Oxophilic Sites Mediated Dynamic Oxygen Replenishment to Stabilize Lattice Oxygen Catalysis in Acidic Water Oxidation.

Developing efficient and durable catalysts for the oxygen evolution reaction (OER) in acidic media is essential for advancing proton exchange membrane water electrolysis (PEMWE). However, catalyst instability caused by lattice oxygen (O) depletion and metal dissolution remains a critical barrier. Here, we propose an oxophilic-site-mediated dynamic oxygen replenishment mechanism (DORM), in which O actively participates in O-O bond formation and is continuously refilled by water-derived species.

Organic Surface Passivation on Rh@CeO Cocatalysts for Photocatalytic Overall Water Splitting.

Decorating Rh cocatalysts with CrO overlayers can enhance the performance of photocatalytic overall water splitting (POWS). However, there is a general concern on the dissolution of CrO, calling for the development of environment-friendly metal oxides. Here, we employ phenylphosphonic acid (PPOA) as a model surface modifier to decorate the model Rh@CeO cocatalysts and demonstrate the critical role of organic surface passivation in H evolution catalysis.

CO Photoreduction by HO: Cooperative Catalysis of Palladium Species on Poly(triazine imide) Crystals.

Photocatalytic CO reduction coupled with HO oxidation has been pursued extensively, albeit facing challenges in efficiency and selectivity. Herein, we develop a Pd/PTI catalyst by co-anchoring atomic and nanoparticulate Pd species on poly(triazine imide) crystals, which exhibits high activity, selectivity, and stability for CO reduction to CO using HO as the reductant. Combined experimental and theoretical studies reveal that the dual Pd species synergistically enhance charge separation and transfer while promoting CO activation, CO desorption, and HO dissociation.

Photocatalytic ethylene production over defective NiO through lattice oxygen participation.

Lattice oxygen-mediated photocatalytic ethane dehydrogenation represents a sustainable strategy for ethylene production, yet achieving a balance between high productivity, selectivity, and durability remains challenging. Here, we report a defective NiO-300 catalyst, where precisely engineered Ni vacancies activate lattice oxygen by weakening Ni-O bond and improving lattice oxygen mobility. This promotes efficient ethane activation and C-H bonds cleavage through photoinduced hole capture, intensifying ethane dehydrogenation via a light-boosted Mars-van Krevelen mechanism.

Triple-Phase Boundaries Enable Selective Urea Production From Simulated Flue Gas in a Zero-Gap Electrolyzer.

Renewable energy-powered co-electrolysis of CO and NO offers a promising pathway toward sustainable urea production. However, achieving high urea selectivity is challenging due to substantial competing side reactions. Here, we show that engendering a high density of CO bubbles on the catalyst surface creates numerous triple-phase boundaries that are key toward enhancing CO versus NO availability for selective urea production.

Synergistic Ru Species on Poly(heptazine imide) Enabling Efficient Photocatalytic CO Reduction with HO beyond 800 nm.

Photocatalytic CO conversion with HO to carbonaceous fuels is a desirable strategy for CO management and solar utilization, yet its efficiency remains suboptimal. Herein, efficient and durable CO photoreduction is realized over a Ru/Ru-PHI catalyst assembled by anchoring Ru single atoms (SAs) and nanoparticles (NPs) onto poly(heptazine imide) (PHI) via the in-plane Ru-N coordination and interfacial Ru-N bonds, respectively. This catalyst shows an unsurpassed CO production (32.

Activating Lattice Oxygen in Perovskite Ferrite for Efficient and Stable Photothermal Dry Reforming of Methane.

Lattice oxygen (LO)-mediated photothermal dry reforming of methane (DRM) presents a promising approach to syngas production. However, realizing high DRM efficiency and durability remains challenging due to the difficulty in activating LOs in catalysts. Herein, we demonstrate that partially substituting Fe sites in perovskite ferrite (LaFeO) by Mn triggers LOs, bestowing the catalyst with superior activity and stability for photothermal DRM after modification with Ru.

Modulating the covalency of Ru-O bonds by dynamic reconstruction for efficient acidic oxygen evolution.

