Effect of W Content on Structure and Catalytic Performance of Pt/GaWZrOx Catalysts in Glycerol Selective Hydrogenolysis

doi:10.6023/A22120509

Abstract

The Pt-WO_x catalyst system has received much attention for its high activity and selectivity in glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO). In this work, the Ga-doped GaWZrO_x solid acid supports (GaWZ) with different W contents were prepared, and then Pt/GaWZ catalysts were prepared by the wetness impregnation method. The effects of the W contents on the physicochemical properties and catalytic performance of the Pt/GaWZ catalysts were systematically investigated. CO chemisorption and X-ray photoelectron spectroscopy (XPS) characterizations revealed that the dispersion of Pt on the GaWZ supports first increasesd with the increase in the W content, reached a maximum of 86% on the Pt/GaWZ(10) catalyst with 10% (w) of W, and then decreased at 15% (w) of W. UV-Vis diffuse reflectance (UV-Vis DRS), Fourier transform infrared (FTIR), and XPS characterization showed that the W in the Pt/GaWZ catalysts interacted with the Zr—OH functional groups on the tetragonal phase ZrO₂, thus forming mono-dispersed WO_x species. When the W content was greater than 7.5% (w), the second layer of the WO_x species began to emerge. The mono-dispersed WO_x species may be conducive to the high dispersion of Pt. The results of the temperature-programmed desorption of NH₃ (NH₃-TPD) and pyridine adsorption infrared (Py-IR) characterizations showed that the higher the W content, the higher the amount of the acid on the catalyst, with the simultaneous increase in the amounts of both the Brønsted acids and Lewis acids. In glycerol hydrogenolysis over the Pt/GaWZ catalysts, with the increase in the W content, the glycerol conversion evolved in a volcano-shaped trend, while the selectivity to the target product 1,3-PDO increased monotonically. The highest yield of 1,3-PDO of 47.5% was achieved over the Pt/GaWZ(10) catalyst, and the catalyst also displayed excellent recycling stability. On the basis of the characterization results, we propose that the Pt dispersion and the synergistic interaction between Pt and WO_x species determine the activity of the Pt/GaWZ catalysts in glycerol hydrogenolysis, and the Brønsted acid site pertaining to the WO_x species is the key to determine the selectivity to 1,3-PDO over the Pt/GaWZ catalysts, as evidenced by the good linear relationship between the 1,3-PDO selectivity and the amount of the Brønsted acid sites.

Key words: W content, glycerol hydrogenolysis, 1,3-propanediol, Pt dispersion, Brønsted acid

Cite this article

Lan Jiang, Yiqiu Fan, Xiaoxin Zhang, Yan Pei, Shirun Yan, Minghua Qiao, Kangnian Fan, Baoning Zong. Effect of W Content on Structure and Catalytic Performance of Pt/GaWZrO_x Catalysts in Glycerol Selective Hydrogenolysis[J]. Acta Chimica Sinica, 2023, 81(3): 231-238.

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Catalyst	w(Pt)^a/%	w(W)^a/%	S_BET^b/ (m²•g^-1)	V_pore^c/ (cm³•g^-1)	d_pore^d/nm	D_Pt^e/%	S_Pt^f/ (m²•g_Pt^-1)	d_Pt^g/nm
Pt/GaWZ(0)	2.87	0	124	0.39	12.6	33	82	1.4
Pt/GaWZ(5)	2.89	4.9	138	0.37	10.8	54	133	0.9
Pt/GaWZ(7.5)	2.91	7.5	139	0.37	10.7	68	168	0.7
Pt/GaWZ(10)	2.90	10.0	145	0.38	9.8	86	212	0.5
Pt/GaWZ(15)	2.94	14.9	142	0.37	10.6	60	148	0.8

Catalyst	w(Pt)^a/%	w(W)^a/%	S_BET^b/ (m²•g^-1)	V_pore^c/ (cm³•g^-1)	d_pore^d/nm	D_Pt^e/%	S_Pt^f/ (m²•g_Pt^-1)	d_Pt^g/nm
Pt/GaWZ(0)	2.87	0	124	0.39	12.6	33	82	1.4
Pt/GaWZ(5)	2.89	4.9	138	0.37	10.8	54	133	0.9
Pt/GaWZ(7.5)	2.91	7.5	139	0.37	10.7	68	168	0.7
Pt/GaWZ(10)	2.90	10.0	145	0.38	9.8	86	212	0.5
Pt/GaWZ(15)	2.94	14.9	142	0.37	10.6	60	148	0.8

Catalyst	Pt 4f_7/2 BE/eV		Pt²⁺/(Pt⁰＋Pt²⁺) ^a	(Pt/Zr)^a/%	W 4f_7/2 BE/eV		W⁵⁺/(W⁵⁺＋W⁶⁺) ^a	(W/Zr)^a/%
Catalyst	Pt⁰	Pt²⁺	Pt²⁺/(Pt⁰＋Pt²⁺) ^a	(Pt/Zr)^a/%	W⁵⁺	W⁶⁺	W⁵⁺/(W⁵⁺＋W⁶⁺) ^a	(W/Zr)^a/%
Pt/GaWZ(0)	71.3	72.8	0.03	6.71	—	—	—	0
Pt/GaWZ(5)	71.1	72.9	0.05	7.11	35.1	35.7	0.06	14.5
Pt/GaWZ(7.5)	71.3	72.9	0.09	7.58	35.0	35.7	0.09	21.2
Pt/GaWZ(10)	71.2	72.8	0.12	8.31	35.1	35.7	0.12	24.2
Pt/GaWZ(15)	71.2	72.9	0.07	5.54	35.1	35.7	0.15	31.0

Catalyst	Pt 4f_7/2 BE/eV		Pt²⁺/(Pt⁰＋Pt²⁺) ^a	(Pt/Zr)^a/%	W 4f_7/2 BE/eV		W⁵⁺/(W⁵⁺＋W⁶⁺) ^a	(W/Zr)^a/%
Catalyst	Pt⁰	Pt²⁺	Pt²⁺/(Pt⁰＋Pt²⁺) ^a	(Pt/Zr)^a/%	W⁵⁺	W⁶⁺	W⁵⁺/(W⁵⁺＋W⁶⁺) ^a	(W/Zr)^a/%
Pt/GaWZ(0)	71.3	72.8	0.03	6.71	—	—	—	0
Pt/GaWZ(5)	71.1	72.9	0.05	7.11	35.1	35.7	0.06	14.5
Pt/GaWZ(7.5)	71.3	72.9	0.09	7.58	35.0	35.7	0.09	21.2
Pt/GaWZ(10)	71.2	72.8	0.12	8.31	35.1	35.7	0.12	24.2
Pt/GaWZ(15)	71.2	72.9	0.07	5.54	35.1	35.7	0.15	31.0

Catalyst	n_L/(mmol•g⁻¹)	n_B/(mmol•g⁻¹)	n_Py/(mmol•g⁻¹)
Pt/GaWZ(0)	0.41	0.01	0.42
Pt/GaWZ(5)	0.42	0.05	0.47
Pt/GaWZ(7.5)	0.45	0.06	0.51
Pt/GaWZ(10)	0.48	0.07	0.55
Pt/GaWZ(15)	0.50	0.08	0.58

W量对Pt/GaWZrO_x催化剂结构及甘油选择氢解性能的影响