Boosting ethyl acetate low-temperature deep oxidation by tuning the initial status of Ag over MnO2: Intrinsic role of Ag nanoparticles and ions

doi:10.1016/S1872-2067(26)64979-0

Abstract

Abstract:

Promoting activity while inhibiting hazardous byproduct formation remains a great challenge in oxygenated volatile organic compounds (OVOCs) purification. Here, we found that the low-temperature oxidation of ethyl acetate (EA) and the generation rate of CO₂ were enhanced by controlling the initial Ag precursor (ions vs. nanoparticles) to engineer catalysts with distinct active site configurations. The reaction rate and TOF_Ag of Ag nanoparticles/310MnO₂ (Ag-NP/310MnO₂) are 4.3 and 4.1 times higher, respectively, than those of Ag ions/310MnO₂ (Ag-IS/310MnO₂) at 150 °C. And Ag-NP/310MnO₂ further shows a 1.9-fold higher CO₂ selectivity compared to that of Ag-IS/310MnO₂. The adsorption ability of EA is much stronger than that of O₂ at Ag site, while the opposite trend is observed at oxygen vacancy. The synergy between Ag site (EA adsorption) and oxygen vacancy (O₂ dissociation) in Ag-NP/310MnO₂ accelerates O₂ activation and subsequent EA oxidation. Moreover, abundant active oxygen species (*O) promote the rate-limiting step of acetic acid decomposition, contributing to superior low-temperature CO₂ selectivity. However, due to the fierce competition from EA, limited O₂ is adsorbed at Ag site-occupied oxygen vacancy, which is difficult to dissociate especially at low temperature, leading to inferior activity of Ag-IS/310MnO₂. This work provides a vital scientific basis for enhancing the low-temperature deep oxidation of OVOCs, showcasing remarkable environmental significance.

Key words: Ethyl acetate, Catalytic oxidation, MnO₂, Ag site, Oxygen vacancy

Jian-Rong Li, Wan-Peng Zhang, Hang Xiao, Mingjiao Tian, Chi He. Boosting ethyl acetate low-temperature deep oxidation by tuning the initial status of Ag over MnO₂: Intrinsic role of Ag nanoparticles and ions[J]. Chinese Journal of Catalysis, 2026, 83: 388-399.

×
share this article

Add to citation manager EndNote|Ris|BibTeX

URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(26)64979-0

https://www.cjcatal.com/EN/Y2026/V83/I4/388

Figures/Tables 7

Fig. 1. Fig. 1. (a) XRD patterns. (b) Raman spectra. (a) 310MnO2. (b) Ag-NP/310MnO2. (c) Ag-IS/310MnO2. (c) EPR spectra. (f) O 1s XPS spectra. (g) Fourier transforms for k2-weighted Ag K-edge EXAFS and fitting results. The wavelet transforms for k2-weighted Ag K-edge EXAFS of Ag-IS/310MnO2 (h) and Ag-NP/310MnO2 (i).

Fig. 2. HRTEM images of Ag-IS/310MnO2 (a) and Ag-NP/310MnO2 (b). Schematic diagram of Ag formation processes for Ag-IS/310MnO2 (c) and Ag-NP/310MnO2 (d). The optimized structure of Ag in Ag-IS/310MnO2 (e) and Ag-NP/310MnO2 (f).

Table 1 Catalytic activity and textural properties of prepared catalysts.

Sample	T₅₀ ^a (°C)	T₉₀ ^a (°C)	Ag ^b (wt%)	Ag dispersion ^c (%)	A_BET ^d (m²·g^-1)	V_pore ^e (cm³·g^-1)	D_pore ^f (nm)	E_a ^g (kJ·mol^-1)	K ^h (N/m)
310MnO₂	165	171	—	—	124.1	0.48	15.0	44.3	307
Ag-IS/310MnO₂	167	178	0.57	58.6	121.8	0.50	15.7	54.7	302
Ag-NP/310MnO₂	157	163	0.61	58.2	120.2	0.47	14.7	31.0	303

Fig. 3. (a) EA conversion of 310MnO2, 110MnO2 and 100MnO2. (b) EA conversion of 310MnO2, Ag-IS/310MnO2, and Ag-NP/310MnO2. (c) CO2 selectivity. The change of relative contents of acetaldehyde/ethanol/formic acid (d) and acetic acid (e) from PTR-MS at different temperatures. (f) Reaction rates and TOFAg values.