Developing ruthenium-based oxide catalysts capable of suppressing lattice oxygen participation in the catalytic reaction process is crucial for maintaining stable oxygen evolution reaction (OER) under acidic conditions. Herein, we delicately construct a RuO nanoparticle-anchored LiCoO nanosheet electrocatalyst (RuO/LiCoO), achieving dynamic optimization of RuO during the reaction process and improving catalytic stability. Benefiting from the unique electrochemical delithiation characteristics of the LiCoO support, the covalency of the Ru-O bond is effectively regulated during the OER process.

Tuning catalyst-support interactions enable steering of electrochemical CO reduction pathways.

Tuning of catalyst-support interactions potentially offers a powerful means to control activity. However, rational design of the catalyst support is challenged by a lack of clear property-activity relationships. Here, we uncover how the electronegativity of a support influences reaction pathways in electrochemical CO reduction.

Isolated iridium oxide sites on modified carbon nitride for photoreforming of plastic derivatives.

The rising concentration of plastics due to extensive disposal and inefficient recycling of plastic waste poses an imminent and critical threat to the environment and ecological systems. Photocatalytic reforming of plastic derivatives to value-added chemicals under ambient conditions proceeds at lower oxidation potential which galvanizes the hydrogen evolution. We report the synthesis of a narrow band gap NCN-functionalized O-bridged carbon nitride (MC) through condensation polymerization of hydrogen-bonded melem (M)-cyameluric acid (C) macromolecular aggregate.

Dynamic Deprotonation Enhancement Triggered by Accelerated Electrochemical Delithiation Reconstruction during Acidic Water Oxidation.

The structure-dependent transition in reaction pathways during acidic oxygen evolution (OER) is pivotal due to the active site oxidation accompanied by the coordination environment changes. In this work, charge-polarized Ir-O-Co units are constructed in alkali metal cobalt oxides (LiCoO, and NaCoO) to modify the lower Hubbard band. Benefiting from the accelerated delithiation reconstruction induced by the altered band structure, typical Ir-LiCoO produces high-valent Ir sites with unsaturated coordination through the charge compensation during OER.

Microenvironment Matters: Copper-Carbon Composites Enable a Highly Efficient Carbon Dioxide Reduction Reaction to C Products.

Copper is the catalyst widely used to produce multicarbon products for the carbon dioxide reduction reaction (CORR). The surrounding microenvironment of copper plays a crucial role in determining its catalytic activity and selectivity. In this study, we compare three copper electrocatalysts with different microenvironments: pure metallic copper, a copper metal-organic framework (MOF), and a MOF-derived copper-carbon composite.

Exploring the Mechanism of Surface Cationic Vacancy Induces High Activity of Metastable Lattice Oxygen in Li- and Mn-Rich Cathode Materials.

Li- and Mn-rich layered oxides exhibit high specific capacity due to the cationic and anionic reaction process during high-voltage cycling (≥4.6 V). However, they face challenges such as low initial coulombic efficiency (~70 %) and poor cycling stability.

A Library of Seed@High-Entropy-Alloy Core-shell Nanocrystals With Controlled Facets for Catalysis.

High-entropy-alloy (HEA) nanocrystals hold immense potential for catalysis, offering virtually unlimited alloy combinations through the inclusion of at least five constituent elements in varying ratios. However, general and effective strategies for synthesizing libraries of HEA nanocrystals with controlled surface atomic structures remain scarce. In this study, a transferable strategy for developing a library of facet-controlled seed@HEA nanocrystals through seed-mediated growth is presented.

Lewis Acid-Mediated Interfacial Water Supply for Sustainable Proton Exchange Membrane Water Electrolysis.

The catalyst-electrolyte interface plays a crucial role in proton exchange membrane water electrolysis (PEMWE). However, optimizing the interfacial hydrogen bonding to enhance both catalytic activity and stability remains a significant challenge. Here, a novel catalyst design strategy is proposed based on the hard-soft acid-base principle, employing hard Lewis acids (LAs = ZrO, TiO, HfO) to mediate the reconfiguration of interfacial hydrogen bonding, thereby enhancing the acidic oxygen evolution reaction (OER) performance of RuO.

Manipulating C-C coupling pathway in electrochemical CO reduction for selective ethylene and ethanol production over single-atom alloy catalyst.

Manipulation C-C coupling pathway is of great importance for selective CO electroreduction but remain challenging. Herein, two model Cu-based catalysts, by modifying Cu nanowires with Ag nanoparticles (AgCu NW) and Ag single atoms (AgCu NW), respectively, are rationally designed for exploring the C-C coupling mechanisms in electrochemical CO reduction reaction (CORR). Compared to AgCu NW, the AgCu NW exhibits a more than 10-fold increase of C selectivity in CO reduction to ethanol, with ethanol-to-ethylene ratio increased from 0.

