CN117258844A - 一种含混合配体的Co(II)可见光催化剂的制备方法 - Google Patents
一种含混合配体的Co(II)可见光催化剂的制备方法 Download PDFInfo
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Abstract
本发明涉及一种含有混配体的Co(II)配位聚合物可见光催化剂的制备方法。本发明是要解决现有的光催化剂光谱响应范围窄,量子转换效率低,太阳能利用率低的问题。本发明的一种有混配体的Co(II)配位聚合物光催化剂的分子式为[Co(ox)(bpy)](ox=草酸根离子,bpy=4,4'‑联吡啶)。该配位聚合物材料的制备方法为:一、搅拌混合;二、调节pH值;三、加热;四、洗涤及干燥。本发明采用水热合成法,对环境友好,简单易行,成本低,产率高,易于大规模工业化生产。
Description
技术领域
本发明涉及的是一种可见光响应的配位聚合物光催化剂的制备,属于新材料技术领域。
背景技术
目前,水污染问题日益严重,尤其是含重金属离子或有机污染物的废水,一旦被排放到水体或土壤中会破坏生态平衡,危害到海洋生物乃至人类的生命健康。因此,加强污水处理工作是关系到社会发展的重要环节。目前,常见的污水处理技术包括生物处理技术、膜分离技术、厌氧处理技术、生物膜技术等,但这些方法普遍存在运行成本高、易造成二次污染等缺点,新型的光催化处理污水技术成为研究重点,光催化法具有绿色、环保、高效的优点,能有效处理废水中的难降解污染物,且不会造成二次污染,因此,光催化法成为当今污水处理技术的主流方法。
光催化主要是利用半导体催化剂光生电子(e)和光敏物质进行光催化氧化还原反应,是一种先进的氧化还原反应。1979年人们最早实现了在酸性条件下, 利用半导体材料为催化剂,将高毒性的Cr (VI)还原为低毒性的Cr (II)。利用半导体材料进行光催化的步骤为:在光照条件下,催化剂被激发为激发态,催化剂分离的产空穴(h)和电子(e)分别进行氧化还原反应。
1972年,日本科学家Fujishima和Honda在Nature杂志上发表了TiO2单晶电极光催化分解水的研究,标志着光催化研究的开端。光催化氧化法是利用光源照射TiO2、ZnO、CdS、WO3、ZnS、SnO2和FegO4等半导体光催化剂(多为宽禁带的n型半导体氧化物)来诱发强氧化自由基,使水中常规条件下难处理物质得以降解。之前的研究已探明光催化氧化的机理,目前研究最多的是TiO2、CdS等2种光催化剂。但是,TiO2光生电子和空穴容易发生复合致使光催化量子效率降低(≤20%),光谱响应范围狭窄而仅能响应紫外光,带隙能偏高(3.2eV)故而对太阳光利用效率较低(约1 %)。另外,TiO2悬浮光催化体系容易团聚、容易失活、分离及回收困难、妨碍光线穿透力、运行成本高。实验经验得知TiO2因质轻致使称量时体积过大,散发轻微难闻气味。而CdS与TiO2相比,其还原能力更强、还原电位足够负、吸收光范围更宽(可吸收太阳光中占较大的可见光)。然而CdS纳米颗粒易团聚,不能与作用底物充分接触,减缓光降解速率。当其直接用于光降解有机污染物后,较难回收,残留的CdS纳米颗粒将引发二次污染。另外,光生载流子经光辐射后迅速复合而造成严重的光腐蚀,致使其光稳定性变差。因此,研究开发高量子效率的可见光响应的光催化材料用于水体有机污染物降解成为当务之急。
近年来,金属-有机骨架材料(MOFs)由于结构有序且多样、拓扑结构丰富、孔隙度超高、比表面积大、骨架结构稳定和易于掺杂其他组分等特点,使其在吸附领域得到了广泛的关注。金属有机骨架(MOFs)是由金属离子或离子簇和有机配体通过配位键自组装形成的无机-有机杂化晶体材料,它在气体储存分离、质子传导、污染物分析、传感、药物传递等方面具有广泛的应用。其中,MOFs在光催化降解水溶液中的污染物方面展现出优异的性能。同时它也是一类新型的半导体材料,可以通过各种功能化的修饰使其具有良好的光电性质和光催化活性,能带间隙可由金属和配体的不同而调控,且具有大的表面积、易回收等特性,因此它在光催化领域具有潜在的应用前景。通过对配位金属中心原子和有机配体的合理选择,可以获得较小能级差的光活性配位聚合物光催化剂,从而可在可见光区对有机污染物进行催化降解。相较于传统的氧化物光催化材料,配位聚合物光催化剂具有优越的结构特点:高度对称而规则的晶体结构能够减少电荷复合位点的数目,增加产生电子和空穴的可能性;孔的均匀性能够增强反应物或者产物的传质能力,进而提高反应效率;同时多孔结构及大的比表面积不仅更有利于反应物在光催化材料表面吸附,同时能够提供更多的反应位点,增强材料的光反应活性。
