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
计量
- 文章访问数: 109
- HTML全文浏览量: 164
- PDF下载量: 0
- 被引次数: 0
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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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)

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 全尺寸图片幻灯片

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

下载: 导出CSV

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

下载: 导出CSV

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

下载: 导出CSV

参考文献(39)

[1]	MEDFORD A J, LAUSCHE A C, ABILD-PEDERSEN F, TEMEL B, SCHJODT N C, NORSKOV J K, STUDT F.Activity and selectivity trends in synthesis gas conversion to higher alcohols[J].Top Catal, 2014, 57(1/4):135-142.
[2]	肖康, 鲍正洪, 齐行振, 王新星, 钟良枢, 房克功, 林明桂, 孙予罕.合成气制混合醇双功能催化研究进展[J].催化学报, 2013, 34(1):116-129. doi: 10.1016/S1872-2067(11)60496-8 XIAO Kang, BAO Zheng-hong, QI Xing-zhen, WANG Xin-xing, ZHONG Liang-shu, FANG Ke-gong, LIN Ming-gui, SUN Yu-han.Advances in bifunctional catalysis for higher alcohol synthesis from syngas[J].Chin J Catal, 2013, 34(1):116-129. doi: 10.1016/S1872-2067(11)60496-8
[3]	ZHANG Q W, LI X H, FUJIMOTO K R.Pd-promoted Cr/ZnO catalyst for synthesis of methanol from syngas[J].Appl Catal A:Gen, 2006, 309(1):28-32. doi: 10.1016/j.apcata.2006.04.026
[4]	SMITH K J, ANDERSON R B.A chain growth scheme for the higher alcohols synthesis[J].J Catal, 1984, 85(2):428-436. doi: 10.1016/0021-9517(84)90232-X
[5]	LI Z R, FU Y L, JIANG M, MENG M, XIE Y N, HU T D, LIU T.Structures and performance of Pd-Mo-K/Al₂O₃ catalysts used for mixed alcohol synthesis from synthesis gas[J].Catal Lett, 2000, 65(1/3):43-48. doi: 10.1023/A:1019017321625
[6]	SHI X R, JIAO H J, HERMANN K, WANG J G.CO hydrogenation reaction on sulfided molybdenum catalysts[J].J Mol Catal A:Chem, 2009, 312(1/2):7-17.
[7]	XIANG M L, LI D B, XIAO H C, ZHANG J L, QI H J, LI W H, ZHONG B, SUN Y H.Synthesis of higher alcohols from syngas over Fischer-Tropsch elements modified K/beta-Mo₂C catalysts[J].Fuel, 2008, 87(4/5):599-603.
[8]	LIU C C, LIN M G, FANG K G, MENG Y, SUN Y H.Preparation of nanostructured molybdenum carbides for CO hydrogenation[J].RSC Adv, 2014, 4(40):20948-20954. doi: 10.1039/c4ra01586j
[9]	MEI D H, ROUSSEAU R, KATHMANN S M, GLEZAKOU V A, ENGELHARD M H, JIANG W L, WANG C M, GERBER M A, WHITE J F, STEVENS D J.Ethanol synthesis from syngas over Rh-based/SiO₂ catalysts:A combined experimental and theoretical modeling study[J].J Catal, 2010, 271(2):325-342. doi: 10.1016/j.jcat.2010.02.020
