制备条件对Cu_2O结构及甲醛乙炔化性能的影响
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摘要
以Cu(NO_3)_2·3H_2O为铜源,在液相还原过程中,调变沉淀剂NaOH、还原剂L-抗坏血酸钠的加入顺序制备了Cu_2O,借助X射线粉末衍射(XRD)、傅里叶变换红外光谱(FT-IR)、拉曼光谱(Raman)、俄歇电子能谱(XAES)和H_2程序升温还原(H_2-TPR)等手段研究了制备条件对Cu_2O结构及催化甲醛乙炔化性能的影响.结果表明,调变NaOH及L-抗坏血酸钠的添加方式改变了Cu_2O的结晶度与粒径尺寸,从而使Cu_2O表现出不同的炔化性能.先加入NaOH,后加入抗坏血酸钠, Cu_2O结晶度高,粒径大,难以转化为活性物种炔化亚铜;先加入抗坏血酸钠,后加入NaOH, Cu_2O被过度还原为非活性的金属Cu,两者均造成催化剂活性较低.而NaOH和抗坏血酸钠混合后添加的方式制备出表面Cu_2O结晶完整而体相Cu_2O分散度高的样品,这使得Cu_2O高效转化为炔化亚铜活性物种,表现出最优的炔化性能,在适宜的反应条件下, 1,4-丁炔二醇收率达到71.7%,经6次循环后,仍保持在56.5%.
Cuprous oxide(Cu_2O) samples were prepared by liquid reduction method using copper nitrate(Cu(NO_3)_2) as copper source, sodium hydroxide(NaOH) as precipitant and sodium ascrobate as reducing agent, by adjusting the addition method of precipitant and reducing agent. The effect of addition method on structure and catalytic performance of Cu_2O for formaldehyde ethynylation was investigated, combined with X-ray powder diffraction(XRD), Fourier transform infrared spectroscopy(FT-IR), Raman spectroscopy(Raman), Auger electron spectroscopy(XAES) and H_2 temperature-programmed reduction(H_2-TPR). The results showed that the adding sequence of NaOH and sodium ascorbate played an important role in the properties and catalytic performance of Cu_2O. Cu_2O(1), prepared by adding NaOH firstly, exhibited highly crystallinity and large crystal size, which made it difficult to convert into active cuprous acetylene species. Cu_2O(3) prepared by adding sodium ascorbate firstly was excessively reduced to inactive metallic Cu~0. Neither Cu_2O(1) and Cu_2O(3) exhibited low catalytic performance for the formaldehyde ethynylation. The Cu_2O(2), which was prepared by co-adding of NaOH and sodium ascorbate, showed high surface crystallinity and high dispersion of bulk Cu_2O, which made the Cu_2O efficiently converted into active species cuprous acetylide. The Cu_2O(2) sample showed the optimal catalytic performance for formaldehyde ethynylation. Under the suitable reaction conditions, 1,4-butynediol yield reached 71.7%, after 6 cycles, remained about 56.5%.
Cuprous oxide(Cu_2O) samples were prepared by liquid reduction method using copper nitrate(Cu(NO_3)_2) as copper source, sodium hydroxide(NaOH) as precipitant and sodium ascrobate as reducing agent, by adjusting the addition method of precipitant and reducing agent. The effect of addition method on structure and catalytic performance of Cu_2O for formaldehyde ethynylation was investigated, combined with X-ray powder diffraction(XRD), Fourier transform infrared spectroscopy(FT-IR), Raman spectroscopy(Raman), Auger electron spectroscopy(XAES) and H_2 temperature-programmed reduction(H_2-TPR). The results showed that the adding sequence of NaOH and sodium ascorbate played an important role in the properties and catalytic performance of Cu_2O. Cu_2O(1), prepared by adding NaOH firstly, exhibited highly crystallinity and large crystal size, which made it difficult to convert into active cuprous acetylene species. Cu_2O(3) prepared by adding sodium ascorbate firstly was excessively reduced to inactive metallic Cu~0. Neither Cu_2O(1) and Cu_2O(3) exhibited low catalytic performance for the formaldehyde ethynylation. The Cu_2O(2), which was prepared by co-adding of NaOH and sodium ascorbate, showed high surface crystallinity and high dispersion of bulk Cu_2O, which made the Cu_2O efficiently converted into active species cuprous acetylide. The Cu_2O(2) sample showed the optimal catalytic performance for formaldehyde ethynylation. Under the suitable reaction conditions, 1,4-butynediol yield reached 71.7%, after 6 cycles, remained about 56.5%.
引文
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[21] Zhao Hua-tao (赵华涛),Wang Dong (王栋),Zhang Lan-yue (张兰月),et al.A simple method for the preparation of Cu2O with different morphologies in high reaction concentration (高反应浓度下制备不同形貌氧化亚铜的简易方法) [J].Chem Inorg J Chin(无机化学学报),2009,29(1):142-146.
