| Title |
Unifying CO2-to-fuel and biomass valorization over a metal-free 2D carbon nitride-fullerene heterostructure: a solar-driven chemical circular economy |
| ID_Doc |
22641 |
| Authors |
Chauhan, DK; Verma, A; Jain, A; Saini, N; Prajapati, PK; Bera, C; Kailasam, K |
| Title |
Unifying CO2-to-fuel and biomass valorization over a metal-free 2D carbon nitride-fullerene heterostructure: a solar-driven chemical circular economy |
| Year |
2023 |
| Published |
Journal Of Materials Chemistry A, 11.0, 35 |
| Abstract |
Photocatalytic CO2 photoreduction integrated with biomass oxidation is highly attractive to produce fuels and fine chemicals. Herein, for the first time, we manifested CO2 photoreduction to CO (>95% sel.) in synergy with biomass-based alcohol oxidation via a metal-free fullerene/2D carbon-nitride (C60/TUCN) semiconductor under solar simulated light. We observed that the composite, 5-C-60/TUCN showed the highest CO2 to CO (selectivity >95%) conversion efficiency along with lignin biomass model substrate p-methoxybenzyl alcohol (p-MBA) oxidation to p-methoxybenzyaldehyde (p-MBAL) under solar simulated light with an excellent CO production rate of 8.92 mmol h(-1) g(-1) and p-MBAL production rate of 0.65 mmol h(-1) g(-1). The apparent quantum yield (AQY) of CO evolution was determined to be 3.38% at ? = 450 nm. DFT calculations confirmed that the C60 loading improved the activation and reduction of CO2 to CO while considerably lowering the formation barrier of COOH* intermediates. Besides, the accelerated separation and charge transfer kinetics of TUCN after C60 modification was confirmed from EPR, PL, and photocurrent studies. (CO2)-C-13 labeling experiments and EPR studies established the mechanistic pathway of the CO2 reduction reaction. Thus, the current study showed an excellent proof-of-concept for upscaling CO2 and biomass synergistically into solar fuels and fine chemicals, featuring a sustainable approach to boost the overall (bio)-chemical economy. |
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