CuFe@SiO<sub>2</sub>催化剂的制备及其在CO加氢合成低碳醇中的应用

侯宾; 韩信有; 林明桂; 房克功

CuFe@SiO₂催化剂的制备及其在CO加氢合成低碳醇中的应用

侯宾^{1, 2},
韩信有^{1, 2},
林明桂¹,
房克功^1, ,

基金项目:

国家自然科学基金 21473230

国家高技术研究发展计划 863计划, 2012AA051002

中国科学院战略先导项目 XDA01020304

详细信息

中图分类号: O643
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出版历程
- 收稿日期: 2015-09-30
- 修回日期: 2015-11-19

Preparation of SiO₂-coated CuFe catalysts for synthesis of higher alcohols from CO hydrogenation

HOU Bin^{1, 2},
HAN Xin-you^{1, 2},
LIN Ming-gui¹,
FANG Ke-gong^{1
, ,}

More Information

Corresponding author: Tel: 0351-4040505, E-mail: kgfang@sxicc.ac.cn

摘要

摘要: 采用共还原-原位包覆法制备一系列SiO₂包覆铜铁双金属纳米颗粒的催化剂 (CuFe@SiO₂), 借助N₂物理吸附、XRD、TEM、SEM-EDS、XPS和H₂-TPR等手段对不同Cu/Fe物质的量比的CuFe@SiO₂催化剂的物理化学性质进行了表征, 并考察了催化剂在CO加氢合成低碳醇中的催化反应性能。结果表明, 所制得的催化剂均为孔分布处于介孔范围的SiO₂包覆的铜铁纳米颗粒。随着Cu/Fe物质的量比降低, 铜铁以复合氧化物存在的比例、总醇及C₂₊OH选择性先增大后减小。其中, 总醇及C₂₊OH选择性在Cu/Fe物质的量比为1时达到最大, 这是由于此时催化剂存在较多的CuFe₂O₄复合氧化物, 铜铁协同作用较强, 同时催化剂也呈现较大的比表面积及孔容, 有利于所生成的醇更快扩散至催化剂表面而避免二次加氢生产烃类。
- 包覆结构 /
- 铜铁双金属 /
- 低碳醇 /
- CO加氢
Abstract: A series of SiO₂-coated CuFe (SiO₂@CuFe) catalysts with different Cu/Fe molar ratios were prepared by co-reduction and in situ coating method.The physicochemical properties of the catalysts were characterized with XRD, TEM, SEM-EDS, XPS and H₂-TPR techniques and N₂ sorption experiment.It was shown that well-dispersed CuFe nanoparticles were completely coated by mesoporous silica in the as-prepared catalysts.The content of Cu-Fe composite oxide in the catalyst and the selectivity of total alcohols and C₂⁺ alcohols both exhibit a volcano trend with the decrease of Cu/Fe molar ratios.When the Cu/Fe molar ratio was 1, the largest amount of CuFe₂O₄ was formed, consequently, causing the strongest interaction between Cu and Fe.In addition, the obtained catalyst possessed higher BET surface area and larger BJH pore volume than the other samples.Thus, alcohol products easily diffuse into/out of its pores, thus avoiding the further hydrogenation to hydrocarbons.As a result, it shows the highest selectivity to total alcohols and C₂⁺ alcohols.
- coated strcture /
- CuFe bimetallic nanoparticle /
- higher alcohols /
- CO hydrogenation

HTML全文

图 1 不同Cu/Fe物质的量比包覆结构催化剂孔径分布图 (a) 及N₂吸附-脱附曲线 (b)

Figure 1. Pore size distribution (a) and N₂ sorption curves (b) of SiO₂@Cu_xFe_y samples

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图 2 不同Cu/Fe物质的量比包覆结构催化剂的XRD谱图

Figure 2. XRD patterns of SiO₂@Cu_xFe_y

a: Cu₄Fe@SiO₂; b: Cu₂Fe@SiO₂; c: CuFe@SiO₂; d: CuFe₂@SiO₂

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图 3 不同Cu/Fe物质的量比包覆结构催化剂的TEM照片