[10]	PRIETO G, CONCEPCION P, MARTINEZ A, MENDOZA E.New insights into the role of the electronic properties of oxide promoters in Rh-catalyzed selective synthesis of oxygenates from synthesis gas[J].J Catal, 2011, 280(2):274-288. doi: 10.1016/j.jcat.2011.03.025
[11]	FANG K G, LI D B, LIN M G, XIANG M L, WEI W, SUN Y H.A short review of heterogeneous catalytic process for mixed alcohols synthesis via syngas[J].Catal Today, 2009, 147(2):133-138. doi: 10.1016/j.cattod.2009.01.038
[12]	GAO W, ZHAO Y F, LIU J M, HUANG Q W, HE S, LI C M, ZHAO J W, WEI M.Catalytic conversion of syngas to mixed alcohols over CuFe-based catalysts derived from layered double hydroxides[J].Catal Sci Technol, 2013, 3(5):1324-1332. doi: 10.1039/c3cy00025g
[13]	LU Y W, YU F, HU J, LIU J.Catalytic conversion of syngas to mixed alcohols over Zn-Mn promoted Cu-Fe based catalyst[J].Appl Catal A:Gen, 2012, 429:48-58.
[14]	林明桂, 房克功, 李德宝, 孙予罕.Zn、Mn助剂对CuFe合成低碳醇催化剂的影响[J].物理化学学报, 2008, 24(5):833-838. http://www.cnki.com.cn/Article/CJFDTOTAL-WLHX200805019.htm LIN Ming-gui, FANG Ke-gong, LI De-bao, SUN Yu-han.Effect of Zn and Mn promoters on copper-iron based catalysts for higher alcohol synthesis[J].Acta Phys Chem Sin, 2008, 24(5):833-838. http://www.cnki.com.cn/Article/CJFDTOTAL-WLHX200805019.htm
[15]	林明桂, 房克功, 李德宝, 孙予罕.Cu-Fe基催化剂上CO加氢反应过程中物相的转化行为[J].催化学报, 2008, 29(6):559-565. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200806011.htm LIN Ming-gui, FANG Ke-gong, LI De-bao, SUN Yu-han.Phase transformation in cu-fe-based catalyst during CO hydrogenation[J].Chin J Catal, 2008, 29(6):559-565. http://www.cnki.com.cn/Article/CJFDTOTAL-CHUA200806011.htm
[16]	XIAO K, BAO Z H, QI X Z, WANG X X, ZHONG L S, FANG K G, LIN M G, SUN Y H.Structural evolution of CuFe bimetallic nanoparticles for higher alcohol synthesis[J].J Mol Catal A:Chem, 2013, 378:319-325. doi: 10.1016/j.molcata.2013.07.006
[17]	LIN M G, FANG K G, LI D B, SUN Y H.CO hydrogenation to mixed alcohols over co-precipitated Cu-Fe catalysts[J].Catal Commun, 2008, 9(9):1869-1873. doi: 10.1016/j.catcom.2008.03.004
[18]	MOURDIKOUDIS S, LIZ-MARZAN L M.Oleylamine in nanoparticle synthesis[J].Chem Mater, 2013, 25(9):1465-1476. doi: 10.1021/cm4000476
[19]	CARUSO F.Nanoengineering of particle surfaces[J].Adv Mater, 2001, 13(1):11-22. doi: 10.1002/(ISSN)1521-4095
[20]	CHAUDHURI R G, PARIA S.Core/shell nanoparticles:Classes, properties, synthesis mechanisms, characterization, and applications[J].Chem Rev, 2012, 112(4):2373-2433. doi: 10.1021/cr100449n
[21]	COSTI R, SAUNDERS A E, BANIN U.Colloidal hybrid nanostructures:A new type of functional materials[J].Angew Chem, 2010, 49(29):4878-4897. doi: 10.1002/anie.v49:29
