Improved electrochemical conversion of CO2 to multicarbon products by using molecular doping

The conversion of CO2 into desirable multicarbon products via the electrochemical reduction reaction holds promise to achieve a circular carbon economy. Here, we report a strategy in which we modify the surface of bimetallic silver-copper catalyst with aromatic heterocycles such as thiadiazole and triazole derivatives to increase the conversion of CO2 into hydrocarbon molecules. By combining operando Raman and X-ray absorption spectroscopy with electrocatalytic measurements and analysis of the reaction products, we identified that the electron withdrawing nature of functional groups orients the reaction pathway towards the production of C2+ species (ethanol and ethylene) and enhances the reaction rate on the surface of the catalyst by adjusting the electronic state of surface copper atoms. As a result, we achieve a high Faradaic efficiency for the C2+ formation of approximate to 80% and full-cell energy efficiency of 20.3% with a specific current density of 261.4 mA cm(-2) for C2+ products. Strategies to systematically tune CO2 electroreduction to multicarbon products are of high interests. Here the authors report electron withdrawing functional group alters the reaction pathway towards C2+ products by adjusting the oxidation state of surface copper.D.V., K.Q., and H.L.W. acknowledge funding from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement no. 804320). L.L., D.V., and H.L.W acknowledge the use of TEM instrumentation provided by the Nation Facility ELECMI ICTS (`Division de Microscopia Electronica', Universidad de Cadiz, DME-UCA). L.L. acknowledges funding from the Andalusian regional government (FEDER-UCA-18-106613), the European Union's Horizon 2020 research and innovation program (grant agreement 823717-ESTEEM3), and the Spanish Ministerio de Economia y Competitividad (PID2019-107578GA-I00). K.Q. and Y.Z. acknowledge financial support from the China Postdoctoral Science Foundation (2018M633127) and the Natural Science Foundation of Guangdong Province (2018A030310602). J.L. acknowledge financial support from the National Natural Science Foundation of China (21808134). We thank Soleil Synchrotron and Andrea Zitolo for allocating beamtime at beamline Samba within the proposal 20200732

Ultrahigh-current-density niobium disulfide catalysts for hydrogen evolution

Metallic transition metal dichalcogenides (TMDs)1???8 are good catalysts for the hydrogen evolution reaction (HER). The overpotential and Tafel slope values of metallic phases and edges9 of two-dimensional (2D) TMDs approach those of Pt. However, the overall current density of 2D TMD catalysts remains orders of magnitude lower (~10???100 mA cm???2) than industrial Pt and Ir electrolysers (>1,000 mA cm???2)10,11. Here, we report the synthesis of the metallic 2H phase of niobium disulfide with additional niobium (2H Nb1+xS2, where x is ~0.35)12 as a HER catalyst with current densities of >5,000 mA cm???2 at ~420 mV versus a reversible hydrogen electrode. We find the exchange current density at 0 V for 2H Nb1.35S2 to be ~0.8 mA cm???2, corresponding to a turnover frequency of ~0.2 s???1. We demonstrate an electrolyser based on a 2H Nb1+ xS2 cathode that can generate current densities of 1,000 mA cm???2. Our theoretical results reveal that 2H Nb1+ xS2 with Nb-terminated surface has free energy for hydrogen adsorption that is close to thermoneutral, facilitating HER. Therefore, 2H Nb1+ xS2 could be a viable catalyst for practical electrolysers

Optimizing the electrocatalytic CO2-to-CO conversion from 2D silver nanoplates via superstructure assembly

International audienc

2D Transition Metal Dichalcogenides for Environnemental applications

International audienc

Solubilisation et fonctionnalisation covalente de nanotubes de carbone et autres formes de carbone nanostructurées

Les nanotubes de carbone ou le graphène sont des formes allotropiques du carbone prometteuses pour un large domaine d'applications, mais des modifications de leur surface carbonée sont nécessaires pour leur manipulation et mise en forme. La fonctionnalisation covalente est un des moyens utilisés avec succès dans ce cadre, même si les modifications induites ne sont pas contrôlables. Les travaux réalisés au cours de cette thèse concernent l'utilisation de la réduction chimique des nanotubes et autres nanoformes de carbone, nanocornes, graphène ou nanodisques, pour d'une part obtenir des solutions stables et concentrées dans une gamme de solvants dépendant du type de nanoforme et d'autre part fonctionnaliser de manière covalente les différents types de surface carbonée de ces objets. Dans le cas des nanotubes, des molécules acceptrices ou donneuses d'électrons ont ainsi été greffées permettant la formation d'ensembles donneur-accepteur. D'autre part, le nombre de fonctions chimique greffées a pu être contrôlé, préservant ainsi les propriétés électroniques des nanotubes.Carbon nanotubes and graphene are promising allotropes of carbon for a large range of applications. Due to their tendency to aggregate, modifications of the carbon surface are required in order to manipulate them. Covalent functionalization is one of the ways commonly used to reach this target even if this route is not controllable. The study presented in this thesis deals with the chemical reduction of carbon nanotubes and other forms of carbon such as nanohorns, graphene, nanocones and nanodisks. Two main results have been demonstrated here. First, adding electrons to these materials renders them soluble at high concentrations in various organic solvents. Second, these reduced materials can be functionalized covalently thanks to the charges excess. Donor-acceptor dyads have thus been prepared by grafting organic dyes such as porphyrin and perylene to the nanotubes. Furthermore the extent of functional groups can be controlled preserving the electronic properties of carbon nanotubes

Molecular doping of metal catalysts for improving the electrochemical conversion of CO2 to multicarbon products

International audienc

Electrocatalysis from two-dimensional materials: an ERC project

International audienc

Exfoliated MoS2 nanosheets for water treatment

International audienc

Heterostructures of 2D materials: Synthesis and applications in energy

International audienc