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[2] a.Wang Z P,Niu Z Z,Hao Q A,et al.Enhancing the ethynylation performance of CuO-Bi2O3 nanocatalysts by tuning Cu-Bi interactions and phase structures [J].Catalysts,2019,9(35):1-18.b.Zhao Fang(赵芳),Wang Chang-zhen(王长真),Tian Ya-ni(田亚妮),et al.Metal promoter effect of Ni-M/SiO2 in hydrogenation of 1,4-butynediol(Ni-M/SiO2催化 1,4-丁炔二醇加氢的金属助剂效应) [J].J Mol Catal(China)(分子催化),2019,33(1):83-89.c.Liao Xin(廖欣),Zhang Yin(张因),Li Hai-tao(李海涛),et al.CeO2 prepared in N2 atmosphere and supported Ni-based catalyst for hydrogenation of maleic anhydride(氮气气氛下焙烧的CeO2载体负载 Ni 基催化剂的顺酐加氢性能研究) [J].J Mol Catal(China)(分子催化),2017,31(1):53-60.
[3] Guo Jiang-yuan (郭江渊),Li Hai-tao (李海涛),Zhang Zhi-long (张智隆),et al.Effect of surface acidity on Ni/SiO2-Al2O3 catalyst performance for 1,4-butynediol hydrogenation (表面酸性对Ni /SiO2-Al2O3催化剂催化1,4-丁炔二醇高压加氢性能的影响) [J].J Mol Catal (China) (分子催化),2016,30(1):37-45.
[4] Liu Lin-li (刘琳丽),Li Hai-tao (李海涛),Wang Chang-zhen (王长真),et al.Effect of Supports on the hydrogenation of 1,4-butynediol over supported Ni catalyst (负载Ni催化剂上1,4-丁炔二醇加氢反应的载体效应研究) [J].J Mol Catal (China) (分子催化),2018,32(2):99-106.
[5] Wang Zhi-peng (王志鹏),Niu Zhu-zhu (牛珠珠),Ban Li-jun (班丽君),et al.Formaldehyde ethynylation reaction over Cu2O supported on TiO2 with different phases (不同晶相TiO2负载 Cu2O催化甲醛乙炔化反应) [J].Chem J Chin Univer(高等学校化学学报),2019,40(2):334-341.
[6] Duncanson I T,Sutherland I W,Cullen B,et al.The hydrogenation of 2-butyne-1,4-diol over a carbon-supported palladium catalyst [J].Catal Lett,2005,103(3):195-199.
[7] Telkar M M,Rode C V,Jaganathan R,et al.Platinum catalyzed hydrogenation of 2-butyne-1,4-diol [J].J Mol Catal A:Chem,2002,187(1):81-93.
[8] Wang Zhi-peng (王志鹏),Niu Zhu-zhu (牛珠珠),Ban Li-jun (班丽君),et al.The influence of N doping on TiO2 supported Cu based catalyst for formaldehyde ethynylation (N掺杂对TiO2负Cu基催化剂甲醛乙炔化性能的影响) [J].J Shanxi Nor Univer(Nat Sci Edit) (陕西师范大学学报),2019,47(1):99-106.
[9] Gao Yu-ming (高玉明),Tian Heng-shui (田恒水),Zhu Yun-feng (朱云峰).Catalytic synthesis on 1,4-butynediol by CuO-Bi2O3 particles (CuO-Bi2O3粉体催化合成1,4-丁炔二醇的研究) [J].Guangdong Chem Indus (广东化工),2008,35(9):53-55.
[10] Jiang Jian (蒋健),Lin Shen (林深),Liu Chun-lian (刘春莲).Preparation and catalytic activity of Cu/Bi2O3 nanoparticles (纳米CuO/Bi2O3粉体的制备及催化性能) [J].Chin J Syn Chem(合成化学),2005,13(1):45-48.
[11] Zheng Yan (郑艳),Sun Zi-jin (孙自瑾),Wang Yong-zhao (王永钊),et al.Preparation of CuO-Bi2O3/SiO2-MgO catalyst and its ethynylation performance (CuO-Bi2O3/SiO2-MgO催化剂的制备及炔化性能) [J].J Mol Catal (China) (分子催化),2012,26(3):233-238.
[12] Yang G H,Xu Y B,Su X T,et al.MCM-41 supported CuO/Bi2O3 nanoparticles as potential catalyst for 1,4-butynediol synthesis[J].Ceram Int,2014,40(3):3969-3973.
[13] Luo Ping (罗平),Zhao Xin-ming (赵新明),Li Hai-xia (李海侠),et al.Research of EQ-201 acetylene catalyst in reppe synthesizing 1,4-butynediol (Reppe法合成1,4-丁炔二醇EQ-201型炔化催化剂的研究) [J].Chem Engineer Des Commun(化工设计通讯),2012,38(5):87-93.
