@article {50211,
	title = {Unraveling the mechanism of higher alcohol production on the ordered PdCu3 nanointermetallic surface during CO2 electroreduction},
	journal = {ACS Catalysis},
	volume = {16},
	year = {2026},
	month = {JUL },
	pages = {12486-12504},
	type = {Article},
	abstract = {<p>
	For advancing electrochemical CO2 reduction, it is crucial to design efficient catalysts with high activity and selectivity for a particular product. Engineering structure at the atomic level by controlled synthesis strategies can effectively tune the product selectivity by optimizing the binding energy of the key intermediates involved in the reaction. Here, we demonstrate a morphology-controlled (spherical and cubic) synthesis route for PdCu3-ordered intermetallic nanoparticles without using any external strong reducing agent. Structurally ordered cubic PdCu3 with predominantly (100) facets exhibits higher selectivity for ethanol (Faradaic efficiency (FE): 44.2\%) and n-propanol (FE: 17.0\%; formation rate: 39.99 mu mol h(-1) cm(-2) mg(-1)) from CO2 compared to spherical PdCu3 with (111) facets (ethanol FE: 32.7\%; n-propanol FE: 9.46\%). Incorporating the electrode-electrolyte interactions, the ab initio calculations highlight the key C-C coupling step enabling the formation of C2+ products. The active Pd sites, depending on their presence and absence on the surface of PdCu3 (100) facets, significantly influence the C-C coupling barrier by controlling CO* and OCCOH* binding. In contrast, this barrier remains unaffected on (111) facets due to the Pd arrangement. This further establishes the important role of alloying Pd with Cu in rationally tailored surfaces for higher alcohol synthesis.</p>
},
	keywords = {CO2 electroreduction, higher alcohol selectivity, In situ spectroscopy, intermetallic catalyst, role of morphology},
	issn = {2155-5435},
	doi = {10.1021/acscatal.6c02384},
	author = {Bagchi, Debabrata and Iyer, Jayendran and Khan, Tuhin S. and Chawla, Geetansh and Dutta, Nilutpal and Giri, Bishnubasu and Singh, Ashutosh Kumar and Saha, Saurav and Kaur, Komalpreet and Vinod, C. P. and Gautam, Ujjal K. and Haider, M. Ali and Peter, Sebastian C.}
}
