High entropy oxide catalysts with SO2 resistance in RWGS reaction

Mengyuan Zhang; Xiaoyan Lu; Kongliang Luo; Jian Ye; Jia li Dong; Nana Lu; Xiaopeng Wang; Qiang Niu; Pengfei Zhang; Sheng Dai

doi:10.1016/j.apcatb.2024.123845

High entropy oxide catalysts with SO₂ resistance in RWGS reaction

Mengyuan Zhang
, Xiaoyan Lu
, Kongliang Luo
, Jian Ye
, Jia li Dong
, Nana Lu
, Xiaopeng Wang
, Qiang Niu
, Pengfei Zhang
, Sheng Dai

Chemical Sciences Division

Research output: Contribution to journal › Article › peer-review

14 Scopus citations

Abstract

Ubiquitous presence of SO₂ usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design SO₂ resistance oxide catalysts is proposed. (Ni_0.2Mg_0.2Cu_0.2Zn_0.2Co_0.2)Fe₂O₄ showed excellent performance (the CO₂ conv. = 41.4%, CO selec. = 99.6% at 400°C) compared to the control samples in the reverse water–gas shift (RWGS). In addition, (Ni_0.2Mg_0.2Cu_0.2Zn_0.2Co_0.2)Fe₂O₄ had the SO₂-tolerant ability (the CO₂ conv. = 38.5%, CO selec. = 99.2% at 400°C) after being poisoned with 1000 ppm SO₂ at 400°C for 1 h. In sharp contrast, the control samples NiFe₂O_4, MgFe₂O_4, CuFe₂O₄ and CoFe₂O₄ lost their activity. O^1S XPS indicated that (Ni_0.2Mg_0.2Cu_0.2Zn_0.2Co_0.2)Fe₂O₄ had higher oxygen vacancy concentrations. SO₂ resistance mechanism was studied by infrared spectroscopy, SO₂-TPD, in situ S 2p XPS and the DFT results, confirming that the low SO₂ adsorption energy of (Ni_0.2Mg_0.2Cu_0.2Zn_0.2Co_0.2)Fe₂O₄, which was attributed to the lower Gibbs free energy. This work may inspire the rational design of SO₂-resistant catalysts.

Original language	English
Article number	123845
Journal	Applied Catalysis B: Environmental
Volume	349
DOIs	https://doi.org/10.1016/j.apcatb.2024.123845
State	Published - Jul 15 2024

Funding

This work was supported by the National Key R & D Program Plan ( 2020YFB0606400 ), the National Natural Science Foundation of China (Grant Nos. 21776174 ; 22178219 ), the Inner Mongolia Key R & D Program Plan ( 2021ZD0042 ), the Shanghai Rising-Star Program ( 20QA1405200 ), and the Shanghai Jiao Tong University Scientific and Technological Innovation Funds (No. 2019QYB06 ). S.D. (discussion of the results) was supported by U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division .

Keywords

Entropy engineering
High entropy oxide
In situ FTIR
In situ XPS
RWGS reaction
SO resistance

Access to Document

10.1016/j.apcatb.2024.123845

Cite this

@article{fb8951d9fd3f45898b24df12b81a232f,

title = "High entropy oxide catalysts with SO2 resistance in RWGS reaction",

abstract = "Ubiquitous presence of SO2 usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design SO2 resistance oxide catalysts is proposed. (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4 showed excellent performance (the CO2 conv. = 41.4\%, CO selec. = 99.6\% at 400°C) compared to the control samples in the reverse water–gas shift (RWGS). In addition, (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4 had the SO2-tolerant ability (the CO2 conv. = 38.5\%, CO selec. = 99.2\% at 400°C) after being poisoned with 1000 ppm SO2 at 400°C for 1 h. In sharp contrast, the control samples NiFe2O4, MgFe2O4, CuFe2O4 and CoFe2O4 lost their activity. O1S XPS indicated that (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4 had higher oxygen vacancy concentrations. SO2 resistance mechanism was studied by infrared spectroscopy, SO2-TPD, in situ S 2p XPS and the DFT results, confirming that the low SO2 adsorption energy of (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4, which was attributed to the lower Gibbs free energy. This work may inspire the rational design of SO2-resistant catalysts.",