[14] Wang Jun-jun (王俊俊),Li Hai-tao (李海涛),Ma Zhi-qiang (马志强),et al.Preparation of magnetic CuO-Bi2O3/Fe3O4-SiO2-MgO catalyst and its catalytic performance for formaldehyde ethynylation (磁性CuO-Bi2O3 /Fe3O4-SiO2-MgO催化剂的制备及甲醛乙炔化性能) [J].J Chem Indus Engineer(化工学报),2015,66(6):2098-2104.
[15] Ma Zhi-qiang (马志强),Zhang Hong-xi (张鸿喜),Li Hai-tao (李海涛),et al.Preparation of core-shell CuO-Bi2O3@meso-SiO2 catalyst and its catalytic performance for formaldehyde ethynylation (核壳结构CuO-Bi2O3@meso-SiO2催化剂的制备及甲醛乙炔化性能) [J].Indus Catal(工业催化),2015,23(5):344-348.
[16] Luo Min (罗敏),Li Hai-tao (李海涛),Ma Zhi-qiang (马志强),et al.Researches on activation process of CuO-Bi2O3/SiO2-MgO catalyst in formaldehyde ethynylation reaction (甲醛乙炔化反应中CuO-Bi2O3 /SiO2-MgO催化剂活化过程研究) [J].Indus Catal(工业催化),2014,22(5):363-368.
[17] Hort E V,Piscataway N J.Ethynylation catalyst and method of production alkynols by low pressure reactions,US 3920759 [P].1975-11-18.
[18] Wang Jun-jun (王俊俊),Zhang Hong-xi (张鸿喜),Li Hai-tao (李海涛),et al.Effect of iron promoter on structure and catalytic performance of CuO/SiO2-MgO catalyst for formaldehyde ethynylation (Fe助剂对CuO/SiO2-MgO催化剂结构和甲醛乙炔化性能的影响) [J].Indus Catal (工业催化),2015,23(6):455-458.
[19] Yang Guo-feng (杨国峰),Li Hai-tao (李海涛),Zhang Hong-xi (张鸿喜),et al.Effect of NaOH concentration on structure and catalytic performance of Cu2O for formaldehyde ethynylation (NaOH浓度对Cu2O结构及甲醛乙炔化性能的影响) [J].J Mol Catal (China)(分子催化),2016,30(6):540-546.
[20] Li Hai-tao (李海涛),Niu Zhu-zhu (牛珠珠),Yang Guo-feng (杨国峰),et al.Support effect of Cu2O/TiO2 employed in formaldehyde ethynylation (Cu2O/TiO2催化甲醛乙炔化反应的载体效应) [J].J Chem Indus Engineer(化工学报),2018,69(6):2512-2518.
[21] Zhao Hua-tao (赵华涛),Wang Dong (王栋),Zhang Lan-yue (张兰月),et al.A simple method for the preparation of Cu2O with different morphologies in high reaction concentration (高反应浓度下制备不同形貌氧化亚铜的简易方法) [J].Chem Inorg J Chin(无机化学学报),2009,29(1):142-146.
[22] Dawson P,Hargreave M M,Wilkinson G R.The dielectric and lattice vibrational spectrum of cuprous oxide [J].J Phys Chem Sol,1973,34(12):2201-2208.
[23] Singhal A,Pai M R,Rao R,et al.Copper(I) oxide nanocrystals one step synthesis,characterization,formation mechanism and photocatalytic properties [J].Euro J Inorg Chem,2013,2013(14):2640-2651.
[24] Ren D,Deng Y L,Handoko A D,et al.Selective electrochemical reduction of carbon dioxide to ethylene and ethanol on copper(I) oxide catalysts [J].ACS Catal,2015,5(5):2814-2821.
[25] Kaviyarasan K,Anandan S,Mangalaraja,et al.Sono chemical synthesis of Cu2O nanocubes for enhanced chemiluminescence applications [J].Ultrason Sono Chem,2016,29:388-393.
[26] Kim J Y,Rodriguez J A,Hanson J C,et al.Reduction of CuO and Cu2O with H2∶H embedding and kinetic in the formation of suboxides [J].J Am Chem Soc,2003,125(35):10684-10692.
[27] Rodriguez J A,Hanson J C,Frenkel A I,et al.Experimental and theoretical studies on the reaction of H2 with NiO:Role of O vacancies and mechanism for oxide reduction [J].J Am Chem Soc,2002,124(2):346-354.
[28] Delmon B,Thomas J M,Bell R G,et al.Handbook of heterogeneous catalysis [M].Germany:Wiley-VCH Verlag Gmbh,1997.264-365.
[29] Kung H H.Studies in surface science and catalysis [M].Netherlands:Elsevier,1989.45.
[30] Gupte S P,Jadkar P B,Chaudhari R V.Kinetics of ethynylation of formaldehyde to butynediol [J].React Kinet Catal Lett,1984,24(1/2):173-177.
[31] Tamhankar S S,Gupte S P,Chaudhari R V.Kinetics of a non-catalytic slurry reaction:reaction of acetylene with cuprous oxide suspended in water [J].Chem Eng J,1981,22:15-24.