Figure 3. TEM images of the coated structure catalysts with different Cu/Fe mol ratios

(a): Cu₄Fe@SiO₂; (b): Cu₂Fe@SiO₂; (c): CuFe@SiO₂; (d): CuFe₂@SiO₂

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图 4 不同Cu/Fe物质的量比包覆结构催化剂反应前 (a-d) 及反应后 (e-h) SEM照片及相应的元素面扫描图

Figure 4. SEM images and elemental mapping pictures of the fresh and spent Cu₄Fe@SiO₂ (a, e), Cu₂Fe@SiO₂ (b, f), CuFe@SiO₂ (c, g) and CuFe₂@SiO₂ (d, h)

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图 5 不同Cu/Fe物质的量比包覆结构催化剂Cu 2p_3/2(a)、Fe 2p(b) 的XPS谱图

Figure 5. Cu 2p_3/2(a), Fe 2p(b) X-ray photoelectron spectra of SiO₂@Cu_xFe_y

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图 6 不同Cu/Fe物质的量比包覆结构催化剂的H₂-TPR谱图

Figure 6. H₂-TPR profiles of SiO₂@Cu_xFe_y

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图 7 不同Cu/Fe物质的量比包覆结构催化剂的CO加氢催化性能

Figure 7. Catalytic results of SiO₂@Cu_xFe_y with different Cu/Fe ratios

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表 1 不同Cu/Fe物质的量比包覆结构催化剂的物理性质

Table 1. extural properties of SiO₂@Cu_xFe_y catalysts with different Cu/Fe molar ratios

Catalyst	BET surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore diameter d/nm	Capacity w_mol/%		Cu/Fe (mol ratio)
Catalyst	BET surface area A/(m²·g^-1)	Pore volume v/(cm³·g^-1)	Pore diameter d/nm	Cu	Fe	Cu/Fe (mol ratio)
Cu₄Fe@SiO₂	257.57	0.41	6.46	0.98	0.46	2.12
Cu₂Fe@SiO₂	221.68	0.23	4.76	0.46	0.27	1.68
CuFe@SiO₂	284.05	0.37	4.97	0.35	0.46	0.76
CuFe₂@SiO₂	251.95	0.31	4.51	0.21	0.62	0.33

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表 2 不同Cu/Fe物质的量比包覆结构催化剂的Cu 2p_3/2 XPS谱图参数

Table 2. XPS parameters of Cu 2p_2/3 of SiO₂@Cu_xFe_y

Catalyst	Binding energy E/eV				Peak intensity ratio
Catalyst	Cu_A²⁺	Cu_B²⁺	Cu_A²⁺satellite	Cu_B²⁺satellite	I(Cu_A²⁺)	I(Cu_B²⁺)
Cu₄Fe@SiO₂	933.58	935.41	941.99	943.85	0.343	0.657
Cu₂Fe@SiO₂	933.52	935.19	941.62	943.74	0.247	0.753
CuFe@SiO₂	933.34	935.20	941.37	943.83	0.280	0.720
CuFe₂@SiO₂	932.98	934.60	941.38	943.49	0.326	0.674

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表 3 不同Cu/Fe物质的量比包覆结构催化剂的Fe 2p XPS谱图参数

Table 3. XPS parameters of Fe 2p of SiO₂@Cu_xFe_y

Catalyst	Binding energy E/eV			Peak intensity ratio
Catalyst	Fe_A³⁺	Fe_B³⁺	Fe_B³⁺satellite	I(Fe_A³⁺)	I(Fe_B³⁺)
Cu₄Fe@SiO₂	710.78	712.73	718.3	0.421	0.579
Cu₂Fe@SiO₂	711.16	712.72	719.52	0.396	0.604
CuFe@SiO₂	710.87	712.52	719.22	0.399	0.601
CuFe₂@SiO₂	710.58	712.30	718.59	0.421	0.579

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