This study provides a significant enhancement in CO2 photoconversion efficiency by the functionalization of a reduced graphene oxide/cadmium sulfide composite (rGO/CdS) with amine. The amine-functionalized graphene/CdS composite (AG/CdS) was obtained in two steps. First, graphene oxide (GO) was selectively deposited via electrostatic interaction with CdS nanoparticles modified with 3-aminopropyltriethoxysilane. Subsequently, ethylenediamine (NH2C2H4NH2) was grafted by an N,N′-dicyclohexylcarbodiimide coupling reaction between the amine group of ethylenediamine and the carboxylic group of GO. As a result, a few layers of amine-functionalized graphene wrapped CdS uniformly, forming a large interfacial area. Under visible light, the photocurrent through the AG/CdS significantly increased because of enhanced charge separation in CdS. The CO2 adsorption capacity on AG/CdS was 4 times greater than that on rGO/CdS at 1 bar. These effects resulted in a methane formation rate of 2.84 μmol/(g h) under visible light and CO2 at 1 bar, corresponding to 3.5 times that observed for rGO/CdS. Interestingly, a high methane formation rate (1.62 μmol/(g h)) was observed for AG/CdS under CO2 at low pressure (0.1 bar), corresponding to a value 20 times greater than that observed for the rGO/CdS. Thus, the enhanced performance for photocatalytic reduction of CO2 on the AG/CdS is due to the improved CO2 adsorption related to the amine groups on amine-functionalized graphene, which sustains the strong absorption of visible light and superior charge-transfer properties in comparison with those of graphene.

Incorporating mesoporosity into zeolite catalysts has been regarded as an innovative technology that improves diffusivity and catalytic lifetime. Here, we propose a facile synthesis of the hierarchically structured ZSM-5 with accompanying intracrystalline mesopores, which was achieved by controlling the growth rate of the zeolite nanocrystals without using extra additives. As the crystallization temperature is strongly related to the formation of primary nanocrystals and their further growth, which fills gaps between those nanocrystals, the hierarchically structured ZSM-5 zeolite was synthesized at low crystallization temperatures (<140 °C). 27 Al MAS NMR and UV-vis-DRS analyses revealed that the hierarchically structured ZSM-5 prepared in the present study contained Al located in the straight channel at a higher proportion than the conventional microporous ZSM-5. The substitution of Al was calculated to be more difficult at the channel intersection than at other T-sites, supporting the experimental results. The hierarchically structured ZSM-5 exhibited excellent stability as well as selectivity for a methanol-to-olefin reaction. Reaction free energies calculated along the hydrocarbon pool mechanism pathway revealed that the Al located in the straight channel drives the reaction through the alkene-based cycle, which is responsible for the high olefin selectivity of the hierarchically structured ZSM-5.

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