Fig. 4. (a) H2-TPR. (b) O2-TPD. (c) EA and acetic acid profiles obtained from EA-TPD. (d) CO2 profiles obtained from EA-TPD.

Fig. 5. In-situ DRIFTS spectra of Ag-IS/310MnO2 (a), Ag-NP/310MnO2 (b) and 310MnO2 (c) catalysts for EA adsorption/oxidation as a function of reaction time in flowing EA+N2 at 50 °C. (d) The optimized structure of O2 absorbed at Ag and oxygen vacancy sites. (e) The optimized structure of EA absorbed at Ag and oxygen vacancy sites. (f) Energy profiles for the reaction paths of O2 adsorption and dissociation at Ag sites of Ag-IS/310MnO2 and Ag-NP/310MnO2. (g) Energy profiles for the reaction paths of O2 adsorption and dissociation at oxygen vacancy sites of 310MnO2 and Ag-NP/310MnO2.

Fig. 6. Reaction mechanism of EA oxidation over prepared catalysts.

References

[1]	N. Wu, S. Wu, J. Yang, Q. Wang, S. Yang, J. Li, Q. Gao, M. Guo, J. Zhong, Chem. Eng. J., 2025, 516, 164003.
[2]	H. Zhang, Z. Wang, L. Wei, Y. Liu, H. Dai, J. Deng, Chin. J. Catal., 2024, 61, 71-96.
[3]	W. Zhang, G. Li, H. Yin, K. Zhao, H. Zhao, T. An, Environ. Sci.: Nano, 2022, 9, 81-104.
[4]	S. Ding, S. Wu, N. Fang, Y. Chu, P. Wang, L. Ding, Sep. Purif. Technol., 2025, 352, 128158.
[5]	W.-P. Zhang, Y.-Y. Li, J. Zhao, K. Wu, H. Xiao, J.-R. Li, J. Colloid Interface Sci., 2024, 671, 611-620.
[6]	X. Zhao, L. Huang, X. Ding, X. Zhang, J. Guo, Y. Sun, L. Liao, Q. Xie, S. Mo, D. Yan, D. Ye, Sep. Purif. Technol., 2024, 346, 127361.
[7]	J.-R. Li, W.-P. Zhang, C. Li, H. Xiao, C. He, Appl. Surf. Sci., 2021, 550, 149179.
[8]	J.-R. Li, W.-P. Zhang, C. Li, C. He, J. Colloid Interface Sci., 2021, 591, 396-408.
[9]	C. He, J. Cheng, X. Zhang, M. Douthwaite, S. Pattisson, Z. Hao, Chem. Rev., 2019, 119, 4471-4568.
[10]	Y. Wang, Z. Jiang, Y. Wu, C. Ai, F. Dang, H. Xu, J. Wan, W. Guan, R. Albilali, C. He, Environ. Sci. Technol., 2024, 58, 18414-18425.
[11]	K. Inoue, S. Somekawa, Chem. Eng. Technol., 2019, 42, 257-260.
[12]	Z. Jiang, X. Feng, J. Deng, C. He, M. Douthwaite, Y. Yu, J. Liu, Z. Hao, Z. Zhao, Adv. Funct. Mater., 2019, 29, 1902041.
[13]	G. Avgouropoulos, E. Oikonomopoulos, D. Kanistras, T. Ioannides, Appl. Catal. B, 2006, 65, 62-69.
[14]	K. Yasuda, M. Nobu, T. Masui, N. Imanaka, Mater. Res. Bull., 2010, 45, 1278-1282.
[15]	C. Ai, J. Wan, Z. Jiang, Y. Wang, F. Dang, S. Chai, M. Tian, Y. Jian, Y. Yu, C. Chen, R. Albilali, C. He, Environ. Sci. Technol., 2024, 58, 11760-11770.
[16]	H. Huang, Y. Xu, Q. Feng, D. Y. C. Leung, Catal. Sci. Technol., 2015, 5, 2649-2669.
[17]	M. Ma, R. Yang, C. He, Z. Jiang, J.-W. Shi, R. Albilali, K. Fayaz, B. Liu, J. Hazard. Mater., 2021, 401, 123281.
[18]	O. Sanz, J. J. Delgado, P. Navarro, G. Arzamendi, L. M. Gandía, M. Montes, Appl. Catal. B, 2011, 110, 231-237.
[19]	J.-R. Li, W.-P. Zhang, J. Zhao, M. Tian, K. Wu, H. Xiao, C. He, ACS Appl. Mater. Interfaces, 2022, 14, 36536-36550.
[20]	Y.-Y. Li, H. Xiao, J.-R. Li, Appl. Surf. Sci., 2025, 703, 163412.
[21]	Y. Zheng, K. Fu, Z. Yu, Y. Su, R. Han, Q. Liu, J. Mater. Chem. A, 2022, 10, 14171-14186.
