Electrocatalytic oxidative dehydrogenation (EOD) of aldehydes enables ultra-low voltage, bipolar H2 production with co-generation of carboxylic acid. Herein, we reported a simple galvanic replacement method to prepare CuM (M = Pt, Pd, Au, and Ag) bimetallic catalysts to improve the EOD of furfural to reach industrially relevant current densities. The redox potential difference between Cu/Cu2+ and a noble metal M/My+ can incorporate the noble metal on the Cu surface and enlarge its surface area. Particularly, dispersing Pt in Cu (CuPt) achieved a record-high current density of 498 mA cm–2 for bipolar H2 production at a low cell voltage of 0.6 V and a Faradaic efficiency of >80% to H2. Future research is needed to deeply understand the synergistic effects of Cu–M toward EOD of furfural, and improve the Cu–M catalyst stability, thus offering great opportunities for future distributed manufacturing of green hydrogen and carbon chemicals with practical rates and low-carbon footprints.
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This content will become publicly available on December 21, 2023
In situ identification of surface sites in Cu–Pt bimetallic catalysts: Gas-induced metal segregation
The effect of gases on the surface composition of Cu–Pt bimetallic catalysts has been tested by in situ infrared (IR) and x-ray absorption spectroscopies. Diffusion of Pt atoms within the Cu–Pt nanoparticles was observed both in vacuum and under gaseous atmospheres. Vacuum IR spectra of CO adsorbed on CuPt x /SBA-15 catalysts (x = 0–∞) at 125 K showed no bonding on Pt regardless of Pt content, but reversible Pt segregation to the surface was seen with the high-Pt-content (x ≥ 0.2) samples upon heating to 225 K. In situ IR spectra in CO atmospheres also highlighted the reversible segregation of Pt to the surface and its diffusion back into the bulk when cycling the temperature from 295 to 495 K and back, most evidently for diluted single-atom alloy catalysts (x ≤ 0.01). Similar behavior was possibly observed under H 2 using small amounts of CO as a probe molecule. In situ x-ray absorption near-edge structure data obtained for CuPt 0.2 /SBA-15 under both CO and He pointed to the metallic nature of the Pt atoms irrespective of gas or temperature, but analysis of the extended x-ray absorption fine structure identified a change in coordination environment around the Pt atoms, from a (Pt–Cu):(Pt–Pt) coordination number ratio of ∼6:6 at or below 445 K to 8:4 at 495 K. The main conclusion is that Cu–Pt bimetallic catalysts are dynamic, with the composition of their surfaces being dependent on temperature in gaseous environments.
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- NSF-PAR ID:
- 10426162
- Date Published:
- Journal Name:
- The Journal of Chemical Physics
- Volume:
- 157
- Issue:
- 23
- ISSN:
- 0021-9606
- Page Range / eLocation ID:
- 234706
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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