Palladium Single-Atom (In)Stability Under Aqueous Reductive Conditions

Rigby, Kali; Huang, Dahong; Leshchev, Denis S.; Lim, Hyun J.; Choi, Hyeyeon; Meese, Aidan F.; Weon, Seunghyun; Stavitski, Eli; Kim, Jae-Hong

doi:10.1021/acs.est.3c03346

Palladium Single-Atom (In)Stability Under Aqueous Reductive Conditions

Journal Article · Thu Aug 31 00:00:00 EDT 2023 · Environmental Science and Technology

DOI:https://doi.org/10.1021/acs.est.3c03346· OSTI ID:2205641

^[1]; ^[2]; ^[3]; Lim, Hyun J. ^[2]; ^[4]; Meese, Aidan F. ^[2]; ^[4]; Stavitski, Eli ^[3]; ^[1]

Yale Univ., New Haven, CT (United States); National Science Foundation (NSF) (United States). NSF Nanosystems Engineering Research Center for Nanotechnology Enabled Water Treatment (NEWT)
Yale Univ., New Haven, CT (United States)
Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Korea Univ., Seoul, (Korea, Republic of)

Here, we investigate the stability and performance of single-atom Pd on TiO₂ for the selective dechlorination of 4-chlorophenol. A challenge inherent to single atoms is their high surface free energy, which results in a tendency for the surface migration and aggregation of metal atoms. This work evaluates various factors affecting the stability of Pd single-atoms, including atomic dispersion, coordination environment, and substrate properties, under reductive aqueous conditions. The transition from single atoms to clusters vastly enhanced dechlorination kinetics without diminishing carbon–chlorine bond selectivity. X-ray absorption spectroscopy analysis using both in situ and ex situ conditions followed the dynamic transformation of single atoms into amorphous clusters, which consist of a unique unsaturated coordination environment and few nanometer diameter. Importantly, the intricate relationship between stability and performance underscores the vital role of detailed characterization to properly determine the true active species for dehalogenation reactions.

View Accepted Manuscript (DOE)

Research Organization:: Brookhaven National Laboratory (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); National Science Foundation (NSF)

Grant/Contract Number:: SC0012704

OSTI ID:: 2205641

Report Number(s):: BNL--224988-2023-JAAM

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 36 Vol. 57; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Palladium Single-Atom (In)Stability Under Aqueous Reductive Conditions

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