[22]	J.-R. Li, J. Zheng, K. Wu, M. He, J. Zhao, Y. Meng, J. He, H.-Y. Ren, H. Xiao, C. He, ACS ES&T Eng., 2023, 3, 487-499.
[23]	S. Rong, P. Zhang, F. Liu, Y. Yang, ACS Catal., 2018, 8, 3435-3446.
[24]	D. Ding, Y. Zhou, T. He, S. Rong, Chem. Eng. J., 2022, 431, 133737.
[25]	J. Li, Z. Qu, Y. Qin, H. Wang, Appl. Surf. Sci., 2016, 385, 234-240.
[26]	W. Yang, X. Zhao, Y. Wang, X. Wang, H. Liu, W. Yang, H. Zhou, Y. A. Wu, C. Sun, Y. Peng, J. Li, Catal. Sci. Technol., 2022, 12, 5932-5941.
[27]	Y. Qin, Y. Wang, J. Li, Z. Qu, Surf. Interfaces, 2020, 21, 100657.
[28]	Y. Dong, J. Sun, Y. Shen, Z. Wang, W. Wang, Z. Song, X. Zhao, Y. Mao, Chem. Eng. J., 2023, 473, 145130.
[29]	W.-P. Zhang, J.-R. Li, Y.-Y. Li, J. Zhao, K. Wu, H. Xiao, C. He, Environ. Sci. Technol., 2023, 57, 20962-20973.
[30]	D. Yan, T. Li, P. Liu, S. Mo, J. Zhong, Q. Ren, Y. Sun, H. Cheng, M. Fu, J. Wu, P. Chen, H. Huang, D. Ye, Chemosphere, 2021, 279, 130658.
[31]	X. Li, J. Ma, H. He, Environ. Sci. Technol., 2020, 54, 11566-11575.
[32]	T. Wen, S. Guo, H. Zhao, Y. Zheng, X. Zhang, P. Gu, S. Zhang, Y. Ai, X. Wang, Chin. J. Catal., 2024, 61, 215-225.
[33]	H. Yang, G. Li, Q. Liu, H. Cheng, X. Wang, J. Cheng, G. Jiang, F. Zhang, Z. Zhang, Z. Hao, Angew. Chem. Int. Ed., 2024, 63, e202400627.
[34]	C. Feng, G. Xiong, C. Chen, Y. Lin, Z. Wang, Y. Lu, F. Liu, X. Li, Y. Liu, R. Zhang, Y. Pan, Chin. J. Catal., 2025, 75, 21-33.
[35]	Y.-D. Yang, L.-L. Long, Z.-A. Gong, J. Cao, S.-H. Tian, X.-J. Yao, Y. Chen, Tungsten, 2025, 7, 497-510.
[36]	D. Manikandan, A. K. Yadav, S. N. Jha, D. Bhattacharyya, D. W. Boukhvalov, R. Murugan, J. Phys. Chem. C, 2019, 123, 3067-3075.
[37]	X. Li, G. He, J. Ma, X. Shao, Y. Chen, H. He, Environ. Sci. Technol., 2021, 55, 16143-16152.
[38]	B. Jin, B. Zhao, S. Liu, Z. Li, K. Li, R. Ran, Z. Si, D. Weng, X. Wu, Appl. Catal. B, 2020, 273, 119058.
[39]	D. Xia, H. Liu, B. Xu, Y. Wang, Y. Liao, Y. Huang, L. Ye, C. He, P. K. Wong, R. Qiu, Appl. Catal. B, 2019, 245, 177-189.
[40]	C. Shan, Y. Zhang, Q. Zhao, K. Fu, Y. Zheng, R. Han, C. Liu, N. Ji, W. Wang, Q. Liu, Environ. Sci. Technol., 2022, 56, 10381-10390.
[41]	J. Yang, S. Hu, Y. Fang, S. Hoang, L. Li, W. Yang, Z. Liang, J. Wu, J. Hu, W. Xiao, C. Pan, Z. Luo, J. Ding, L. Zhang, Y. Guo, ACS Catal., 2019, 9, 9751-9763.
[42]	D. Zhu, Y. Huang, R. Li, S. Peng, P. Wang, J.-J. Cao, Environ. Sci. Technol., 2023, 57, 17598-17609.
[43]	H. Chen, Y. Liu, R. Gao, T. Dong, Z. Hou, L. Jing, E. Duan, J. Deng, H. Dai, J. Hazard. Mater., 2022, 437, 129358.
[44]	X. Wang, L. Wu, Z. Wang, Y. Feng, Y. Liu, H. Dai, Z. Wang, J. Deng, Appl. Catal. B, 2023, 322, 122075.
[45]	F. Bi, J. Wei, Z. Zhou, Y. Zhang, B. Gao, N. Liu, J. Xu, B. Liu, Y. Huang, X. Zhang, JACS Au, 2025, 5, 363-380.
[46]	W. Wang, Q. Wang, Z. Shen, X. Meng, E. Gao, X. Jiang, J. Miao, S. Yao, Z. Wu, J. Li, J. Zhu, Y. Zhong, Q. Guo, Sep. Purif. Technol., 2024, 349, 127862.
[47]	J. Xu, Z. Wu, E. Gao, J. Zhu, S. Yao, J. Li, Appl. Surf. Sci., 2023, 618, 156643.

