventually, four TM@TGCN catalysts (TM = Ni, Rh, Os, and Ir) are selected using a five-step screening method, in which Rh@TGCN and Ni@TGCN show a low limiting potential of -0.

Unraveling Synergistic Effect of Defects and Piezoelectric Field in Breakthrough Piezo-Photocatalytic N Reduction.

Piezo-photocatalysis is a frontier technology for converting mechanical and solar energies into crucial chemical substances and has emerged as a promising and sustainable strategy for N fixation. Here, for the first time, defects and piezoelectric field are synergized to achieve unprecedented piezo-photocatalytic nitrogen reduction reaction (NRR) activity and their collaborative catalytic mechanism is unraveled over BaTiO with tunable oxygen vacancies (OVs). The introduced OVs change the local dipole state to strengthen the piezoelectric polarization of BaTiO , resulting in a more efficient separation of photogenerated carrier.

SiCN monolayer as a universal anode for alkali metal-ion batteries.

Our density functional theory calculations show that silicon doping in g-CN (SiCN) can improve the electrochemical performance of g-CN as an anode of alkali metal-ion batteries and solve the problems of too high adsorption ability and migration energy barrier commonly found in porous carbon nitride. The stability of SiCN was verified by molecular dynamics simulations and phonon spectroscopy. Elastic constant calculations revealed that the Si doping in g-CN can improve its mechanical properties.

Atomically Site Synergistic Effects of Dual-Atom Nanozyme Enhances Peroxidase-like Properties.

Pursuing effective and generalized strategies for modulating the electronic structures of atomically dispersed nanozymes with remarkable catalytic performance is exceptionally attractive yet challenging. Herein, we developed a facile "formamide condensation and carbonization" strategy to fabricate a library of single-atom (M-NC; 6 types) and dual-atom (M/M-NC; 13 types) metal-nitrogen-carbon nanozymes (M = Fe, Co, Ni, Mn, Ru, Cu) to reveal peroxidase- (POD-) like activities. The FeCo-NC dual-atom nanozyme with Fe-N/Co-N coordination displayed the highest POD-like activity.

Materials design of edge-modified polymeric carbon nitride nanoribbons for the photocatalytic CO reduction reaction.

Nanoribbon construction and modification with functional groups are important methods to improve the performance of photocatalysts. In this paper, density functional theory (DFT) calculations are applied to assess the electron absorption capacity of different model structures in the photocatalytic CO reduction reaction (CORR), , melon-based carbon nitride nanoribbons (MNRs) and edge-modified melon-based carbon nitride nanoribbons (X-MNRs, X = NO, CF, CN, CHO, F, Cl, CCH, OH, SH, CH, and H). It is found that X-MNRs (X = NO, CN, CHO, CCH, OH, and H) have a significantly reduced band gap.

Mechanism of CO photoreduction by selenium-doped carbon nitride with cobalt clusters as cocatalysts.

Doping is an efficient strategy for improving the photocatalytic activity and tuning the electronic structure of carbon nitride. Selenium-doped melon carbon nitride (Se-doped melon CN) as a promising photocatalyst for CO reduction is investigated using density functional theory calculations. In addition, considering the special role of a cocatalyst in CO reduction, we have explored the electronic and optical properties of Co clusters loaded on the Se-doped melon CN surface.

Defect and strain engineered MoS/graphene catalyst for an enhanced hydrogen evolution reaction.

Molybdenum disulfide (MoS) has been demonstrated as a promising non-precious metal electrocatalyst for the hydrogen evolution reaction (HER). However the efficiency of the HER falls short of expectations due to the large inert basal plane and poor electrical conductivity. In order to activate the MoS basal plane and enhance the hydrogen evolution reaction (HER) activity, two strategies on the hybrid MoS/graphene, including intrinsic defects and simultaneous strain engineering, have been systematically investigated based on density functional theory calculations.

Iron(II) Phthalocyanine Adsorbed on Defective Graphenes: A Density Functional Study.

The adsorptions of iron(II) phthalocyanine (FePc) on graphene and defective graphene were investigated systematically using density functional theory. Three types of graphene defects covering stone-wales (SW), single vacancy (SV), and double vacancy (DV) were taken into account, in which DV defects included DV(5-8-5), DV(555-777), and DV(5555-6-7777). The calculations of formation energies of defects showed that the SW defect has the lowest formation energy, and it was easier for DV defects to form compared with the SV defect.

Reactions of Thorium Oxide Clusters with Water: The Effects of Oxygen Content.

Thorium oxide has many important applications in industry. In this article, theoretical calculations have been carried out to explore the hydrolysis reactions of the ThO (n=1-3) clusters. The reaction mechanisms of the O-deficient ThO and the O-rich ThO are compared with the stoichiometric ThO .

Nitrogen reduction on crystalline carbon nitride supported by homonuclear bimetallic atoms.

Electrocatalytic nitrogen reduction reaction (eNRR) is a new method for sustainable NH production, which has attracted much attention in recent years. However, the low Faradaic efficiency due to the competitive hydrogen evolution reaction (HER) and inert N≡N triple bond activation hinders its practical application. To find highly efficient electrocatalysts with excellent activity, stability and selectivity, we have studied a series of transition metal dimers (TM) loaded on poly triazine imide, (PTI) a crystalline carbon nitride, by density functional theory calculations.

The role of Mo species in Ni-Mo catalysts for dry reforming of methane.

The Ni-Mo catalyst has attracted significant attention due to its excellent coke-resistance in dry reforming of methane (DRM) reaction, but its detailed mechanism is still vague. Herein, Mo-doped Ni (Ni-Mo) and MoO adsorbed Ni surfaces (MoO@Ni) are employed to explore the DRM reaction mechanism and the effect of coke-resistance. Due to the electron donor effect of Mo, the antibonding states below the Fermi level between Ni and C increase and the adsorption of C decrease, thereby inhibiting the carbonization of Ni.

Structures and electron affinity energies of polycyclic quinones.

In this study, quinoid structures, semiquinone radical structures, and electron affinity energies (EAEs) of many polycyclic quinones containing heteroatoms (O, B, and F) or heterocycles (pyrrole, imidazole, and pyrazine) were calculated. Quinones with unstable quinoid structures and stable semiquinone radical structures had high EAEs. The main factors of quinoid structural instability were spatial repulsion and antiaromaticity, and the stability factors of the semiquinone radical structure comprised inductive effects, hydrogen bonds, electrostatic interactions, and orbital interactions.

Theoretical study on Y-doped NaZrO as a high-capacity Na-rich cathode material based on anionic redox.

First-principles calculations based on density functional theory were utilized to study the performance of NaZrO (NZO) and yttrium-doped NaZrO (Y-NZO) as cathode materials for sodium ion batteries (SIBs), including the stability of the desodiated structures, desodiation energy, redox mechanism, and the diffusion of Na. When 62.5% sodium is removed from NZO, its structure and volume change little and the layered structure is retained, whereas the structure starts to distort and shift to the ZrO phase with the extraction of more than 62.