Effect of Hydroxylation and Carboxylation on the Catalytic Activity of Fe2O3/Graphene for Oxidative Desulfurization and Denitration

Iron-based particles loaded on porous carbon materials have attracted extensive attention as catalysts for denitration and desulfurization reactions. However, the carbon support of a high-temperature denitration catalyst is inevitably oxidized in the presence of H2O and O2. The mechanism of denitration catalyst oxidation and its influence on the catalytic reaction remain to be further explored. Fe2O3-loaded graphene models with carbon vacancy (Gdef), hydroxyl (HyG), and carboxyl (CyG) were constructed to investigate the effects of hydroxylation and carboxylation on the catalytic activity of Fe2O3/graphene for oxidative desulfurization and denitration by using density functional theory (DFT) calculations. According to the analysis of structural properties and adsorption energy, the adsorption process of Fe2O3 on HyG and CyG was observed to have proceeded more favorably than that on Gdef. The density-of-states (DOS) results also affirmed that HyG and CyG promote the electron delocalization of Fe2O3 around the Fermi level, enhancing the chemical activity of Fe2O3. Moreover, adsorption energy analysis indicates that hydroxylation and carboxylation enhanced the adsorption of SO2 and H2O2 on Fe2O3/graphene while also maintaining preferable adsorption stability of NO. Furthermore, mechanistic research explains that adsorbed H2O2 on HyG and CyG directly oxidizes NO and SO2 into HNO2 and H2SO4 following a one-step reaction. The results provide a fundamental understanding of the oxidized catalyst on catalytic denitration and desulfurization reactions.

[1]  S. Shahhosseini,et al.  Cobalt-based sandwich-type polyoxometalate supported on amino-silane decorated magnetic graphene oxide: A recoverable catalyst for extractive-catalytic oxidative desulfurization of model oil , 2022, Journal of Environmental Chemical Engineering.

[2]  Ahmed M. Shawky,et al.  Borophene and Pristine Graphene 2D Sheets as Potential Surfaces for the Adsorption of Electron-Rich and Electron-Deficient π-Systems: A Comparative DFT Study , 2022, Nanomaterials.

[3]  Shaohua Wu,et al.  The Combination of Two-Dimensional Nanomaterials with Metal Oxide Nanoparticles for Gas Sensors: A Review , 2022, Nanomaterials.

[4]  Hameed Hussein Alwan,et al.  Oxidative desulfurization of a model fuel using MoO3 nanoparticles supported on carbon nanotubes catalyst: examine most significance variables, optimization, kinetics and thermodynamics study , 2022, South African Journal of Chemical Engineering.

[5]  Guozhao Ji,et al.  Degradation of antibiotic pollutants by persulfate activated with various carbon materials , 2022, Chemical Engineering Journal.

[6]  G. Ji,et al.  The promotion and inhibition effect of graphene oxide on the process of microbial denitrification at low temperature. , 2021, Bioresource technology.

[7]  L. Lavagna,et al.  Catalytic oxidative desulphurization of pyrolytic oils to fuels over different waste derived carbon-based catalysts , 2021, Fuel.

[8]  H. Neomagus,et al.  Spray drying absorption for desulphurization: a review of recent developments , 2021, Clean Technologies and Environmental Policy.

[9]  Haifeng Zhao,et al.  Simultaneous removal of SO2 and NOx from flue gas by low-temperature adsorption over activated carbon , 2020, Scientific Reports.

[10]  Saad H. Ammar,et al.  Catalytic-oxidative/adsorptive denitrogenation of model hydrocarbon fuels under ultrasonic field using magnetic reduced graphene oxide-based phosphomolybdic acid (PMo-Fe3O4/rGO). , 2020, Ultrasonics sonochemistry.

[11]  F. Gholami,et al.  Technologies for the nitrogen oxides reduction from flue gas: A review. , 2020, The Science of the total environment.

[12]  A. E. Martinelli,et al.  Sulfur removal from model fuel by Zn impregnated retorted shale and with assistance of design of experiments , 2018, Environmental Science and Pollution Research.

[13]  H. Ahmed,et al.  Oxidative desulfurization using graphene and its composites for fuel containing thiophene and its derivatives: An update review , 2017, Egyptian Journal of Petroleum.

[14]  S. Prabhu.  A Review on Selective Catalytic Reduction ( SCR )-A Promising Technology to mitigate NO x of Modern Automobiles , 2018 .

[15]  Tao Chen,et al.  Density functional study on the heterogeneous oxidation of NO over α-Fe 2 O 3 catalyst by H 2 O 2 : Effect of oxygen vacancy , 2017 .

[16]  Ran Zhao,et al.  Study on desulfurization and denitrification by modified activated carbon fibers with visible-light photocatalysis , 2015 .

[17]  Q. Zhong,et al.  Simultaneous desulfurization and denitrification of flue gas by catalytic ozonation over Ce–Ti catalyst , 2014 .

[18]  I. D. Mall,et al.  Catalytic Activity of Cu/SBA‐15 for Peroxidation of Pyridine Bearing Wastewater at Atmospheric Condition , 2013 .

[19]  T. Waite,et al.  Fenton-like copper redox chemistry revisited: Hydrogen peroxide and superoxide mediation of copper-catalyzed oxidant production , 2013 .

[20]  Shuangchen Ma,et al.  Experimental study on removals of SO2 and NOX using adsorption of activated carbon/microwave desorption , 2012, Journal of the Air & Waste Management Association.

[21]  Shuangchen Ma,et al.  Advances on simultaneous desulfurization and denitrification using activated carbon irradiated by microwaves , 2012, Environmental technology.

[22]  Xin Li,et al.  A Theoretical Study on the Catalytic Synergetic Effects of Pt/Graphene Nanocomposites , 2010 .

[23]  Xin Li,et al.  Density functional theory calculations and molecular dynamics simulations of the adsorption of biomolecules on graphene surfaces. , 2010, Biomaterials.

[24]  Aimee M. Morey,et al.  Green decomposition of organic dyes using octahedral molecular sieve manganese oxide catalysts. , 2009, The journal of physical chemistry. A.

[25]  S. Seal,et al.  Fenton-like reaction catalyzed by the rare earth inner transition metal cerium. , 2008, Environmental science & technology.

[26]  Yasuji Inada,et al.  Efficiency of numerical basis sets for predicting the binding energies of hydrogen bonded complexes: Evidence of small basis set superposition error compared to Gaussian basis sets , 2008, J. Comput. Chem..

[27]  Luwei Chen,et al.  Preparation of nanosized Mn3O4/SBA-15 catalyst for complete oxidation of low concentration EtOH in aqueous solution with H2O2 , 2007 .

[28]  T. Valdés-Solís,et al.  Encapsulation of nanosized catalysts in the hollow core of a mesoporous carbon capsule , 2007 .

[29]  Hongming Yuan,et al.  Synthesis and Structure of Copper Hydroxyphosphate and Its High Catalytic Activity in Hydroxylation of Phenol by H2O2 , 2001 .

[30]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.