Boosting ethyl acetate low-temperature deep oxidation by tuning the initial status of Ag over MnO₂: Intrinsic role of Ag nanoparticles and ions

RichHTML

PDF (PC)

Knowledge

Supporting Information

Abstract

Cite this article

share this article

share this article

Figures/Tables 7

References

Related Articles 15

Recommended Articles

Metrics

[1]	Jiaxing Li, Yue Peng, Yifan Li, Yunpeng Long, William Orbell, Chuan Gao, Xiao Zhu, Xing Yuan, Lin Chen, Junhua Li. Modulation of Pt-Cu interaction in Pt/Cu-SSZ-13 for selective catalytic oxidation of ammonia [J]. Chinese Journal of Catalysis, 2026, 83(4): 376-387.
[2]	Keshan Tang, Wanyi Deng, Ningyuan Wang, Yang Xia, Xinhe Wu, Heng Yang. Triazine-based COF/TiO₂ S-scheme heterojunction with oxygen vacancies for efficient photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2026, 83(4): 244-257.
[3]	Yao-Yao Xie, Chang-Long Tan, Liang Mao, Zi-Rong Tang, Yi-Jun Xu. Highly efficient hydroxyethyl radicals-mediated photocatalytic benzimidazole synthesis and hydrogen evolution over defect-engineered Pt/Nb₂O₅ [J]. Chinese Journal of Catalysis, 2026, 83(4): 132-142.
[4]	Feng Li, Ye Ma, Mingyu Wan, Yating Lv, Jiamin Yuan, Shichao Han, Houyu Ma, Liang Wang, Xiangju Meng, Anmin Zheng, Yanhang Ma, Feng-Shou Xiao. Pure silica Beta zeolite supported Ag-Mn catalyst for efficient ozone decomposition [J]. Chinese Journal of Catalysis, 2026, 82(3): 292-300.
[5]	Feng Chao, Xiong Gaoyan, Chen Chong, Lin Yan, Wang Zhong, Lu Yukun, Liu Fang, Li Xuebing, Liu Yunqi, Zhang Runduo, Pan Yuan. Highly dispersed Pt/Co₃O₄ catalyst constructed by vacancy defect inductive effect for enhanced catalytic propane total oxidation [J]. Chinese Journal of Catalysis, 2025, 75(8): 21-33.
[6]	Li Yuanrui, Zhang Xiaolei, Li Tong, Hu Cheng, Chen Fang, Cai Hao, Huang Hongwei. Few-layer oxygen vacant Bi₂O₂(OH)NO₃ for dual-channel piezocatalytic H₂O₂ production from H₂O and air [J]. Chinese Journal of Catalysis, 2025, 75(8): 105-114.
[7]	Wang Qiuyue, Yang Chenyu, Zhu Shenggan, Zhang Yuansen, Wang Xuan, Li Yongting, Ding Weiping, Guo Xuefeng. Interface engineering of oxygen-vacancy-rich MgO/Ni@NiAlO enables low-temperature coke-free methane dry reforming [J]. Chinese Journal of Catalysis, 2025, 75(8): 9-20.
