Tackling the Activity Trend of Metal-Loaded Metal Nitride Catalysts for NH Synthesis by a First-Principles Microkinetic Study.

Ammonia (NH) is one of the most widely produced chemicals globally, primarily synthesized through the Haber-Bosch process, which requires high temperatures and pressures. Dual-site catalysts can activate N and H at spatially separated sites, enabling efficient NH synthesis under milder conditions. Despite the rapid experimental progress of the dual-site catalysts (e.

Preparation Techniques for Perovskite Single Crystal Films: From Nucleation to Growth.

Thickness-controllable perovskite single crystal films exhibit tremendous potential for various optoelectronic applications due to their capacity to leverage the relationship between diffusion length and absorption depth. However, the fabrication processes have suffered from difficulties in large-area production and poor quality with abundant surface defects. While post-treatments, such as passivation and polishing, can provide partial improvement in surface quality, the fundamental solution lies in the direct growth of high-quality single crystal films.

The effect of a distorted MO octahedral unit on the activity and stability for the oxygen evolution reaction.

Metal oxides have garnered significant attention in the oxygen evolution reaction (OER), where a distorted MO octahedral unit has a marked impact on their performance. This study introduces the distortion coefficient to quantify the MO distortion composed of its volume and shape, and reports the effect of MO distortion on the activity and stability in rutile metal oxides for the OER. This provides a fundamental understanding for designing effective MO active units for the OER.

Oxygen Plasma Triggered Co-O-Fe Motif in Prussian Blue Analogue for Efficient and Robust Alkaline Water Oxidation.

In the context of oxygen evolution reaction (OER), the construction of high-valence transition metal sites to trigger the lattice oxygen oxidation mechanism is considered crucial for overcoming the performance limitations of traditional adsorbate evolution mechanism. However, the dynamic evolution of lattice oxygen during the reaction poses significant challenges for the stability of high-valence metal sites, particularly in high-current-density water-splitting systems. Here, we have successfully constructed Co-O-Fe catalytic active motifs in cobalt-iron Prussian blue analogs (CoFe-PBA) through oxygen plasma bombardment, effectively activating lattice oxygen reactivity while sustaining robust stability.

Optimizing the Lattice Nitrogen Coordination to Break the Performance Limitation of Metal Nitrides for Electrocatalytic Nitrogen Reduction.

Metal nitrides (MNs) are attracting enormous attention in the electrocatalytic nitrogen reduction reaction (NRR) because of their rich lattice nitrogen (N) and the unique ability of N vacancies to activate N. However, continuing controversy exists on whether MNs are catalytically active for NRR or produce NH via the reductive decomposition of N without N activation in the in situ electrochemical conditions, let alone the rational design of high-performance MN catalysts. Herein, we focus on the common rocksalt-type MN(100) catalysts and establish a quantitative theoretical framework based on the first-principles microkinetic simulations to resolve these puzzles.

Anionic Metal-Organic Framework Derived Cu Catalyst for Selective CO Electroreduction to Hydrocarbons.

Metal-organic frameworks (MOFs)-related Cu materials are promising candidates for promoting electrochemical CO reduction to produce valuable chemical feedstocks. However, many MOF materials inevitable undergo reconstruction under reduction conditions; therefore, exploiting the restructuring of MOF materials is of importance for the rational design of high-performance catalyst targeting multi-carbon products (C). Herein, a facile solvent process is choosed to fabricate HKUST-1 with an anionic framework (a-HKUST-1) and utilize it as a pre-catalyst for alkaline CORR.

In situ/Operando Synchrotron Radiation Analytical Techniques for CO/CO Reduction Reaction: From Atomic Scales to Mesoscales.

Electrocatalytic carbon dioxide/carbon monoxide reduction reaction (CORR) has emerged as a prospective and appealing strategy to realize carbon neutrality for manufacturing sustainable chemical products. Developing highly active electrocatalysts and stable devices has been demonstrated as effective approach to enhance the conversion efficiency of CORR. In order to rationally design electrocatalysts and devices, a comprehensive understanding of the intrinsic structure evolution within catalysts and micro-environment change around electrode interface, particularly under operation conditions, is indispensable.

Universal growth of perovskite thin monocrystals from high solute flux for sensitive self-driven X-ray detection.

