The electrochemical reduction of CO2 (CO2RR) to ethanol represents a key strategy for sustainable fuel production; however, achieving high selectivity toward ethanol under industrially relevant current densities remains a formidable challenge. Here, we report a pulse-electrodeposited CuPd alloy catalyst with atomic-level Pd incorporation into a face-centered cubic Cu lattice, which dramatically enhances ethanol formation while suppressing ethylene production. At 400 mA cm−2, the optimized Cu96Pd4 catalyst delivers a Faradaic efficiency of 57 % for ethanol, with ethylene suppressed below 3 %, corresponding to a ∼ 43-fold increase in ethanol-to-ethylene selectivity compared to pure Cu. Structural and compositional analyses confirm uniform Pd distribution without phase segregation. Operando infrared spectroscopy reveals a Pd-induced shift in *CO adsorption from linear to bridge-bound configurations, which correlates with enhanced CC coupling and ethanol selectivity. Complementary density functional theory (DFT) calculations indicate that Pd selectively destabilizes C1-site hydrogenation of *CH2CHO while favoring C2-site protonation, thereby steering the pathway toward ethanol. This work establishes a direct correlation between atomic-scale alloying, intermediate adsorption geometry, and product distribution, offering a rational strategy for engineering CO2RR catalysts with enhanced selectivity under practical operating conditions.
Ethanol and ethylene production pathway on Cu and CuPd. [Display omitted]
•Atomic-level Pd incorporation in Cu enables selective CO₂-to-ethanol conversion.•Ethanol Faradaic efficiency reaches 57 % with ethylene suppressed below 3 %.•Operando SEIRAS reveals bridge-bound CO correlates with ethanol selectivity.•DFT shows Pd promotes C2-site protonation and inhibits C1 hydrogenation.•Catalyst shows stable ethanol production at 300 mA cm−2 over 12 h electrolysis.
- Selective electrochemical reduction of CO₂ to ethanol via atomic-level Pd-incorporated cu alloy catalysts under industrially relevant conditions
- Hsin Huang (Author) - National Tsing Hua UniversityTsung-Han Tsai (Author) - National Taiwan Normal UniversityZi-Yin Huang (Author) - National Tsing Hua UniversityMing-Kang Tsai (Author) - National Taiwan Normal UniversityTsu-Chin Chou (Corresponding Author) - National Tsing Hua University
- Elsevier B.V
- 12
- NSTC (National Science and Technology Council) , Taiwan: 113-2221-E-007-043, 112-2636-E-007-007 Advanced Materials Characterization Lab, Institute osf Atomic & Molecular Sciences (IAMS) , Academia Sinica
This research was funded by NSTC (National Science and Technology Council) , Taiwan (113-2221-E-007-043- and 112-2636-E-007-007-) . Technical support from the Advanced Materials Characterization Lab, Institute osf Atomic & Molecular Sciences (IAMS) , Academia Sinica, is gratefully acknowledged.
- Journal article
- 01/11/2025
- Chemical engineering journal (Lausanne, Switzerland : 1996), Vol.523, p.168675
- English