铜硅催化剂中层状硅酸铜的形成过程
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摘要
采用一种在催化剂制备过程中取样的方法,研究了Cu/SiO_2催化剂中层状硅酸铜的形成过程。通过对样品进行N_2-吸附、FTIR、XRD和TEM表征,发现层状硅酸铜主要形成于催化剂制备的蒸氨阶段,而在老化阶段则主要发生了铜氨离子与硅溶胶表面羟基之间的离子交换反应。
The formation of copper phyllosilicate in Cu / SiO_2 catalyst was intensively studied in this paper.Samples were taken during the catalyst preparation procedure and systematically characterized by N_2-adsorption,FTIR,XRD,and TEM. The characterization showed that the ion-exchange between copper ammonia complex and Si—OH took place in the aging stage while copper phyllosilicate formed during the ammonia evaporation process.
The formation of copper phyllosilicate in Cu / SiO_2 catalyst was intensively studied in this paper.Samples were taken during the catalyst preparation procedure and systematically characterized by N_2-adsorption,FTIR,XRD,and TEM. The characterization showed that the ion-exchange between copper ammonia complex and Si—OH took place in the aging stage while copper phyllosilicate formed during the ammonia evaporation process.
引文
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[12]Chen L,Guo P,Qiao M,et al.Cu/Si O2catalysts prepared by the ammonia-evaporation method:Texture,structure,and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol[J].Journal of Catalysis,2008,257(1):172-180
[13]Yin A,Guo X,Dai W,et al.Highly active and selective copper-containing HMS catalyst in the hydrogenation of dimethyl oxalate to ethylene glycol[J].Applied Catalysis A:General,2008,349(1/2):91-99
[14]Van Der Grift C J G,Elber P A,Mulder A,et al.Preparation of silica-supported copper catalysts by means of deposition-precipitation[J].Applied Catalysis,1990,59(1):275-289
[15]Toupance T,Kermarec M,Lambert J F,et al.Conditions of formation of copper phyllosilicates in silica-supported copper catalysts prepared by selective adsorption[J].Journal of Physical Chemistry B,2002,106(9):2 277-2 286
[16]Yue H,Zhao Y,Zhao S,et al.A copper-phyllosilicate core-sheath nanoreactor for carbon-oxygen hydrogenolysis reactions[J].Nature Communications,2013,4(9):2 339-2 339
[17]Poels E K,Brands D S.Modification of Cu/Zn O/Si O2catalysts by high temperature reduction[J].Applied Catalysis A:General,2000,191(1/2):83-96
[18]Hidemitsu T,Yoshio O,Tominaga K.Spectroscopic study of Cu(II)ions supported on silica gel by cation exchange method[J].Journal of Catalysis,1975,40(2):197-202
[2]Zhao S,Yue H,Zhao Y,et al.Chemoselective synthesis of ethanol via hydrogenation of dimethyl oxalate on Cu/Si O2:Enhanced stability with boron dopant[J].Journal of Catalysis,2013,297(1):142-150
[3]Zhao L,Zhao Y,Wang S,et al.Hydrogenation of dimethyl oxalate using extruded Cu/Si O2catalysts:Mechanical strength and catalytic performance[J].Industrial&Engineering Chemistry Research,2012,51(43):13 935-13 943
[4]Gong J,Yue H,Zhao Y,et al.Synthesis of ethanol via syngas on Cu/Si O2catalysts with balanced Cu-0-Cu+sites[J].Journal of the American Chemical Society,2012,134(34):13 922-13 925
[5]Yue H,Zhao Y,Ma X,et al.Ethylene glycol:Properties,synthesis,and applications[J].Chemical Society Reviews,2012,41(11):4 218-4 244
[6]Yue H,Zhao Y,Zhao L,et al.Hydrogenation of dimethyl oxalate to ethylene glycol on a Cu/Si O2/cordierite monolithic catalyst:Enhanced internal mass transfer and stability[J].AICh E Journal,2012,58(9):2 798-2 809
[7]Yin A,Wen C,Dai W,et al.Surface modification of HMS material with silica sol leading to a remarkable enhanced catalytic performance of Cu/Si O2[J].Applied Surface Science,2011,257(13):5 844-5 849
[8]Yin A,Guo X,Fan K,et al.Influence of copper precursors on the structure evolution and catalytic performance of Cu/HMS catalysts in the hydrogenation of dimethyl oxalate to ethylene glycol[J].Applied Catalysis A:General,2010,377(1/2):128-133
[9]Yin A,Guo X,Fan K,et al.Ion-Exchange temperature effect on Cu/HMS catalysts for the hydrogenation of dimethyl oxalate to ethylene glycol[J].Chem Cat Chem,2010,2(2):206-213
[10]Guo X,Yin A,Dai W,et al.One pot synthesis of ultra-high copper contented Cu/SBA-15 material as excellent catalyst in the hydrogenation of dimethyl oxalate to ethylene glycol[J].Catalysis Letters,2009,132(1/2):22-27
[11]Yin A,Guo X,Dai W,et al.The nature of active copper species in Cu-HMS catalyst for hydrogenation of dimethyl oxalate to ethylene glycol:New insights on the synergetic effect between Cu0 and Cu+[J].Journal of Physical Chemistry C,2009,113(25):11 003-11 013
[12]Chen L,Guo P,Qiao M,et al.Cu/Si O2catalysts prepared by the ammonia-evaporation method:Texture,structure,and catalytic performance in hydrogenation of dimethyl oxalate to ethylene glycol[J].Journal of Catalysis,2008,257(1):172-180
[13]Yin A,Guo X,Dai W,et al.Highly active and selective copper-containing HMS catalyst in the hydrogenation of dimethyl oxalate to ethylene glycol[J].Applied Catalysis A:General,2008,349(1/2):91-99
[14]Van Der Grift C J G,Elber P A,Mulder A,et al.Preparation of silica-supported copper catalysts by means of deposition-precipitation[J].Applied Catalysis,1990,59(1):275-289
[15]Toupance T,Kermarec M,Lambert J F,et al.Conditions of formation of copper phyllosilicates in silica-supported copper catalysts prepared by selective adsorption[J].Journal of Physical Chemistry B,2002,106(9):2 277-2 286
[16]Yue H,Zhao Y,Zhao S,et al.A copper-phyllosilicate core-sheath nanoreactor for carbon-oxygen hydrogenolysis reactions[J].Nature Communications,2013,4(9):2 339-2 339
[17]Poels E K,Brands D S.Modification of Cu/Zn O/Si O2catalysts by high temperature reduction[J].Applied Catalysis A:General,2000,191(1/2):83-96
[18]Hidemitsu T,Yoshio O,Tominaga K.Spectroscopic study of Cu(II)ions supported on silica gel by cation exchange method[J].Journal of Catalysis,1975,40(2):197-202