Metal-halide perovskite thin monocrystals featuring efficient carrier collection and transport capabilities are well suited for radiation detectors, yet their growth in a generic, well-controlled manner remains challenging. Here, we reveal that mass transfer is one major limiting factor during solution growth of perovskite thin monocrystals. A general approach is developed to overcome synthetic limitation by using a high solute flux system, in which mass diffusion coefficient is improved from 1.

Ultrahigh Bifunctional Photocatalytic CO Reduction and H Evolution by Synergistic Interaction of Heteroatomic Pt-Ru Dimerization Sites.

Diatomic-site catalysts (DASCs) inherit the excellent performance of single-atom catalysts (SACs) by utilizing two adjacent atomic metal species to achieve functional complementarity and synergistic effects that improve the carbon dioxide reduction reaction (CORR) and H evolution reaction (HER) kinetics. Herein, we report a method to further improve the catalytic efficiency of Pt by using Pt and Ru single atoms randomly anchored on a g-CN surface, yielding partial Pt-Ru dimers. The synthesized catalyst exhibits extraordinary photocatalytic activity and stability in both the CORR and HER processes.

Crystal Facet Engineering on SrTiO Enhances Photocatalytic Overall Water Splitting.

Single-crystal semiconductor-based photocatalysts exposing unique crystallographic facets show promising applications in energy and environmental technologies; however, crystal facet engineering through solid-state synthesis for photocatalytic overall water splitting is still challenging. Herein, we develop a novel crystal facet engineering strategy through solid-state recrystallization to synthesize uniform SrTiO single crystals exposing tailored {111} facets. The presynthesized low-crystalline SrTiO precursors enable the formation of well-defined single crystals through kinetically improved crystal structure transformation during solid-state recrystallization process.

Polar Aromatic Two-dimensional Dion-Jacobson Halide Perovskites for Efficient Photocatalytic H Evolution.

Polar materials with spontaneous polarization (P) have emerged as highly promising photocatalysts for efficient photocatalytic H evolution owing to the P-enhanced photogenerated carrier separation. However, traditional inorganic polar materials often suffer from limitations such as wide band gaps and poor carrier transport, which hinders their photocatalytic H evolution efficiency. Here, we rationally synthesized a series of isostructural two-dimensional (2D) aromatic Dion-Jacobson (DJ) perovskites, namely (2-(2-Aminoethyl)pyridinium)PbI (2-APDPI), (3-(2-Aminoethyl)pyridinium)PbI (3-APDPI), and (4-(2-Aminoethyl)pyridinium)PbI (4-APDPI), where 2-APDPI and 4-APDPI crystalize in polar space groups with piezoelectric constants (d) of approximately 40 pm V and 3-APDPI adopts a centrosymmetric structure.

Interface-confined intermediate phase in TiO enables efficient photocatalysis.

As a prototypical photocatalyst, TiO[Formula: see text] has been extensively studied. An interesting yet puzzling experimental fact was that P25-a mixture of anatase and rutile TiO[Formula: see text]-outperforms the individual phases; the origin of this mysterious fact, however, remains elusive. Employing rigorous first-principles calculations, here we uncover a metastable intermediate structure (MIS), which is formed due to confinement at the anatase/rutile interface.

Self-Reconstruction of Sulfate-Terminated Copper Oxide Nanorods for Efficient and Stable 5-Hydroxymethylfurfural Electrooxidation.

The electrochemical 5-hydroxymethylfurfural oxidation reaction (HMFOR) has been regarded as a viable alternative to sustainable biomass valorization. However, the transformation of the catalysts under harsh electrooxidation conditions remains controversial. Herein, we confirm the self-construction of cuprous sulfide nanosheets (CuS NSs) into sulfate-terminated copper oxide nanorods (CuO-SO NRs) during the first-cycle of the HMFOR, which achieves a near-quantitative synthesis of 2,5-furandicarboxylic acid (FDCA) with a >99.

Direct OC-CHO coupling towards highly C products selective electroreduction over stable Cu/Cu interface.

Electroreduction of CO to valuable multicarbon (C) products is a highly attractive way to utilize and divert emitted CO. However, a major fraction of C selectivity is confined to less than 90% by the difficulty of coupling C-C bonds efficiently. Herein, we identify the stable Cu/Cu interfaces derived from copper phosphate-based (CuPO) electrocatalysts, which can facilitate C production with a low-energy pathway of OC-CHO coupling verified by in situ spectra studies and theoretical calculations.

