Theoretical and experimental evidence for rGO-4-PP Nc as a metal-free Fenton-like catalyst by tuning the electron distribution

Abstract

The application of the classical Fenton reaction has long been limited by several problems, such as metallic sludge and narrow pH range, which derived from the metal components in the catalyst. Developing a metal-free Fenton catalyst may efficiently address these problems. Here, we firstly perform a density functional theory (DFT) study to explore the possibility of developing the 4-phenoxyphenol moleculedoped reduced graphene oxide nanocomposite (rGO-4-PP Nc) as a metal-free Fenton-like catalyst by tuning the electron distribution. The theoretical calculation results reveal that rGO-4-PP Nc can act as an efficient Fenton-like catalyst for H 2 O 2 activation and pollutant degradation through formation of electron-rich O and electron-deficient C centers on the C-O-C bridge. The actual rGO-4-PP Nc is also prepared via a surface complexation and copolymerization process. The experimental evidence, such as that gained from XRD, FIIR and EPR analysis, confirm the theoretical models and the dual-reactioncenter Fenton-like mechanism. This work provides a basis for theoretical calculation to guide the actual synthesis and prediction of catalytic activity of the Fenton-like catalysts, and also offers a creative perspective to develop new generation metal-free Fenton catalysts by tuning the electron distribution using organic polymers.

Composites of Platinum-Iridium Alloy Nanoparticles and Graphene Oxide for the Dimethyl Amine Borane (DMAB) dehydrogenation at ambient conditions: An Experimental and Density Functional Theory Study

“…Besides, the negative and positive regions electrostatic potential (ESP) distribution (shown in Fig. 12) on the van der Waals surface were represented by the red and blue colors, respectively 61,62 . The ESP distribution’s analysis of PtIr@GO cluster result shows that blue color regions (positiveregion) are localized on Pt and Ir atoms (mostly Ir atoms).…”

Synergistic Features of Superoxide Molecule Anchoring and Charge Transfer on Two-Dimensional Ti3C2Tx MXene for Efficient Peroxymonosulfate Activation

“…As crucial parameters for studying electronic structure, frontier orbitals [highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO)] are closely related to the chemical activity of the electronic system . It is generally recognized that interaction between two reactants can be affected by compatibility between the HOMO of the electron donor and the LUMO of the charge acceptor and can thus control electron transfer efficiency. , Moreover, smaller HOMO–LOMO gaps in the catalyst can represent lower kinetic stability and higher catalytic activity as it is energetically favorable for the LUMO to obtain electrons or for HOMO to lose electrons. , …”

“…17,18 Moreover, smaller HOMO−LOMO gaps in the catalyst can represent lower kinetic stability and higher catalytic activity as it is energetically favorable for the LUMO to obtain electrons or for HOMO to lose electrons. 19,20 As a new family of 2D materials, MXenes are easy to realize the transformation from the bulk structure to monolayer geometry via facile exfoliation because of the anisotropic property. 21,22 Moreover, the transition metals in MXenes possess multiple valence states, which can serve as an abundance of electron output sites, rendering MXenes as an ideal platform for studying the elusive Fenton-like catalytic process.…”

Use of silica-based homogeneously distributed gold nickel nanohybrid as a stable nanocatalyst for the hydrogen production from the dimethylamine borane

“…Moreover, the negative and positive distribution of electrostatic potential (ESP) regions (Fig. 12) on the surface of the van der Waals was shown between the colors red and blue 47,48 . Analysis of the ESP distribution of AuNi@SiO 2 cluster data demonstrations that positive regions are located smoothly on Au and Ni atoms (mainly Ni atom).…”