Metal-catalyst-free gas-phase synthesis of long-chain hydrocarbons

Abstract

8 pags, 4 figs. -- The online version contains supplementary material available at https://doi.org/10.1038/s41467-021-26184-0 ; Development of sustainable processes for hydrocarbons synthesis is a fundamental challenge in chemistry since these are of unquestionable importance for the production of many essential synthetic chemicals, materials and carbon-based fuels. Current industrial processes rely on non-abundant metal catalysts, temperatures of hundreds of Celsius and pressures of tens of bars. We propose an alternative gas phase process under mild reaction conditions using only atomic carbon, molecular hydrogen and an inert carrier gas. We demonstrate that the presence of CH2 and H radicals leads to efficient C-C chain growth, producing micron-length fibres of unbranched alkanes with an average length distribution between C23-C33. Ab-initio calculations uncover a thermodynamically favourable methylene coupling process on the surface of carbonaceous nanoparticles, which is kinematically facilitated by a trap-and-release mechanism of the reactants and nanoparticles that is confirmed by a steady incompressible flow simulation. This work could lead to future alternative sustainable synthetic routes to critical alkane-based chemicals or fuels. ; We thank Jose Criado for the artwork schematics of the system, in figures 4 and S1; Funding: We thank the European Research Council for funding support under Synergy grant ERC-2013-SyG, G.A. 610256 (NANOCOSMOS). Also, we acknowledge partial support from the Spanish MINECO through grants PID2020-113142RB-C21, PID2019106315RB-I00, and PID2019-106315RB-I00, EU ERC CoG HyMAP 648319, and from the regional government through project S2018-NMT-4367 (FotoArt-CM). AM acknowledges to the Spanish Ministry of Science (RYC2018-024561-I), to the Regional Government of Aragon (DGA E13_20R), to the National Natural Science Foundation of China (NFSC-21850410448, NSFC-21835002), and to the The Centre for Highresolution Electron Microscopy (ChEM), supported by SPST of ShanghaiTech University under contract No. EM02161943. S.K. and G.H. acknowledge funding from the Turbulent Superstructures Program of the German National Science Foundation (DFG) ; Peer reviewed