Ruthenium and Iron Co-doped Molybdenum Carbide as a Stable Hydrogen Evolution Electrocatalyst in Harsh Electrolyte.

Electrocatalytic water splitting is one of the most commercially valuable pathways of hydrogen production especially combined with renewable electricity; however, efficient and durable electrocatalysts are urgently needed to reduce electric energy consumption. Here, we reported a Ru and Fe co-doped Mo C on nitrogen doped carbon via a controllable two-step method, which can be used for efficient and enduring hydrogen evolution reaction. At 10, 100 and 200 mA cm in acidic electrolyte, the resultant Ru-Fe/Mo C@NC delivered low overpotentials of 31, 78 and 103 mV, respectively, which are comparable to that of the commercial Pt/C (20 wt %).

Construction of a ruthenium-doped CoFe-layered double hydroxide as a bifunctional electrocatalyst for overall water splitting.

In this study, ruthenium-doped CoFe-based layered double hydroxides on Ni foam (CoFe-ZLDH/Ru@NF) were fabricated an etching-precipitation strategy. The resultant CoFe-ZLDH/Ru@NF exhibited excellent activity, showing low overpotentials of 219.8 mV and 60.

Heterogeneous Fe-Doped Ni(OH) Grown on Nickel Mesh by Electrodeposition for Efficient Alkaline Oxygen Evolution Reaction.

Designing highly excellent and stable catalysts for alkaline oxygen evolution reaction (OER) is gradually pivotal for clean energy development. In this work, a heterogeneous Fe-doped Ni(OH) (Ni/Fe-0.1) was developed via simple one-step electrodeposition onto nickel mesh.

Scalable synthesis of coordinatively unsaturated metal-nitrogen sites for large-scale CO electrolysis.

Practical electrochemical CO-to-CO conversion requires a non-precious catalyst to react at high selectivity and high rate. Atomically dispersed, coordinatively unsaturated metal-nitrogen sites have shown great performance in CO electroreduction; however, their controllable and large-scale fabrication still remains a challenge. Herein, we report a general method to fabricate coordinatively unsaturated metal-nitrogen sites doped within carbon nanotubes, among which cobalt single-atom catalysts can mediate efficient CO-to-CO formation in a membrane flow configuration, achieving a current density of 200 mA cm with CO selectivity of 95.

Amorphous Oxysulfide Reconstructed from Spinel NiCo S for Efficient Water Oxidation.

The progress of effective and durable electrocatalysts for oxygen evolution reaction (OER) is urgent, which is essential to promote the overall efficiency of green hydrogen production. To improve the performance of spinel cobalt-based oxides, which serve as promising water oxidation electrocatalysts in alkaline electrolytes, most researches have been concentrated on cations modification. Here, an anionic regulation mechanism is employed to adopt sulfur(S) anion substitution to supplant NiCo O by NiCo S , which contributed to an impressive OER performance in alkali.

Tuning the Microenvironment in Monolayer MgAl Layered Double Hydroxide for CO -to-Ethylene Electrocatalysis in Neutral Media.

The electrocatalytic reduction of carbon dioxide provides a feasibility to achieve a carbon-neutral energy cycle. However, there are a number of bottleneck issues to be resolved before industrial application, such as the low conversion efficiency, selectivity and reaction rate, etc. Engineering local environment is a critical way to address these challenges.

Isolation of Highly Reactive Cobalt Phthalocyanine via Electrochemical Activation for Enhanced CO Reduction Reaction.

Electrochemical CO -to-CO conversion offers an attractive and efficient route to recycle CO greenhouse gas. Molecular catalysts, like CoPc, are proved to be possible replacement for precious metal-based catalysts. These molecules, a combination of metal center and organic ligand molecule, may evolve into single atom structure for enhanced performance; besides, the manipulation of molecules' behavior also plays an important role in mechanism research.

Positive Valent Metal Sites in Electrochemical CO Reduction Reaction.

The discovery of high-performance catalysts for the electrochemical CO reduction reaction (CO RR) has faced an enormous challenge for years. The lack of cognition about the surface active structures or centers of catalysts in complex conditions limits the development of advanced catalysts for CO RR. Recently, the positive valent metal sites (PVMS) are demonstrated as a kind of potential active sites, which can facilitate carbon dioxide (CO ) activation and conversation but are always unstable under reduction potentials.