Designing neighboring-site activation of single atom via tunnel ions for boosting acidic oxygen evolution.

Realizing an efficient turnover frequency in the acidic oxygen evolution reaction by modifying the reaction configuration is crucial in designing high-performance single-atom catalysts. Here, we report a "single atom-double site" concept, which involves an activatable inert manganese atom redox chemistry in a single-atom Ru-Mn dual-site platform with tunnel Ni ions as the trigger. In contrast to conventional single-atom catalysts, the proposed configuration allows direct intramolecular oxygen coupling driven by the Ni ions intercalation effect, bypassing the secondary deprotonation step instead of the kinetically sluggish adsorbate evolution mechanism.

Modulating Spin of Atomic Manganese Center for High-Performance Oxygen Reduction Reaction.

Single atom catalysts (SACs) are promising non-precious catalysts for oxygen reduction reaction (ORR). Unfortunately, the ORR SACs usually suffer from unsatisfactory activity and in particular poor stability. Herein, we report atomically dispersed manganese (Mn) embedded on nitrogen and sulfur co-doped graphene as an efficient and robust electrocatalyst for ORR in alkaline electrolyte, realizing a half-wave potential (E) of 0.

Accelerated Proton Transfer in Asymmetric Active Units for Sustainable Acidic Oxygen Evolution Reaction.

The poor durability of Ru-based catalysts limits the practical application in proton exchange membrane water electrolysis (PEMWE). Here, we report that the asymmetric active units in RuMO (M = Sb, In, and Sn) binary solid solution oxides are constructed by introducing acid-resistant p-block metal sites, breaking the activity and stability limitations of RuO in acidic oxygen evolution reaction (OER). Constructing highly asymmetric Ru-O-Sb units with a strong electron delocalization effect significantly shortens the spatial distance between Ru and Sb sites, improving the bonding strength of the overall structure.

Incorporation of Pd Single-Atom Sites in Perovskite with an Excellent Selectivity toward Photocatalytic Semihydrogenation of Alkynes.

Semihydrogenation is a crucial industrial process. Noble metals such as Pd have been extensively studied in semihydrogenation reactions, owing to their unique catalytic activity toward hydrogen activation. However, the overhydrogenation of alkenes to alkanes often happens due to the rather strong adsorption of alkenes on Pd active phases.

A catalyst family of high-entropy alloy atomic layers with square atomic arrangements comprising iron- and platinum-group metals.

We report a catalyst family of high-entropy alloy (HEA) atomic layers having three elements from iron-group metals (IGMs) and two elements from platinum-group metals (PGMs). Ten distinct quinary compositions of IGM-PGM-HEA with precisely controlled square atomic arrangements are used to explore their impact on hydrogen evolution reaction (HER) and hydrogen oxidation reaction (HOR). The PtRuFeCoNi atomic layers perform enhanced catalytic activity and durability toward HER and HOR when benchmarked against the other IGM-PGM-HEA and commercial Pt/C catalysts.

Enhanced Carbon-Carbon Coupling at Interfaces with Abrupt Coordination Number Changes.

Cu-catalyzed electrochemical CO reduction reaction (CORR) produces multi-carbon (C) chemicals with considerable selectivities and activities, yet required high overpotentials impede its practical application. Here, we design interfaces with abrupt coordination number (CN) changes that greatly reduce the applied potential for achieving high C Faradaic efficiency (FE). Encouraged by the mechanistic finding that the coupling between *CO and *CO(H) is the most probable C-C bond formation path, we use CuO- and Cu-phthalocyanine-derived Cu (OD-Cu and PD-Cu) to build the interface.

Dynamic chloride ion adsorption on single iridium atom boosts seawater oxidation catalysis.

Seawater electrolysis offers a renewable, scalable, and economic means for green hydrogen production. However, anode corrosion by Cl pose great challenges for its commercialization. Herein, different from conventional catalysts designed to repel Cl adsorption, we develop an atomic Ir catalyst on cobalt iron layered double hydroxide (Ir/CoFe-LDH) to tailor Cl adsorption and modulate the electronic structure of the Ir active center, thereby establishing a unique Ir-OH/Cl coordination for alkaline seawater electrolysis.