Catalysts (Jan 2020)
Plasma Generating—Chemical Looping Catalyst Synthesis by Microwave Plasma Shock for Nitrogen Fixation from Air and Hydrogen Production from Water for Agriculture and Energy Technologies in Global Warming Prevention
Abstract
Simultaneous generation of plasma by microwave irradiation of perovskite or the spinel type of silica supported porous catalyst oxides and their reduction by nitrogen in the presence of oxygen is demonstrated. As a result of plasma generation in air, NOx generation is accompanied by the development of highly heterogeneous regions in terms of chemical and morphological variations within the catalyst. Regions of almost completely reduced catalyst are dispersed within the catalyst oxide, across micron-scale domains. The quantification of the catalyst heterogeneity and evaluation of catalyst structure are studied using Scanning Electron Microscopy, Energy Dispersive X-ray Spectroscopy and XRD. Plasma generating supported spinel catalysts are synthesized using the technique developed by the author (Catalysts; 2016; 6; 80) and BaTiO3 is used to exemplify perovskites. Silica supported catalyst systems are represented as M/Si = X (single catalysts) or as M(1)/M(2)/Si = X/Y/Z (binary catalysts) where M; M(1) M(2) = Cr; Mn; Fe; Co; Cu and X, Y, Z are the molar ratio of the catalysts and SiO2 support. Composite porous catalysts are synthesized using a mixture of Co and BaTiO3. In all the catalysts, structural heterogeneity manifests itself through defects, phase separation and increased porosity resulting in the creation of the high activity sites. The chemical heterogeneity results in reduced and oxidized domains and in very large changes in catalyst/support ratio. High electrical potential activity within BaTiO3 particles is observed through the formation of electrical treeing. Plasma generation starts as soon as the supported catalyst is synthesized. Two conditions for plasma generation are observed: Metal/Silica molar ratio should be > 1/2 and the resulting oxide should be spinel type; represented as MaOb (a = 3; b = 4 for single catalyst). Composite catalysts are represented as {M/Si = X}/BaTiO3 and obtained from the catalyst/silica precursor fluid with BaTiO3 particles which undergo fragmentation during microwave irradiation. Further irradiation causes plasma generation, NOx formation and lattice oxygen depletion. Partially reduced spinels are represented as MaOb−c. These reactions occur through a chemical looping process in micron-scale domains on the porous catalyst surface. Therefore; it is possible to scale-up this process to obtain NOx from MaOb for nitric acid production and H2 generation from MaOb−c by catalyst re-oxidized by water. Re-oxidation by CO2 delivers CO as fuel. These findings explain the mechanism of conversion of combustion gases (CO2 + N2) to CO and NOx via a chemical looping process. Mechanism of catalyst generation is proposed and the resulting structural inhomogeneity is characterized. Plasma generating catalysts also represent a new form of Radar Absorbing Material (RAM) for stealth and protection from radiation in which electromagnetic energy is dissipated by plasma generation and catalytic reactions. These catalytic RAMs can be expected to be more efficient in frequency independent microwave absorption.
Keywords
