Polymer‐Based Synthetic Routes to Carbon‐Based Metal‐Free Catalysts

Abstract

Carbons are increasingly important as possible alternatives to expensive metal catalysts owing to the wide range of chemical properties they can exhibit and the growing set of synthetic routes available to produce them. This Progress Report discusses the process of making catalytic carbons from polymeric precursors, focusing on mechanisms of carbonization and how the polymer structures and synthetic procedures affect the resulting carbons. In considering what is necessary to move laboratory catalytic carbons to industrial and commercial applications, the cost and complexity to produce them are a considerable challenge to overcome. Industrially produced carbons are typically made from biopolymers such as lignin while many of the catalytic carbons studied in literature are from synthetic polymers. Thus, studying polymer-derived carbons can provide insights into the carbonization process and the properties of catalytic carbons, which can subsequently be translated to improve biopolymerderived carbons in an economical way. Aspects of polymer carbonization discussed include carbonization mechanisms, effects of crosslinkers, polymer microstructure, heteroatom control, and effects nanostructuring.

The Constructions and Pyrolysis of 3D Kerogen Macromolecular Models: Experiments and Simulations

“…[23,24] The ReaxFF method has been successfully applied to reaction kinetics simulation researches, including applications of the organic micromolecular system, the polymer system, and the high energy material system. [23][24][25][26][27][28][29][30] The result of ReaxFF method has been verified to be consistent with that of the quantum mechanics (QM) method and the experiment. [27] In order to enable chemical reactions occurring in computational time which is much smaller than the experimental time scale, ReaxFF simulations take temperatures higher than that of experiments.…”

“…The connectivity between atoms in the molecule of the reactive force field (ReaxFF) is determined by the interatomic bond order at that time, which means the chemical bond can be broken and formed freely, so that the chemical reaction process can be obtained . The ReaxFF method has been successfully applied to reaction kinetics simulation researches, including applications of the organic micromolecular system, the polymer system, and the high energy material system . The result of ReaxFF method has been verified to be consistent with that of the quantum mechanics (QM) method and the experiment .…”

Tailoring Polymer Colloids Derived Porous Carbon Spheres Based on Specific Chemical Reactions

“…[4][5][6] Among many existing PCSs, synthetic colloidal polymer derived PCSs occupy a pivotal role because of their well-defined pore structures, high purity, and good reproducibility. [7][8][9] The immense body of research in polymer chemistry about polymer structures, properties, and reactions provides good foundation for the understanding of synthetic polymer derived carbons. [7] Till present, colloidal polymer derived PCSs are mainly synthesized via classical polymerization reactions.…”

Metal‐Modulated Nitrogen‐Doped Carbon Electrocatalyst for Efficient Carbon Dioxide Reduction

“…NH 3 ), direct pyrolysis conversion of N‐containing precursors ( e. g . MOF or polymer), or in‐situ growth of N−C layers from N‐containing gaseous species could be used. Each approach leads to different N chemical states in the synthetic materials.…”

“…It is well-known that modulation of heteroatom dopants in carbon-based catalysts relies on synthesis approaches and precursors used. For synthesis of common N-doped carbon catalysts, three approaches by etching reaction of carbon with external N sources (e. g. NH 3 ), [26,27] direct pyrolysis conversion of N-containing precursors (e. g. MOF or polymer), [28][29][30] or in-situ growth of NÀ C layers from N-containing gaseous species [31,32] could be used. Each approach leads to different N chemical states in the synthetic materials.…”