Synergistic sites over the ZnxZrO catalyst for targeted cleavage of the C-H bonds of ethane in tandem with CO2 activation

doi:10.1016/S1872-2067(24)60235-4

Abstract

Abstract:

The CO₂-assisted oxidative dehydrogenation of ethane (CO₂-ODHE) provides a promising way to produce ethylene and utilize CO₂. Simultaneous upgrading of ethane into the high value-added chemical products and the reduction of greenhouse gas CO₂ emissions could be achieved. However, the targeted breaking of the C-C/C-H bonds of ethane is still a challenge for the designed catalysts. In this paper, ZnO-doped ZrO₂ bifunctional catalysts (Zn_xZrO) with different Zn/Zr molar ratios were prepared by the deposition-precipitation method, and the functions of various sites for CO₂-ODHE reaction were revealed by in situ characterizations and ethane pulse experiment: the medium-strength acidic Zn-O-Zr sites are responsible for the purposefully cracking of ethane C-H bonds to ethylene, while the more oxygen vacancies (O_V) created by the introduction of Zn²⁺ are responsible for the efficient activation C=O bonds of CO₂, thus promoting the RWGS reaction. In addition, the Zn_0.2ZrO catalyst demonstrated excellent catalytic performances, with C₂H₆ conversion, C₂H₄ yield, and CO₂ conversion about 19.1%, 10.5%, and 10.6% within 5 h, respectively (600 °C, GHSV = 3000 mL/(g·h)). Especially, the initial ethylene space-time yield of 355.5 μmol/(min·g) was obtained under 6000 mL/(g·h); Finally, the tandem reaction mechanism of ethane dehydrogenation and RWGS was revealed.

Key words: Zn-O-Zr site, Oxygen vacancies, CO₂, Ethylene space-time yield, Tandem reaction

Wenjun Qiang, Duohua Liao, Maolin Wang, Lingzhen Zeng, Weiqi Li, Xuedong Ma, Liang Yang, Shuang Li, Ding Ma. Synergistic sites over the Zn_xZrO catalyst for targeted cleavage of the C-H bonds of ethane in tandem with CO₂ activation[J]. Chinese Journal of Catalysis, 2025, 70: 272-284.

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Figures/Tables 15

Fig. 1. The proposed reaction mechanism of CO2-ODHE over the ZnxZrO catalysts.

Fig. 2. (a) XRD patterns of ZrO2, ZnO, and ZnxZrO catalysts. (b) The partially enlarged XRD patterns of ZrO2, ZnO, and ZnxZrO catalysts. (c) Raman spectra of ZrO2, ZnO, and ZnxZrO catalysts.

Table 1 Crystal structures, the ZrO2 lattice parameters, cell volume, average grain size, and relative concentration of OV for ZrO2, ZnO, and ZnxZrO catalysts.

Catalyst	Crystal structure	ZrO₂ lattice parameter ^a		Cell volume ^a (Å^3)	Average grain size ^a (nm)	I₅₈₂/I₄₃₈ ^b
Catalyst	Crystal structure	a (Å)	c (Å)	Cell volume ^a (Å^3)	Average grain size ^a (nm)	I₅₈₂/I₄₃₈ ^b
ZrO₂	t-ZrO₂/m-ZrO₂	3.5931	5.1309	67.01	12	-
Zn_0.02ZrO	t-ZrO₂	3.5987	5.1140	66.77	17	0.27
Zn_0.05ZrO	t-ZrO₂	3.6004	5.1098	66.50	19	0.37
Zn_0.1ZrO	t-ZrO₂	3.6013	5.1089	66.42	23	0.42
Zn_0.2ZrO	t-ZrO₂	3.5926	5.0935	66.33	27	0.53
Zn₁ZrO	t-ZrO₂/h-ZnO	3.5982	5.2506	67.29	40	0.44
ZnO	h-ZnO	3.2491	5.2048	47.58	>100	0.34

Fig. 3. HRTEM images of ZrO2, ZnO, and ZnxZrO catalysts. (a,b) ZrO2; (c,d) Zn0.02ZrO; (e,f) Zn0.05ZrO; (g,h) Zn0.1ZrO; (i,j) Zn0.2ZrO; (k-n) Zn1ZrO; (o,p) ZnO.

