7 Computational and Experimental Analysis of Carbon Functional Nanomaterials
271
that showcase the development of DFT methodology is a direct non-oxidative
conversion of methane to ethylene, aromatics, and H 2 [23]. Obtaining accurate
information on the energetics for these processes is challenging. Advanced quantum
chemical methods with faster computers are enabling the prediction of accurate
energetics of chemical transformations of the larger molecules involved in the
processes [24].
The chemical interactions and transformations at the gas-solid, liquid-solid, and
gas-liquid interfaces are facilitated by the solid or liquid surface form the basis of
the advanced functional catalysis that drives the production of many value-added
chemicals [25, 26]. Recently, one approach to circumventing ongoing challenges
is through the use of metal-free catalysts as substitutes. Although organocatalysts
have been effective in this role [27], carbon-based catalysts derived from graphite,
graphene (Gr), or graphene oxides (GO) and other similar materials may serve
as useful alternatives [28]. It has been reported that graphene-based catalysts can
also work in oxidation of aryl and alkyl alcohols [29, 30], hydrochlorination [31],
nitrobenzene reduction [32], and so on. In addition, other applications of graphene
materials in catalysis may contain hydrogenation (HYD), hydrodesulfurization
(HDS), hydrodenitrogenation (HDN), hydrocracking (HCR), hydrodeoxygenation
(HDO), and hydrodechlorination (HDCl). Beyond the exploration of its novel
fundamental reactivity, the use of GO as a catalyst is attractive from a practical
perspective, owing to the abundance of natural carbon sources, the catalyst’s low
density, extensive chemical functionalization, hydrophilicity, low cost, and ease for
preparation [33]. For deeply understanding the reaction processes, it is strongly
suggested to combine DFT computational results with experimental observation.
On the other hand, the graphene catalysts co-doped with two or three heteroatoms
were also extended [34]. For instance, Zhao et al. reported a universal strategy
to synthesize an N-P-O co-doped free-standing three-dimensional (3D) graphene
through a one-pot red phosphorus-assisted “cutting-thin” technique [35]. The DFT
calculations verified that the enhancement of charge delocalization should be
beneficial for the electrochemical applications [36, 37]. We will introduce the
DFT computations in this section to rationalize experimental results in graphenebased catalysis, due to their extensive applications when combined with the related
characterization techniques [38, 39].
In this chapter, we comprehensively summarized the theoretical chemistry for
graphene-based nanomaterials by computation methods covering active surface
sites and surface defect structure analysis, binding ability determination, and
reaction mechanism investigation. We reviewed the advantages/disadvantages and
challenges and further provided key information to catalysis community on how to
adopt suitable computation methods for their research. In addition, the electronic
and sensing properties of fluorescent carbon nanomaterials are reviewed from a
theoretical perspective.
271
that showcase the development of DFT methodology is a direct non-oxidative
conversion of methane to ethylene, aromatics, and H 2 [23]. Obtaining accurate
information on the energetics for these processes is challenging. Advanced quantum
chemical methods with faster computers are enabling the prediction of accurate
energetics of chemical transformations of the larger molecules involved in the
processes [24].
The chemical interactions and transformations at the gas-solid, liquid-solid, and
gas-liquid interfaces are facilitated by the solid or liquid surface form the basis of
the advanced functional catalysis that drives the production of many value-added
chemicals [25, 26]. Recently, one approach to circumventing ongoing challenges
is through the use of metal-free catalysts as substitutes. Although organocatalysts
have been effective in this role [27], carbon-based catalysts derived from graphite,
graphene (Gr), or graphene oxides (GO) and other similar materials may serve
as useful alternatives [28]. It has been reported that graphene-based catalysts can
also work in oxidation of aryl and alkyl alcohols [29, 30], hydrochlorination [31],
nitrobenzene reduction [32], and so on. In addition, other applications of graphene
materials in catalysis may contain hydrogenation (HYD), hydrodesulfurization
(HDS), hydrodenitrogenation (HDN), hydrocracking (HCR), hydrodeoxygenation
(HDO), and hydrodechlorination (HDCl). Beyond the exploration of its novel
fundamental reactivity, the use of GO as a catalyst is attractive from a practical
perspective, owing to the abundance of natural carbon sources, the catalyst’s low
density, extensive chemical functionalization, hydrophilicity, low cost, and ease for
preparation [33]. For deeply understanding the reaction processes, it is strongly
suggested to combine DFT computational results with experimental observation.
On the other hand, the graphene catalysts co-doped with two or three heteroatoms
were also extended [34]. For instance, Zhao et al. reported a universal strategy
to synthesize an N-P-O co-doped free-standing three-dimensional (3D) graphene
through a one-pot red phosphorus-assisted “cutting-thin” technique [35]. The DFT
calculations verified that the enhancement of charge delocalization should be
beneficial for the electrochemical applications [36, 37]. We will introduce the
DFT computations in this section to rationalize experimental results in graphenebased catalysis, due to their extensive applications when combined with the related
characterization techniques [38, 39].
In this chapter, we comprehensively summarized the theoretical chemistry for
graphene-based nanomaterials by computation methods covering active surface
sites and surface defect structure analysis, binding ability determination, and
reaction mechanism investigation. We reviewed the advantages/disadvantages and
challenges and further provided key information to catalysis community on how to
adopt suitable computation methods for their research. In addition, the electronic
and sensing properties of fluorescent carbon nanomaterials are reviewed from a
theoretical perspective.