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.

Catania Astrophysical Observatory Via Santa Sofia 78 95123 Catania Italy

Center for High Resolution Electron Microscopy School of Physical Science and Technology ShanghaiTech University 393 Middle Huaxia Road Pudong Shanghai 201210 China

Department of Chemistry Ben Gurion University of the Negev Beer Sheva 84105 Israel

Department of Mechanical and Aerospace Engineering Princeton University Princeton NJ 08544 USA

ESISNA group Instituto de Ciencia de Materiales de Madrid c Sor Juana Inés de la Cruz 3 28049 Madrid Spain

Institute for Mechanical Systems ETH Zurich Leonhardstrasse 21 8092 Zurich Switzerland

Institute of Chemical Physics Université Paris Saclay 91400 Orsay France

Institute of Physics of the CAS Cukrovarnicka 10 Prague Czech Republic

Instituto de Ciencia y Tecnología de Polímeros ICTP CSIC c Juan de la Cierva 3 28006 Madrid Spain

Instituto de Física Fundamental c Serrano 123 28006 Madrid Spain

Instituto de Nanociencia y Materiales de Aragon University of Zaragoza 50009 Zaragoza Spain

Instituto de Química Física Rocasolano c Serrano 119 28006 Madrid Spain

Laboratorio de Microscopias Avanzadas University of Zaragoza 50009 Zaragoza Spain

Photoactivated Processes Unit IMDEA Energía Av Ramón de la Sagra 3 28935 Móstoles Spain

School of Engineering Brown University Providence RI 02912 USA

Synchrotron Soleil L'Orme des Merisiers Saint Aubin BP 48 91192 Gif sur Yvette France

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