Fig. 4. Zn K-edge XANES (a) and phase-uncorrected FT-EXAFS (b) spectra of Zn foil, ZnO, and ZnxZrO catalysts (The EXAFS spectra have been obtained by transforming the corresponding k3 χ(k) EXAFS function).

Fig. 5. XPS spectra of ZrO2, ZnO, and ZnxZrO catalysts. (a) Zr 3d; (b) Zn 2p; (c) O 1s.

Fig. 6. CO2-TPD profiles (a), Py-IR spectra after desorption at 200 °C (b) and NH3-TPD profiles (c) of ZnO, ZrO2, and ZnxZrO catalysts.

Table 2 The acid-base properties of ZrO2 and ZnxZrO catalysts.

Catalyst	The type of basic sites ^a (mmol/g)			The type of acid sites ^b (mmol/g)
Catalyst	Weak	Strong	Total	Weak	Medium	Strong
ZrO₂	0.1012	0.1142	0.2154	0.0433	0.0425	0.0768
Zn_0.02ZrO	0.0782	0.1224	0.2006	0.0387	0.0494	0.0729
Zn_0.05ZrO	0.0459	0.1377	0.1837	0.0243	0.0509	0.0649
Zn_0.1ZrO	0.0316	0.1441	0.1757	0.0156	0.0709	0.0521
Zn_0.2ZrO	0.0191	0.1501	0.1692	0.0195	0.0771	0.0483
Zn₁ZrO	0.0093	0.1237	0.1316	0.0223	0.0520	0.0382

Fig. 7. C2H6 conversion (a), C2H4 yield (b), and C2H4 selectivity and CO2 conversion (c) over ZrO2, ZnO, and ZnxZrO catalysts. Reaction conditions: T = 600 °C, C2H6:CO2:N2 = 1:1:2, GHSVC2H6 = 3000 mL/(g·h).

Fig. 8. (a) XRD patterns of fresh and spent Zn0.2ZrO catalysts. (b) TG diagram of spent Zn0.2ZrO catalysts.

Fig. 9. XPS spectra of fresh and spent Zn0.2ZrO catalysts. (a) Survey; (b) Zr 3d; (c) Zn 2p; (d) O 1s.

Fig. 10. (a) The C2H6 conversion, C2H4 selectivity, and C2H4 STY over Zn0.2ZrO catalyst compared with other catalysts reported in the literature. Reaction conditions: T = 600 or 700 °C, C2H6:CO2:N2 = 1:1:2, GHSVC2H6 = 3000 mL/(g·h), Reference numbers were marked along with symbols. (b) The apparent activation energy of Zn0.2ZrO and other catalysts reported in the literature. Reaction conditions: T = 550, 575, 600, and 700 °C, C2H6:CO2:N2 = 1:1:2, GHSVC2H6 = 3000 mL/(g·h).

Fig. 11. (a) Raman spectra of Zn0.2ZrO pretreated with CO at 500 and 600 °C. (b,c) XPS spectra of Zn0.2ZrO pretreated with HNO3 solution. C2H6 conversion and C2H4 yield over Zn0.2ZrO: pretreated with CO at 500 and 600 °C (d) and pretreated with HNO3 solution (e). Reaction conditions: T = 600 °C, C2H6:CO2:N2 = 1:1:2, GHSVC2H6 = 3000 mL/(g·h).

Fig. 12. In situ FTIR spectra of reaction intermediates over the Zn0.2ZrO catalyst. (a) C2H6:N2 = 1:3; (b) CO2:N2 = 1:3; (c) C2H6:CO2:N2 = 1:1:2. Reaction conditions: T = 300 °C, GHSV = 12000 mL/(g·h)). α: HCOO*, HCO3*, and H3CO* stretching vibrations [76]; β: O-H stretching vibrations and gas CO2 stretching vibrations; γ: C-H and C=C stretching vibrations (ethylene); δ: C-H stretching vibrations (ethane) [77]; λ: C=O stretching vibrations (CO2) [78]; ε: HCOO* stretching vibrations [28].

Fig. 13. C2H6 Conversion (a) and C2H4 selectivity (b) over Zn0.2ZrO catalyst in C2H6 pulse experiment. Reaction conditions: T = 600 °C, C2H6:N2 = 1:3, GHSVC2H6 = 3000 mL/(g·h).

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Synergistic sites over the Zn_xZrO catalyst for targeted cleavage of the C-H bonds of ethane in tandem with CO₂ activation

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