Enhanced CO2 reduction with hydrophobic cationic-ionomer layer-modified zero-gap MEA in acidic electrolyte.

A hydrophobic cationic-ionomer layer of quaternary ammonium poly(N-methyl-piperidine-co-p-terphenyl) and PTFE is presented to enhance the CO2 electroreduction in a zero-gap membrane electrode assembly (MEA) electrolyzer under acidic and low alkali ion concentration conditions. The modified MEA achieved a maximum CO faradaic efficiency of 95.6% at 100 mA cm-2.

Defect-poor BaSn(OH)6 enhanced charge separation for efficient photocatalytic degradation of toluene.

Crystal defect is well-known to have a significant effect on the photocatalytic performance of semiconductors. Herein, defect-rich and -poor BaSn(OH)6 (BSOH-Sn and BSOH-Ba) photocatalysts were synthesized by exchanging the addition order of Ba and Sn. Results show that the defect-poor BSOH-Ba exhibited more efficient toluene degradation under ultraviolet (UV) light, which could attribute to the great suppression of photogenerated electron-hole (e--h+) pairs recombination by tuning the defect concentration. The low defect concentration in BSOH-Ba finally promotes the charge separation efficiency, the generation of reactive oxygen species (ROS), and the photocatalytic toluene degradation reactions. This work not only provides an effective way to inhibit the recombination of photogenerated carriers and improve the photocatalytic performance, but also promotes the understanding of defective perovskite-type hydroxide for more photoreactions.

Template-Sacrificing Synthesis of Well-Defined Asymmetrically Coordinated Single-Atom Catalysts for Highly Efficient CO2 Electrocatalytic Reduction.

Although various single-atom catalysts have been designed, atomically engineering their coordination environment remains a great challenge. Herein, a one-pot template-sacrificing pyrolysis approach is developed to synthesize well-defined Ni-N4-O catalytic sites on highly porous graphitic carbon for electrocatalytic CO2 reduction to CO with high Faradaic efficiency (maximum of 97.2%) in a wide potential window (-0.56 to -1.06 V vs RHE) and with high stability. In-depth experimental and theoretical studies reveal that the axial Ni-O coordination introduces asymmetry to the catalytic center, leading to lower Gibbs free energy for the rate-limiting step, strengthened binding with *COOH, and a weaker association with *CO. The present results demonstrate the successful atomic-level coordination environment engineering of high-surface-area porous graphitic carbon-supported Ni single-atom catalysts (SACs), and the demonstrated method can be applied to synthesize an array of SACs (metal-N4-O) for various catalysis applications.

Metal-organic framework derived carbon-supported bimetallic copper-nickel alloy electrocatalysts for highly selective nitrate reduction to ammonia.

Developing electrocatalysts for efficient reduction of nitrate contaminant to value-added ammonia as energy carrier is a pivotal part for restoring the nitrogen cycle. However, the selectivity of ammonia is far from satisfaction, often suffering from accumulation of toxic nitrite byproduct. Herein, a series of CuNi alloy nanoparticles embedded in nitrogen-doped carbon matrix (CuNi/NC) with hierarchical pores were fabricated by pyrolysis of bimetallic metal-organic frameworks (MOFs). The catalysts exhibited excellent selectivity (94.4%) and faradaic efficiency (79.6%) for nitrate reduction to ammonia, greatly outperforming the performance of monometallic Cu/NC (selectivity of 60.8% and faradaic efficiency of 60.6%). Impressively, the introduction of nickel distinctly suppressed the production of toxic byproduct of nitrite. Online differential electrochemical mass spectrometry (DEMS) and in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) tests were utilized to reveal the key intermediates and the reaction pathway. Density functional theory (DFT) calculations demonstrated that the introducing of nickel into copper lattice modified both the electronic and geometric structures of the catalysts. The copper and nickel sites in the CuNi alloy catalysts operate synergistically to facilitate the hydrogenation of NO2* to HNO2* and suppress the hydrogen evolution reaction, boosting the selective formation of ammonia. This work could provide a new synthetic route for bimetallic catalysts and mechanistic understanding for nitrate to ammonia reaction.

The Crystal Plane is not the Key Factor for CO2 -to-Methane Electrosynthesis on Reconstructed Cu2 O Microparticles.

Cu2 O microparticles with controllable crystal planes and relatively high stability have been recognized as a good platform to understand the mechanism of the electrocatalytic CO2 reduction reaction (CO2 RR). Herein, we demonstrate that the in situ generated Cu2 O/Cu interface plays a key role in determining the selectivity of methane formation, rather than the initial crystal plane of the reconstructed Cu2 O microparticles. Experimental results indicate that the methane evolution is dominated on all three different crystal planes with similar Tafel slopes and long-term stabilities. Density functional theory (DFT) calculations further reveal that *CO is protonated via a similar bridge configuration at the Cu2 O/Cu interface, regardless of the initial crystal planes of Cu2 O. The Gibbs free energy changes (ΔG) of *CHO on different reconstructed Cu2 O planes are close and more negative than that of *OCCOH, indicating the methane formation is more favorable than ethylene on all Cu2 O crystal planes.

Substrate Engineering for CVD Growth of Single Crystal Graphene.

Single crystal graphene (SCG) has attracted enormous attention for its unique potential for next-generation high-performance optoelectronics. In the absence of grain boundaries, the exceptional intrinsic properties of graphene are preserved by SCG. Currently, chemical vapor deposition (CVD) has been recognized as an effective method for the large-scale synthesis of graphene films. However, polycrystalline films are usually obtained and the present grain boundaries compromise the carrier mobility, thermal conductivity, optical properties, and mechanical properties. The scalable and controllable synthesis of SCG is challenging. Recently, much attention has been attracted by the engineering of large-size single-crystal substrates for the epitaxial CVD growth of large-area and high-quality SCG films. In this article, a comprehensive and comparative review is provided on the selection and preparation of various single-crystal substrates for CVD growth of SCG under different conditions. The growth mechanisms, current challenges, and future development and perspectives are discussed.

Efficient photocatalytic toluene degradation over heterojunction of GQDs@BiOCl ultrathin nanosheets with selective benzoic acid activation.

Photocatalytic toluene degradation has attracted tremendous attention because of the growing environmental problem. However, conventional photocatalytic materials used for toluene degradation usually suffer from low carrier separation efficiency and poor stability which will degrade the catalytic performance. Herein, we report the synthesis of a novel heterostructure of GQDs@BiOCl ultrathin nanosheets where the GQDs can rapidly capture and transport photogenerated electrons for effective charge separation, promoting the generation of more reactive oxygen species (·O2- and ·OH radicals) for toluene degradation. In situ DRIFTS measurement and theoretical calculation are performed to unveil the reaction intermediates and the underlying toluene oxidation mechanism. The GQDs@BiOCl heterojunction could facilitate the adsorption and conversion of toluene and the reaction intermediates. Especially, the heterojunction greatly enhances the activation and conversion of benzoic acid and thus expedites the complete toluene degradation. This work presents a new insight on the design of high-performance photocatalysts for efficient degradation of typical air pollutants.