Zn含量对于Cu-Mn-Zn/ZrO<sub>2</sub>催化剂CO<sub>2</sub>加氢合成甲醇性能的影响研究

WANG Shiwei; YANG Jinhai; XIAO Fukui; ZHAO Ning

doi:10.1016/S1872-5813(23)60391-3

Zn含量对于Cu-Mn-Zn/ZrO₂催化剂CO₂加氢合成甲醇性能的影响研究

doi: 10.1016/S1872-5813(23)60391-3

王世威^{1, 2,},
杨金海^{1, 2,},
肖福魁^{1, 2, ,},
赵宁^{1, 2, ,}

1.
中国科学院山西煤炭化学研究所, 煤炭高效低碳转化全国重点实验室山西太原 030001
2.
中国科学院大学, 北京 100049

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出版历程
- 收稿日期: 2023-08-30
- 修回日期: 2023-09-27
- 录用日期: 2023-09-28
- 网络出版日期: 2023-10-31

Performance of Cu-Mn-Zn/ZrO₂ catalysts for methanol synthesis from CO₂ hydrogenation: the effect of Zn content

WANG Shiwei^{1, 2
,},
YANG Jinhai^{1, 2
,},
XIAO Fukui^{1, 2
, ,},
ZHAO Ning^{1, 2
, ,}

1.
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, China
2.
University of Chinese Academy of Sciences, Beijing 100049, China

Funds: The project was supported by The Natural Science Foundation of Shanxi Province (20220321221303), Science and Technology Major Project of Shanxi Province (202005D121002), The Central Project Guide Local Science and Technology for Development (2020SW26).

More Information

Corresponding author: E-mail: xiaofk@sxicc.ac.cn (Fukui Xiao); zhaoning@sxicc.ac.cn (Ning Zhao)

摘要

摘要: 通过溶胶-凝胶方法制备了一系列不同Zn含量的Cu-Mn-Zn/ZrO₂催化剂，并通过XRD、BET、TPR、N₂O吸附、XPS、TPD和 in-situ DRIFTS进行了表征。结果表明，随着Zn含量增加，催化剂上CO₂加氢反应的反应活性增加。在所有样品中，Cu₃MnZn_0.5Zr_0.5（CMZZ-0.5）在250 ℃和5 MPa条件下具有最高的CO₂转化率（6.5%）和甲醇选择性（73.7%）。表征结果显示，Zn进入Cu_1.5Mn_1.5O₄尖晶石结构，形成ZnO_x，导致催化剂表面羟基含量的增加，同时增加了Cu⁰和Cu^α+的含量，改善了H₂和CO₂的活化能力。此外，通过原位漫反射红外光谱研究了 CO₂转化为甲醇的途径。
- CO₂加氢 /
- 甲醇 /
- Cu-基催化剂 /
- 表面羟基
Abstract: A series of Cu-Mn-Zn/ZrO₂ catalysts with different Zn contents were prepared by sol-gel method and characterized by XRD, BET, TPR, N₂O-adsorption, XPS, TPD and in-situ DRIFTS. It was found that by increasing a certain amount of Zn, the catalytic activity for CO₂ hydrogenation increased. Among all samples, Cu₃MnZn_0.5Zr_0.5 (CMZZ-0.5) possessed the best CO₂ conversion (6.5%) and methanol selectivity (73.7%) at 250 ^oC and 5 MPa. Characterization results showed that Zn entered the Cu_1.5Mn_1.5O₄ spinel structure, forming ZnO_x and thus more surface OH groups. This increased the content of Cu⁰ and Cu^α+, which improved the activation of H₂ and CO₂. The pathway of CO₂ to methanol was also clarified through in situ DRIFTS.
- CO₂ hydrogenation /
- methanol /
- copper-based catalyst /
- surface hydroxyl

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Figure 1 (A) TEM, (B) HR-TEM images and (C) relevant element mapping of the reduced Cu₃MnZn_0.5Zr_0.5 catalysts

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Figure 2 XRD patterns of the fresh (A) and reduced (B) catalysts