[22]	ZHONG C J, MAYE M M.Core-shell assembled nanoparticles as catalysts[J].Adv Mater, 2001, 13(19):1507-1511. doi: 10.1002/1521-4095(200110)13:19<>1.0.CO;2-S
[23]	LI K T, HSU M H, WANG I.Palladium core-porous silica shell-nanoparticles for catalyzing the hydrogenation of 4-carboxybenzaldehyde[J].Catal Commun, 2008, 9(13):2257-2260. doi: 10.1016/j.catcom.2008.05.012
[24]	LI L, HE S C, SONG Y Y, ZHAO J, JI W J, Au C T.Fine-tunable Ni@porous silica core-shell nanocatalysts:Synthesis, characterization, and catalytic properties in partial oxidation of methane to syngas[J].J Catal, 2012, 288:54-64. doi: 10.1016/j.jcat.2012.01.004
[25]	ZENG B, HOU B, JIA L T, LI D B, SUN Y H.Fischer-Tropsch synthesis over different structured catalysts:The effect of silica coating onto nanoparticles[J].J Mol Catal A:Chem, 2013, 379:263-268. doi: 10.1016/j.molcata.2013.08.008
[26]	JOO S H, PARK J Y, TSUNG C K, YAMADA Y, YANG P, SOMORJAI G A.Thermally stable Pt/mesoporous silica core-shell nanocatalysts for high-temperature reactions[J].Nat Mater, 2009, 8(2):126-131. doi: 10.1038/nmat2329
[27]	HU Y J, WANG Y Q, LU Z H, CHEN X S, XIONG L H.Core-shell nanospheres Pt@SiO₂ for catalytic hydrogen production[J].Appl Surf Sci, 2015, 341:185-189. doi: 10.1016/j.apsusc.2015.02.094
[28]	KIRILLOV S A.Surface area and pore volume of a system of particles as a function of their size and packing[J].Microporous Mesoporous Mater, 2009, 122(1/3):234-239. http://www.baidu.com/link?url=X4KTjeqOu27V0fh1Nt0AaSlA3VuNQ8ecFWQWxahnuNyAxVJCHOzhcdd7fUrd8vfJj82qi8W7n3_cuZ0JqqJfvCUGY_E9UxT92LR8zQPaqWmAyF0ml8HcPtTbrHlZ4lp_OJb8xGUt53MkkXmwz4H7Df21N_uysvSZAg7nJm_uprUno9X-efYJbTI-TYA8oWOL2VMX7CizxcyJo9JIOZKZTcyZ0npa9cgHSFXqh8hbkluFZGknVFFDlgzdQElAVh2KWHlbX9OeZ3lDJ-4sXNKFKWyuoSqmnIXZp7-rYWNdmI8AalgZWu48oI8d47WGxU8GACie7vmmPpepdOuz4UNTBFIAnxTCyAMKpcR25iGutqYJEAq_qBm7zZPZj939e11j&wd=&eqid=8402a8be0004847b0000000558bfe184
[29]	辛勤, 罗孟飞.现代催化研究方法[M].北京:科学出版社, 2009. XIN Qing, LUO Meng-fei.Modern catalysis research methods[M].Beijing:Science Press, 2009.
[30]	YAO Q, LU Z H, ZHANG Z, CHEN X, LAN Y.One-pot synthesis of core-shell Cu@SiO₂ nanospheres and their catalysis for hydrolytic dehydrogenation of ammonia borane and hydrazine borane[J].Scientific Rep, 2014, 4:7597. doi: 10.1038/srep07597
[31]	肖康.铜基双金属纳米颗粒混合醇合成研究[D].上海:中国科学院上海高等研究院, 2013. XIAO Kang.Cu-based bimetallic nanoparticles for higher alcohols synthesis[D].Shanghai:Shanghai Adv ResInst, Chin Acad Sci, 2013.
