TY - JOUR
T1 - In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation
AU - Hülsey, Max J.
AU - Zhang, Bin
AU - Ma, Zhirui
AU - Asakura, Hiroyuki
AU - Do, David A.
AU - Chen, Wei
AU - Tanaka, Tsunehiro
AU - Zhang, Peng
AU - Wu, Zili
AU - Yan, Ning
N1 - Publisher Copyright:
© 2019, The Author(s).
PY - 2019/12/1
Y1 - 2019/12/1
N2 - Single-atom catalysts have recently been applied in many applications such as CO oxidation. Experimental in situ investigations into this reaction, however, are limited. Hereby, we present a suite of operando/in situ spectroscopic experiments for structurally well-defined atomically dispersed Rh on phosphotungstic acid during CO oxidation. The identification of several key intermediates and the steady-state catalyst structure indicate that the reactions follow an unconventional Mars-van Krevelen mechanism and that the activation of O 2 is rate-limiting. In situ XPS confirms the contribution of the heteropoly acid support while in situ DRIFT spectroscopy consolidates the oxidation state and CO adsorption of Rh. As such, direct observation of three key components, i.e., metal center, support and substrate, is achieved, providing a clearer picture on CO oxidation on atomically dispersed Rh sites. The obtained information are used to engineer structurally similar catalysts that exhibit T 20 values up to 130 °C below the previously reported Rh 1 /NPTA.
AB - Single-atom catalysts have recently been applied in many applications such as CO oxidation. Experimental in situ investigations into this reaction, however, are limited. Hereby, we present a suite of operando/in situ spectroscopic experiments for structurally well-defined atomically dispersed Rh on phosphotungstic acid during CO oxidation. The identification of several key intermediates and the steady-state catalyst structure indicate that the reactions follow an unconventional Mars-van Krevelen mechanism and that the activation of O 2 is rate-limiting. In situ XPS confirms the contribution of the heteropoly acid support while in situ DRIFT spectroscopy consolidates the oxidation state and CO adsorption of Rh. As such, direct observation of three key components, i.e., metal center, support and substrate, is achieved, providing a clearer picture on CO oxidation on atomically dispersed Rh sites. The obtained information are used to engineer structurally similar catalysts that exhibit T 20 values up to 130 °C below the previously reported Rh 1 /NPTA.
UR - http://www.scopus.com/inward/record.url?scp=85063342959&partnerID=8YFLogxK
U2 - 10.1038/s41467-019-09188-9
DO - 10.1038/s41467-019-09188-9
M3 - Article
C2 - 30902990
AN - SCOPUS:85063342959
SN - 2041-1723
VL - 10
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 1330
ER -