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Figure 3 N₂ adsorption-desorption isotherms (A) and pore size distribution (B) of the CMZZ-X catalysts

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Figure 4 XPS spectra for (A)Cu LMM,(B) Zn LMM,(C)C 1s,(D)O 1s of the CMZZ-X catalysts

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Figure 5 H₂-TPR profiles of the CMZZ-X catalysts

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Figure 6 CO₂-TPD profiles of the CMMZ-X catalysts

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Figure 7 H₂-TPD profiles (A) and the amount of H₂ desorption (B) of CMZZ-X catalysts

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Figure 8 The relationships between desorbed H₂ and CO₂ conversion (250 ^oC)

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Figure 9 The relationship between the TOF and the content of O_OH

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Figure 10 In-situ DRIFTS spectra of CO₂ hydrogenation over CMZZ-0 (A), CMZZ-0.25 (B), and CMZZ-0.5 (C), and CMZZ-1.5 (D) at 250 °C

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Figure 11 In-situ DRIFTS spectra of the reduction process for CMZZ-0 (A), CMZZ-0.25 (C), and introduction of CO₂ over CMZZ-0 (B), and CMZZ-0.5 (D) at 250 °C

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Figure 12 Proposed reaction mechanism of CO₂ hydrogenation to methanol over CMZZ-X catalysts

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Table 1 Texture parameters of the CMZZ-X catalysts

Catalyst	A_BET¹ /($ {m}^{2}{g}^{-1} $)	Pore volume¹ /（$ {cm}^{3}{g}^{-1} $）	Pore size¹ /nm	D_cu² /%	A_cu² /($ {m}^{2}{g}^{-1} $)	d_Cu² /nm
CMZZ-0	10.6	0.085	32.7	5.5	3.7	18.3
CMZZ-0.25	9.9	0.048	24.8	7.9	5.4	12.6
CMZZ-0.5	8.1	0.069	28.6	10.4	7.0	9.6
CMZZ-1	7.7	0.033	26.7	7.8	5.3	12.8
CMZZ-1.5	5.1	0.047	27.2	6.3	4.3	15.9
¹: the data were obtained by N₂ adsorption-desorption experiment; ²: the data were calculated by N₂O adsorption-desorption experiment.

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Table 2 Bulk / surface elemental percentages (% molar ratio) of the CMZZ-X catalysts

Catal.	Cu		Mn		Zn		Zr
Catal.	Bulk¹	Surface²	Bulk	Surface	Bulk	Surface	Bulk	Surface
CMZZ-0	77.9	45.3	18.6	35.8	0.1	1.9	3.4	17.0
CMZZ-0.25	68.7	31.9	25.2	48.9	3.5	6.4	2.6	12.8
CMZZ-0.5	73.6	33.9	14.6	32.1	9.5	12.6	2.3	21.4
CMZZ-1	63.5	33.3	18.9	38.3	13.3	16.7	4.3	11.7
CMZZ-1.5	63.0	26.4	14.6	28.3	18.1	20.8	4.3	24.5
¹: calculated from ICP; ²: calculated from XPS.

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Table 3 The relative surface concentration of Cu of the catalysts

Catalyst	Molar ratio /%
Catalyst	Cu⁰/Cu	Cu^α+/Cu	Cu⁺/Cu	Cu²⁺/Cu
CMZZ-0	34.5	16.8	34.2	14.5
CMZZ-0.25	38.2	20.3	32.3	9.2
CMZZ-0.5	40.8	22.3	28.0	8.9
CMZZ-1	40.1	22.7	28.3	8.9
CMZZ-1.5	38.8	21.3	29.5	10.4

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Table 4 The relative surface concentration of Zn of the catalysts

Catalyst	Molar ratio /%
Catalyst	Zn⁰/Zn	Zn²⁺/Zn
CMZZ-0	−	−
CMZZ-0.25	9.1	90.9
CMZZ-0.5	16.7	83.3
CMZZ-1	19.9	80.1
CMZZ-1.5	20.9	79.1

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Table 5 Relative surface concentration of C of the catalysts