[8]	Xiong Qi, Shi Quanquan, Wang Binli, Baiker Alfons, Li Gao. Facet-induced reduction directed AgBr/Ag⁰/TiO₂{100} Z-scheme heterojunction for tetracycline removal [J]. Chinese Journal of Catalysis, 2025, 75(8): 164-179.
[9]	Cunjun Li, Jie He, Tianle Cai, Xianlei Chen, Hengcong Tao, Yingtang Zhou, Mingshan Zhu. Surface oxygen vacancies of BiOBr regulating piezoelectricity for enhancing efficiency and selectivity of photocatalytic CO₂ reduction [J]. Chinese Journal of Catalysis, 2025, 74(7): 130-143.
[10]	Pengkun Zhang, Qinhan Wu, Haoyu Wang, Dong-Hau Kuo, Yujie Lai, Dongfang Lu, Jiqing Li, Jinguo Lin, Zhanhui Yuan, Xiaoyun Chen. Z-scheme heterojunction Zn₃(OH)₂(V₂O₇)(H₂O)₂/V-Zn(O,S) for enhanced visible-light photocatalytic N₂ fixation via synergistic heterovalent vanadium states and oxygen vacancy defects [J]. Chinese Journal of Catalysis, 2025, 74(7): 279-293.
[11]	Rui Li, Pengfei Feng, Bonan Li, Jiayu Zhu, Yali Zhang, Ze Zhang, Jiangwei Zhang, Yong Ding. Photocatalytic reduction of CO₂ over porous ultrathin NiO nanosheets with oxygen vacancies [J]. Chinese Journal of Catalysis, 2025, 73(6): 242-251.
[12]	Yan Wang, Xiaorui Yan, Zeyang Sun, Jinjun Liu, Yiwen Wang, Chenchao Hu, Yilin Deng, Meng Xie, Jimin Xie, Wei Zhang, Yuanguo Xu. Synergistic catalysis of oxygen vacancy and S-scheme heterojunction in NiFe₂O_4‒_x/NiS regulates peroxymonosulfate activation for enhanced photo-Fenton-like reaction [J]. Chinese Journal of Catalysis, 2025, 79(12): 186-204.
[13]	Yuqing Tang, Yanjun Chen, Aqsa Abid, Zichun Meng, Xiaoying Sun, Bo Li, Zhen Zhao. Revisiting the origin of the superior performance of defective zirconium oxide catalysts in propane dehydrogenation: Double-edged oxygen vacancy [J]. Chinese Journal of Catalysis, 2025, 68(1): 272-281.
[14]	Yunying Huo, Cong Guo, Yongle Zhang, Jingyi Liu, Qiao Zhang, Zhiting Liu, Guangxing Yang, Rengui Li, Feng Peng. Realizing efficient electrochemical oxidation of 5-hydroxymethylfurfural on a freestanding Ni(OH)₂/nickel foam catalyst [J]. Chinese Journal of Catalysis, 2024, 63(8): 282-291.
[15]	Xinyu Chen, Cong-Cong Zhao, Jing Ren, Bo Li, Qianqian Liu, Wei Li, Fan Yang, Siqi Lu, YuFei Zhao, Li-Kai Yan, Hong-Ying Zang. An oxygen-vacancy-rich polyoxometalate-aided Ag-based heterojunction electrocatalyst for nitrogen fixation [J]. Chinese Journal of Catalysis, 2024, 62(7): 209-218.