W量对Pt/GaWZrOx催化剂结构及甘油选择氢解性能的影响

doi:10.6023/A22120509

摘要/Abstract

在甘油选择氢解制1,3-丙二醇(1,3-PDO)反应中, Pt-WO_x催化剂体系因其高活性和高选择性而受到研究者的广泛关注. 本工作制备了W量不同的Ga掺杂GaWZrO_x固体酸(GaWZ), 然后作为载体采用浸渍法制备了Pt/GaWZ催化剂, 系统考察了W的量对催化剂物化性质和催化性能的影响. CO化学吸附和X射线光电子能谱(XPS)表征发现, 随着GaWZ载体中W量的增加, 其上负载的Pt的分散度先增加, 在10% (w) W的Pt/GaWZ(10)催化剂上达到最高值86%, 然后在15% (w) W时降低. 紫外-可见漫反射(UV-Vis DRS)、傅里叶变换红外(FTIR)和XPS表征表明, Pt/GaWZ催化剂中的W与四方相ZrO₂表面的Zr—OH基团存在较强作用, 形成了单分散的WO_x物种; 当大于7.5% (w) W时, 开始出现第二层WO_x物种. 单分散的WO_x物种可能是Pt分散度提高的重要原因. 由程序升温氨脱附(NH₃-TPD)和吡啶吸附红外(Py-IR)表征结果可见, W的量越高, 催化剂的酸量越大, Brønsted酸和Lewis酸同时增加. 在甘油氢解反应中, 随着W的增加, Pt/GaWZ催化剂上的甘油转化率呈火山型变化趋势, 而目标产物1,3-PDO的选择性则持续提高. 1,3-PDO得率在Pt/GaWZ(10)催化剂上达到最高, 为47.5%, 而且该催化剂有良好的套用稳定性. 根据表征结果, 我们推测Pt的分散度及Pt与WO_x物种之间的协同作用决定了Pt/GaWZ催化剂在甘油氢解反应中的活性; 而1,3-PDO选择性与Brønsted酸量之间呈现的良好的线性关系, 说明WO_x物种上的Brønsted酸位是决定Pt/GaWZ催化剂上1,3-PDO选择性的关键.

关键词: 钨含量, 甘油氢解, 1,3-丙二醇, 铂分散度, Brønsted酸

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

引用此文

姜兰, 范义秋, 张晓昕, 裴燕, 闫世润, 乔明华, 范康年, 宗保宁. W量对Pt/GaWZrO_x催化剂结构及甘油选择氢解性能的影响[J]. 化学学报, 2023, 81(3): 231-238.

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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图/表 11

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

表1. Pt/GaWZ(x)催化剂的基本物化性质

Table 1. Basic physicochemical properties of the Pt/GaWZ(x) catalysts

图1. Pt/GaWZ(x)催化剂的XRD谱. (a) 0, (b) 5%, (c) 7.5%, (d) 10%和(e) 15% (w) W

Figure 1. XRD patterns of the Pt/GaWZ(x) catalysts with (a) 0, (b) 5%, (c) 7.5%, (d) 10%, and (e) 15% (w) of W

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

表2. Pt/GaWZ(x)催化剂的Pt 4f和W 4f谱拟合结果

Table 2. The Pt 4f and W 4f fitting results of the Pt/GaWZ(x) catalysts

图2. Pt/GaWZ(x)催化剂在373 K下的Py-IR谱. (a) 0, (b) 5%, (c) 7.5%, (d) 10%和(e) 15% (w) W

Figure 2. Py-IR spectra of the Pt/GaWZ(x) catalysts with (a) 0, (b) 5%, (c) 7.5%, (d) 10%, and (e) 15% (w) of W acquired at 373 K

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

表3. Pt/GaWZ(x)催化剂的酸性质

Table 3. Acidic properties of the Pt/GaWZ(x) catalysts

Catalyst	Conv.^b/%	CTL^b/%	Sel. (x(C)/% in liquid products)^b				Yield_1,3-PDO/%	STY/ (g•g_Pt^-1•h^-1)
Catalyst	Conv.^b/%	CTL^b/%	1,3-PDO	1,2-PDO	1-PO	2-PO	Yield_1,3-PDO/%	STY/ (g•g_Pt^-1•h^-1)
Pt/GaWZ(0)	4.2	2.7	6.3	52.5	28.0	4.6	0.2	0.02
Pt/GaWZ(5)	17.5	16.2	40.2	21.4	30.7	6.2	6.5	0.60
Pt/GaWZ(7.5)	50.8	41.4	50.3	8.3	33.4	6.7	20.8	1.91
Pt/GaWZ(10)	96.5	87.5	54.3	0.4	38.8	6.4	47.5	4.37
Pt/GaWZ(15)	71.3	66.5	60.7	2.1	29.6	6.6	40.4	3.71

表4. Pt/GaWZ(x)催化剂上的甘油催化氢解反应结果

Table 4. The catalytic results of the Pt/GaWZ(x) catalysts in the hydrogenolysis of glycerol a

图3. Pt/GaWZ(10)催化剂上的甘油氢解反应进程

Figure 3. The reaction course of glycerol hydrogenolysis over the Pt/GaWZ(10) catalyst Reaction conditions: 0.10 g of catalyst, 2.0 g of 30% (w) glycerol aqueous solution, temperature of 413 K, H2 pressure of 6.0 MPa, and stirring rate of 500 r?min-1

Catalyst	Substrate	Conv.^b/ %	CTL^b/ %	Sel. (x(C)/% in liquid products)^b
Catalyst	Substrate	Conv.^b/ %	CTL^b/ %	1,3-PDO	1,2-PDO	1-PO	2-PO
Pt/GaWZ(10)	glycerol	96.5	87.5	54.3	0.4	38.8	6.4
	1,3-PDO	22.0	21.7	—	n.d. ^c	98.5	0.9
	1,2-PDO	84.2	83.4	n.d.	—	93.2	6.7
Pt/GaWZ(0)	glycerol	4.2	2.7	6.3	52.5	28.0	4.6
	1,3-PDO	4.6	4.5	—	n.d.	93.2	3.6
	1,2-PDO	1.9	1.6	n.d.	—	55.0	9.3

表5. Pt/GaWZ(10)和Pt/GaWZ(0)催化剂上甘油、1,3-PDO及1,2-PDO的氢解结果比较

Table 5. Comparison of the hydrogenolysis results of glycerol, 1,3-PDO, and 1,2-PDO over the Pt/GaWZ(10) and Pt/GaWZ(0) catalysts a

图4. Pt/GaWZ(10)催化剂的套用稳定性

Figure 4. The recycling stability of the Pt/GaWZ(10) catalyst

图5. Pt/GaWZ(x)催化剂上甘油转化率与活性比表面积的关系

Figure 5. The relationship between the glycerol conversion and the active surface area of the Pt/GaWZ(x) catalysts

图6. Pt/GaWZ(x)催化剂上1,3-PDO选择性与Br?nsted酸量的关系

Figure 6. A plot of the selectivity to 1,3-PDO against the amount of the Br?nsted acid on the Pt/GaWZ(x) catalysts

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