@article {49844,
	title = {Utilizing nature{\textquoteright}s endowment: artificial leaf concept for methane activation to C-C coupled ethanol or ethylene},
	journal = {Sustainable Energy \& Fuels},
	volume = {9},
	year = {2025},
	month = {DEC},
	pages = {6798-6810},
	type = {Article},
	abstract = {<p>
	Methane activation (MA) to platform chemicals under ambient conditions still remains an open challenge to be fully realised. The present work shows the fabrication of CeVO4 quantum dots (CV-QDs) by a bottom-up approach; they are assembled from Ce3+ and metavanadate ions, and structurally and electronically integrated into the micro-/meso-pores of TiO2 (CV-QD-TiO2 (CVT)), demonstrating the conversion of MA to ethanol/ethylene by visible light-driven photocatalysis. CV-QDs in confined pores modify the quantum confinement effects and are characterized by physicochemical methods. The current synthetic strategy is potentially scalable and results in sub-quadrillion heterojunctions in a 1 mg CVT photoanode spread over 1 cm2. MA with CVT under one-sun conditions demonstrates similar to 100\% selectivity to ethanol, yielding 4.36 mu mol h-1 cm-2, with a solar-to-fuel efficiency (STFE) of 0.56. Further, by employing a co-catalyst, significant STFE (5.08) and yield (39.5 mu mol h-1 cm-2) are achieved selectively towards ethylene. A deliberate addition of methanol increases the rate of ethanol production by 17.2 times, indicating that the methyl-methoxy interaction is the origin of C-C coupling. Weight is normalized to a gram of CV-QDs in a large area CVT photoanode to yield 109 mmol h-1 gCV-QD-1 of ethanol and 988 mmol h-1 gCV-QD-1 of ethylene. Enhanced activity and selectivity towards the C2-product is attributed to band-edge modulation and trillions of heterojunctions, which in turn facilitate charge separation and charge transfer for effective charge utilisation at redox sites.</p>
},
	issn = {2398-4902},
	doi = {10.1039/d5se01178g},
	author = {Kanungo, Subhashree S. and Mishra, Abhaya Kumar and Avani, Mangaladasan J. and Bajpai, Himanshu and Salgaonkar, Kranti N. and Javaregowda, Bharathkumar H. and Gopinath, Chinnakonda S.}
}
