Cobalt Spinel Nanocubes on N-Doped Graphene: A Synergistic Hybrid Electrocatalyst for the Highly Selective Reduction of Carbon Dioxide to Formic Acid

Carbon dioxide reduction into useful chemical products is a key technology to address urgent climate and energy challenges. In this study, a nanohybrid made by Co₃O₄ and graphene is proposed as an efficient electrocatalyst for the selective reduction of CO₂ to formate at low overpotential. A comparison between samples with different metal oxide to carbon ratios and with or without doping of the graphene moiety indicates that the most active catalyst is formed by highly dispersed and crystalline nanocubes exposing {001} oriented surfaces, whereas the nitrogen doping is critical to obtain a controlled morphology and to facilitate a topotactic transformation during electrocatalytic conditions to CoO, which results in the true active phase. The nanohybrid made up by intermediate loading of Co₃O₄ supported on nitrogen-doped graphene is the most active catalyst, being able to produce 3.14 mmol of formate in 8 h at −0.95 V vs SCE with a Faradaic efficiency of 83%

Visualization of Light Elements using 4D STEM: The Layered‐to‐Rock Salt Phase Transition in LiNiO2 Cathode Material

The layered oxide LiNiO2 (LNO) has been extensively investigated as a cathode active material for lithium‐ion batteries. Despite LNO\u27s high gravimetric capacity, instability issues hinder its commercialization. It suffers from capacity loss during electrochemical cycling and is difficult to synthesize without defects. This is related to poor structural stability, leading to decomposition into the parent rock‐salt‐type oxide. In order to understand such phase transformations and to develop measures to inhibit them, the development of techniques able to image all atoms is crucial. In this study, the use of a fast, pixelated detector and 4D imaging in scanning transmission electron microscopy are explored to tackle this challenge. Selecting specific angular regions in the diffraction patterns and calculating virtual annular bright‐field images significantly enhances the contrast of the lithium atoms, such that all atoms are visible even in realistic samples. The developed technique is applied to image the layered‐to‐rock salt phase transition region. The data show that in this region, nickel atoms are in tetrahedral positions and the oxygen atoms are asymmetrically distributed. Taken together, the results shed light on the phase transformation mechanism at the atomic scale and can guide future research toward stabilizing LNO

Operando Laboratory-Based Multi-Edge X-Ray Absorption Near-Edge Spectroscopy of Solid Catalysts

Laboratory-based X-ray absorption spectroscopy (XAS) and especially X-ray absorption near-edge structure (XANES) offers new opportunities in catalyst characterization and presents not only an alternative, but also a complementary approach to precious beamtime at synchrotron facilities. We successfully designed a laboratory-based setup for performing operando , quasi-simultaneous XANES analysis at multiple K edges, more specifically, operando XANES of mono-, bi-, and trimetallic CO 2 hydrogenation catalysts containing Ni, Fe, and Cu. Detailed operando XANES studies of the multi-element solid catalysts revealed metal-dependent differences in the reducibility and re-oxidation behavior and their influence on the catalytic performance in CO 2 hydrogenation. The applicability of operando laboratory-based XANES at multiple K edges paves the way for advanced multi-element catalyst characterization complementing detailed studies at synchrotron facilities.Peer reviewe

Operando Laboratory-based Multi-edge X-ray Absorption Near-Edge Spectroscopy of Solid Catalysts

Laboratory-based X-ray absorption spectroscopy (XAS) and especially X-ray absorption near-edge structure (XANES) offers new opportunities in catalyst characterization and presents not only an alternative, but also a complementary approach to precious beamtime at synchrotron facilities. We successfully designed a laboratory-based setup for performing operando , quasi-simultaneous XANES analysis at multiple K edges, more specifically, operando XANES of mono-, bi-, and trimetallic CO 2 hydrogenation catalysts containing Ni, Fe, and Cu. Detailed operando XANES studies of the multi-element solid catalysts revealed metal-dependent differences in the reducibility and re-oxidation behavior and their influence on the catalytic performance in CO 2 hydrogenation. The applicability of operando laboratory-based XANES at multiple K edges paves the way for advanced multi-element catalyst characterization complementing detailed studies at synchrotron facilities

High mobility solution processed MoS2 thin film transistors

A simple wet-chemical synthesis of layered MoS2 thin films on sapphire is reported. The gap in understanding solution processed MoS2 deposition needs to be closed to exploit all its excellent properties for low-cost applications. In this work, as deposited Mo-precursor thin films were prepared based on the solubility and coating properties of Molybdenum(V) chloride in 1-Methoxy-2-propanol. Subsequent annealing of the deposited amorphous Mo-precursor films in the presence of sulfur resulted in the formation of highly crystalline layered MoS2 films on sapphire. Improved crystallinity of the deposited films was achieved by increasing the process temperature and performing the post-annealing treatment. Post-annealing at temperatures above 900??C increased the uniformity of multilayer films, together with the increase of MoS2 grain size. For charge transport analysis, top-gate top-contact thin film transistors (TFTs) based on these solution processed MoS2 films were fabricated. Ionic liquid gating of the TFT devices exhibited n-type semiconducting behaviour with field-effect mobility as high as 12.07?cm2/Vs and Ion/off ratio???106. X-ray photoelectron spectroscopy measurements revealed that the films annealed between 900??C and 980??C had an average chemical composition of S/Mo???1.84. This facile liquid phase synthesis method with centimeter-scale uniformity and controllable film thickness up to 1.2???0.65?nm is suitable for low-cost preparation of other transition metal dichalcogenides thin films in next-generation electronics