[32]	LI F, ZHANG L H, EVANS D G, DUAN X.Structure and surface chemistry of manganese-doped copper-based mixed metal oxides derived from layered double hydroxides[J].Colloids Surf A:Phys Eng Asp, 2004, 244(1):169-177. http://www.baidu.com/link?url=5Wt3VeRtJeB_xS0TGHvH0ZV4Q6ujrs9WGMUNvma4rZRWOXt6PsseyyJyseJiFxeJW2qT84FpTat2waHQpH3CMLf64Asb-W-LTSTE5M6Mt9XhDM9zB_ALeK1UXvPB5xls6V0UQHCZsrvej96c06tBLGx81KYtMtrqHwZCqHb9SvDUJpL7QrEDhx8Gsvk_3O-h0T_mh8NLDAg9F4zcLxmBM4i4apgc_XFrVPIpQ7mcmZwNpWan0PBIQuMY9jXFrUdLmxY0SLF5cOsvjqNfFQoxYQxjhnYbJ_W7S4nxLMhf2ANbvUGARWHfE0ZeVsRVoCkSW4mztgcnUE6oz1p2M38EG0DzNLNKGCBy3mUmwtfpNTZovFzqxPFS4wWmfGXrtI8gicnuNPCpct-cftl_jHde8q&wd=&eqid=f7596a54000493ec0000000558bfe176
[33]	LENGLET M, FOULATIER P, DVEB J, ARSÉNE J.Caractérisation de la liaison Cu-O dans les oxydes mixtes CuMM'O 4(M=Fe, Cr;M'=Al, Ga, Mn).Corrélation avec l'effet Jahn-Teller[J].Phys Status Solidi, 1986, 94(2):461-466. doi: 10.1002/(ISSN)1521-396X
[34]	冉宏峰, 房克功, 林明桂, 孙予罕.Cu/Fe组成对CuFe基低碳醇催化剂的反应性能的影响[J].天然气化工, 2010, 35(4):1-5. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH201004002.htm RAN Hong-feng, FANG Ke-gong, LIN Ming-gui, SUN Yu-han.Effect of Cu/Fe ratios on catalytic performances of co-precipitated Cu-Fe based catalysts for higher alcohols synthesis[J].Nat Gas Chem Ind, 2010, 35(4):1-5. http://www.cnki.com.cn/Article/CJFDTOTAL-TRQH201004002.htm
[35]	LINDNER U, PAPP H.XPS and ISS characterization of potassium or copper containing Fe/Mn oxide catalysts for Fischer-Tropsch synthesis[J].Appl Surf Sci, 1988, 32(1/2):75-92. http://www.baidu.com/link?url=5pH182qh8Z1d-KMAQgDIKsjap_BRyFlSaTL_GV8NCMuOf1YDnPqb5_EkgekC1iWkWGtNAHGJjXuxyAgQilyXv0acOISoX8aohfGXpZ8TfwCLmLF-BEqN3fG7ARs1rg1QqlP_NGZ2Oa9BnbXiF55WuqjDsXtvsNY3zn1XqdoTJLWlZe2losqRwoEAhXP2vDc79NGKpewJGQzWrZpY7YTjTvF6b8NvzjHbPcKAziOdvEbOSDeG7TXr3_l-q6h2sIv2nBkn9dyFAIJARnehbgIJa-CQv4YrcSxINR2tZ2OTH1daJjvWXsCLGx9VQnco5eDNb7830Dx0GWrXGacid_AMAZwknR_8upNfBLp0G5vVmqmhuINoXFVvRKhF98YW8KtDNMQncEI99ezCqQu-30iACa&wd=&eqid=f799fbf600041b330000000558bfe168
[36]	DING M Y, YANG Y, WU B S, XU J, ZHANG C H, XIANG H W, LI Y W.Study of phase transformation and catalytic performance on precipitated iron-based catalyst for Fischer-Tropsch synthesis[J].J Mol Catal A:Chem, 2009, 303(1):65-71.
[37]	GRZYBEK T, KLINIK J, BUCZEK B.XPS studies of no selective reduction catalysts after SO₂ poisoning[J].Surf Interface Anal, 1995, 23(12):815-822. doi: 10.1002/(ISSN)1096-9918
[38]	GRZYBEK T, PAPP H, BAERNS N.Fe/Mn oxide catalysts for fischer-tropsch synthesis:Part VXPS surface characterization of calcined and reduced samples[J].Appl Catal, 1987, 29(2):335-350. doi: 10.1016/S0166-9834(00)82903-6
[39]	ALLEN G C, HALLAM K R.Characterisation of the spinels M (x) Co (1-x) Fe (2) O (4)(M=Mn, Fe or Ni) using X-ray photoelectron spectroscopy[J].Appl Surf Sci, 1996, 93(1):25-30. doi: 10.1016/0169-4332(95)00186-7