Catalyst	Molar ratio /%
Catalyst	CO₃^2-/(CO₃^2- + C)	C/(CO₃^2- + C)
CMZZ-0	12.3	87.7
CMZZ-0.25	11.9	88.1
CMZZ-0.5	12.3	87.7
CMZZ-1	12.1	87.9
CMZZ-1.5	12.4	87.6

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Table 6 Relative surface concentration of O of the catalysts

Catalyst	Molar ratio /%
Catalyst	O_latt/O	O_ads/O	O_OH/O
CMZZ-0	57.8	29.5	12.7
CMZZ-0.25	57.8	24.4	17.8
CMZZ-0.5	56.7	22.6	20.7
CMZZ-1	56.8	22.7	20.5
CMZZ-1.5	59.2	22.5	18.3

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Table 7 Center of reduction peaks with corresponding contributions derived from H₂-TPR profiles of CMZZ-X catalysts

Catalyst	Location of reduction peaks /(°C) and proportion of each peak /(%)
Catalyst	α	β
CMZZ-0	365.5（69.3）	400.0（30.7）
CMZZ-0.25	364.0（75.9）	391.3（24.1）
CMZZ-0.5	359.7（85.8）	391.3（14.2）
CMZZ-1	351.0（76.4）	387.6（23.6）
CMZZ-1.5	353.3（86.8）	390.3（13.2）

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Table 8 Basic sites distribution of the CMZZ-X catalysts

Catalyst	The ratio of basic sites /(%)			Number of total basic sites /(μmol g_cat.⁻¹)
Catalyst	α	β	γ	Number of total basic sites /(μmol g_cat.⁻¹)
CMZZ-0	70.9	21.1	8.0	240.7
CMZZ-0.25	53.6	17.5	28.9	228.5
CMZZ-0.5	25.7	12.3	62.0	239.1
CMZZ-1	22.9	57.2	19.9	237.8
CMZZ-1.5	20.5	62.2	17.3	248.9

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Table 9 Catalytic performance of the catalysts

Catalyst	CO₂ conv. /（%）	CH₃OH sele. /（C-mol%）	STY /（$ mg/ml\cdot {h}^{-1} $）	TOF /（10⁻³ $ {s}^{-1} $）
CMZZ-0	1.9	54.5	11.5	0.6
CMZZ-0.25	4.2	68.5	35.5	1.4
CMZZ-0.5	6.5	73.7	63.6	2.2
CMZZ-1	6.1	67.4	49.8	2.0
CMZZ-1.5	5.1	62.9	41.1	1.7
Reaction conditions: 250 °C, 5 MPa, H₂/CO₂=3∶1, 4,000 mL (mL_cat·h)⁻¹.

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Zn含量对于Cu-Mn-Zn/ZrO₂催化剂CO₂加氢合成甲醇性能的影响研究

doi: 10.1016/S1872-5813(23)60391-3

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Performance of Cu-Mn-Zn/ZrO₂ catalysts for methanol synthesis from CO₂ hydrogenation: the effect of Zn content

Corresponding author: E-mail: xiaofk@sxicc.ac.cn (Fukui Xiao); zhaoning@sxicc.ac.cn (Ning Zhao)

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2023年《燃料化学学报（中英文）》评优结果公布！

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Zn含量对于Cu-Mn-Zn/ZrO2催化剂CO2加氢合成甲醇性能的影响研究

doi: 10.1016/S1872-5813(23)60391-3

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Performance of Cu-Mn-Zn/ZrO2 catalysts for methanol synthesis from CO2 hydrogenation: the effect of Zn content

Corresponding author: E-mail: xiaofk@sxicc.ac.cn (Fukui Xiao); zhaoning@sxicc.ac.cn (Ning Zhao)

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出版历程

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2023年《燃料化学学报（中英文）》评优结果公布！

Zn含量对于Cu-Mn-Zn/ZrO₂催化剂CO₂加氢合成甲醇性能的影响研究

Performance of Cu-Mn-Zn/ZrO₂ catalysts for methanol synthesis from CO₂ hydrogenation: the effect of Zn content