keywords = "Entropy engineering, High entropy oxide, In situ FTIR, In situ XPS, RWGS reaction, SO resistance",

author = "Mengyuan Zhang and Xiaoyan Lu and Kongliang Luo and Jian Ye and Dong, \{Jia li\} and Nana Lu and Xiaopeng Wang and Qiang Niu and Pengfei Zhang and Sheng Dai",

note = "Publisher Copyright: {\textcopyright} 2024 Elsevier B.V.",

year = "2024",

month = jul,

day = "15",

doi = "10.1016/j.apcatb.2024.123845",

language = "English",

volume = "349",

journal = "Applied Catalysis B: Environmental",

issn = "0926-3373",

publisher = "Elsevier",

}

TY - JOUR

T1 - High entropy oxide catalysts with SO2 resistance in RWGS reaction

AU - Zhang, Mengyuan

AU - Lu, Xiaoyan

AU - Luo, Kongliang

AU - Ye, Jian

AU - Dong, Jia li

AU - Lu, Nana

AU - Wang, Xiaopeng

AU - Niu, Qiang

AU - Zhang, Pengfei

AU - Dai, Sheng

PY - 2024/7/15

Y1 - 2024/7/15

N2 - Ubiquitous presence of SO2 usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design SO2 resistance oxide catalysts is proposed. (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4 showed excellent performance (the CO2 conv. = 41.4%, CO selec. = 99.6% at 400°C) compared to the control samples in the reverse water–gas shift (RWGS). In addition, (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4 had the SO2-tolerant ability (the CO2 conv. = 38.5%, CO selec. = 99.2% at 400°C) after being poisoned with 1000 ppm SO2 at 400°C for 1 h. In sharp contrast, the control samples NiFe2O4, MgFe2O4, CuFe2O4 and CoFe2O4 lost their activity. O1S XPS indicated that (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4 had higher oxygen vacancy concentrations. SO2 resistance mechanism was studied by infrared spectroscopy, SO2-TPD, in situ S 2p XPS and the DFT results, confirming that the low SO2 adsorption energy of (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4, which was attributed to the lower Gibbs free energy. This work may inspire the rational design of SO2-resistant catalysts.

AB - Ubiquitous presence of SO2 usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design SO2 resistance oxide catalysts is proposed. (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4 showed excellent performance (the CO2 conv. = 41.4%, CO selec. = 99.6% at 400°C) compared to the control samples in the reverse water–gas shift (RWGS). In addition, (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4 had the SO2-tolerant ability (the CO2 conv. = 38.5%, CO selec. = 99.2% at 400°C) after being poisoned with 1000 ppm SO2 at 400°C for 1 h. In sharp contrast, the control samples NiFe2O4, MgFe2O4, CuFe2O4 and CoFe2O4 lost their activity. O1S XPS indicated that (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4 had higher oxygen vacancy concentrations. SO2 resistance mechanism was studied by infrared spectroscopy, SO2-TPD, in situ S 2p XPS and the DFT results, confirming that the low SO2 adsorption energy of (Ni0.2Mg0.2Cu0.2Zn0.2Co0.2)Fe2O4, which was attributed to the lower Gibbs free energy. This work may inspire the rational design of SO2-resistant catalysts.

KW - Entropy engineering

KW - High entropy oxide

KW - In situ FTIR

KW - In situ XPS

KW - RWGS reaction

KW - SO resistance

UR - https://www.scopus.com/pages/publications/85185703286

U2 - 10.1016/j.apcatb.2024.123845

DO - 10.1016/j.apcatb.2024.123845

M3 - Article

AN - SCOPUS:85185703286

SN - 0926-3373

VL - 349

JO - Applied Catalysis B: Environmental

JF - Applied Catalysis B: Environmental

M1 - 123845

ER -