基于以上优点,近年来,配位聚合物作为光催化剂降解有机污染物的研究备受瞩目(Huang Y. B.; Liang J.; Wang X. S.; Cao R., Multifunctional Metal-OrganicFramework Catalysts: Synergistic Catalysis and Tandem Reactions, Chemical Society Reviews, 46(2017), 126-157)。2004年,陈开创了配位聚合物在环保应用中的先河(Yu Z. T.; Liao Z. L.; Jiang Y. S.; Li G. H.; Li G. D.; Chen J. S.,Construction of a Microporous Inorganic-Organic Hybrid Compound with UranylUnits, Chemical Communications, 16 (2004) 1814-1815)。2018年,Wang DB 证明,MOFs可以有效应用于四环素类抗生素的降解。(Wang D. B.;Jia F. Y.;Wang H.;Chen F.;FangY.;Dong W. B.;Zeng G. M., Simultaneously efficient adsorption andphotocatalytic degradation of tetracycline by Fe-based MOFs,Journly of Colloid and Interface Science,519(2018)273-284)2021年,Guo XM 发现扩大MOFs有机配体的共轭度可以有效提高其光吸收。(Guo X. M.;Tian X. Y.;Xu, X.;He J. R.,Enhancing visible-light-activity of Ti-based MOFs based on extending theconjugated degree of organic ligands and photocatalytic degradation processand mechanism in real industrial textile wastewaters,Journal of Environmental Chemicalengineering,9(2021)6)。这些工作证明MOFs是一类具有研究价值和应用前景的良好光催化材料。然而,迄今为止,可见光响应型的MOFs光催化剂报道较少,降解率高、稳定性好的可见光配位聚合物光催化材料仍然有待进一步开发。
发明内容
本发明的目的在于提供一种可见光响应的配位聚合物光催化剂的制备方法。
本发明的材料是一种含草酸根(ox)和4,4'-联吡啶(bpy)混配体的Co(II)可见光催化剂,分子式为[Co(ox)(bpy)],其结构特征在于:
1)以bpy、1,2,4-偏三酸、水合肼、氯化钴、草酸为主反应物,一步合成了1种新的含有混配体的Co(II)配位聚合物[Co(ox)(bpy)];
2)是bpy和ox连接Co2+形成的2D层状结构。其空间群为-I,其不对其不对称单元包含一个Co2+离子,一个bpy分子及一个ox分子。晶胞参数为:a = 5.4021(5) Å,b = 10.9756(11) Å,c = 11.3896(10) Å;
3)红外吸收峰(cm-1):3434 s, 2358 s, 1619 s, 1413 w, 1064 m, 808 m, 652w, 480 mm;
4)bpy和ox均采取了µ 2配位模式。首先,bpy配体利用其上的两个N原子单齿连接两个Co2+中心沿c方向拓展为1D无限链结构。然后,利用ox上的两个氧原子,以ox分子为桥,将1D链结构拓展为ac上的2D层状结构。
制备方法特征在于:
1)混合搅拌:将bpy、1,2,4-偏三酸、水合肼、氯化钴、草酸和水以一定的物质的量比混合,然后在室温下搅拌大约四小时;
2)调节pH值:将步骤1)得到的混合物用H2ox调至pH = 7;
3)加热:将步骤2)得到的混合物装入25 ml带有聚四氟乙烯内衬的不锈钢反应釜中,填充度为80%,密封,将其放入150~180°C烘箱内,在自生压力作用下,加热晶化4天。关闭烘箱电源,逐渐冷却至室温,打开反应釜即得到黄色的针状晶体;
4)洗涤及干燥:以步骤3)得到的黄色针状晶体用蒸馏水洗涤1-3次,然后在室温下干燥3-6 h,即可得到含混配体的Co(II)可见光催化剂;
5)本制备方法所得目标产物的产率在70%左右(以Co计算);
6)该产物在水中稳定存在。
本发明提供了一种含混配体的Co(II)可见光催化剂及其制备方法,其优点在于:
1)本发明所得的Co(II)配位聚合物光催化剂稳定性好,可重复利用,可以在空气中长时间放置不变质;
2)本发明的Co(II)配位聚合物光催化剂是在水热条件下得到的,具有很好的水稳定性;
3)本发明的Co(II)配位聚合物以氯化钴、bpy、草酸为主反应物,晶体结构新颖、独特,
4)本发明以低成本的bpy、草酸为原料,采用水热法合成,合成反应对环境友好,简单易行,成本低,产率高,易于大规模工业化生产;
5)本发明所制备含有混配体的Co(II)配位聚合物在可见光下对MB的光催化效果较好,可应用于污水治理领域。
附图说明
图1 实施例1所得含混配体的Co(II)可见光催化剂结构图。
具体实施方式:
下面通过实施例来对本发明作进一步的阐述,但本发明要求保护的范围并不局限于实施例表述的范围。
实施例1 [Co(ox)(bpy)]的制备方法一
将15 ml的蒸馏水加入到50 ml烧杯中,继续加入btca (1,2,4-偏三酸) (96 mg,0.5 mmol),N2H4×H2O (0.13 mL),CoCl2·6H2O (119 mg, 0.5 mmol),bpy (78 mg, 0.5mmol),用H2ox (32 mg, 0.5 mmol)调pH = 7,然后在室温下搅拌4小时;将得到的混合物装入25 mL带有聚四氟乙烯内衬的不锈钢反应釜中,填充度80%,密封,将其放入170 °C烘箱内,在自生压力作用下,加热晶化4天。关闭烘箱电源,逐渐冷却至室温,打开反应釜即得到黄色的针状晶体;将得到的晶体用蒸馏水洗涤3次,然后在温度40 ℃的条件下干燥4 h,即可得到含混配体的配位聚合物光催化剂。所得晶体在Rigaku R-AXIS RAPID IP衍射仪上,用石墨单色化的钼靶Mo-K α射线 (λ = 0.71073 Å),以ω扫描方式在293K温度下收集衍射数据。单晶结构解析用SHELXTL程序完成。利用直接法确定金属原子位置,然后用差值函数法和最小二乘法求出全部非氢原子坐标,并且对非氢原子进行各向异性修正,得到该发明的配位聚合物光催化剂的结构为 Co[(ox)(bpy)]。表1为该配位聚合物的主要晶体学数据。图1为根据测定结果由常用晶体作图软件作出的结构图。
表1
实施例2 [Co(ox)(bpy)]的制备方法二
将btca (1,2,4-偏三酸) (96 mg, 0.5 mmol),N2H4×H2O (0.13 mL),CoCl2·6H2O (119 mg, 0.5 mmol),bpy (78 mg, 0.5 mmol)和水(15 mL)以物质的量比1:1:1:1:833的比例混合,用H2ox (32 mg, 0.5 mmol)调pH = 7然后在室温下搅拌四小时;将得到的混合物装入25 mL带有聚四氟乙烯内衬的不锈钢反应釜中,填充度为80%,密封,将其放入160 °C烘箱内,在自生压力作用下,加热晶化四天。关闭烘箱电源,逐渐冷却至室温,打开反应釜即得到黄色的针状晶体;将得到的晶体用蒸馏水洗涤3次,然后在温度70 ℃的条件下干燥4 h,即可得到含有混合配体Co(II)配位聚合物光催化剂。所得晶体在Rigaku R-AXISRAPID IP衍射仪上,用石墨单色化的钼靶Mo-Kα射线 (λ = 0.71073 Å),以ω扫描方式在293K温度下收集衍射数据。单晶结构解析用SHELXTL程序完成。利用直接法确定金属原子位置,然后用差值函数法和最小二乘法求出全部非氢原子坐标,并且对非氢原子进行各向异性修正,得到该发明的配位聚合物光催化剂的结构为 [Co(ox)(bpy)]。该配位聚合物光催化剂的主要晶体学数据和红外光谱图同实施例1。
实施例3 [Co(ox)(bpy)]的制备方法三
将btca (1,2,4-偏三酸) (96 mg, 0.5 mmol),N2H4×H2O (0.13 mL),CoCl2·6H2O (119 mg, 0.5 mmol),bpy (78 mg, 0.5 mmol)和水(15 mL)以物质的量比1:1:1:1:833的比例混合,用H2ox (32 mg, 0.5 mmol)调pH = 7,然后在室温下搅拌四小时;将得到的混合物装入25 mL带有聚四氟乙烯内衬的不锈钢反应釜中,填充度为80%,密封,将其放入180 °C烘箱内,在自生压力作用下,加热晶化四天。关闭烘箱电源,逐渐冷却至室温,打开反应釜即得到黄色的针状晶体;将得到的晶体用蒸馏水洗涤3次,然后在温度60 ℃的条件下干燥4 h,即可得到含有混合配体Co(II)配位聚合物光催化剂。所得晶体在Rigaku R-AXISRAPID IP衍射仪上,用石墨单色化的钼靶Mo-K α射线 (λ = 0.71073 Å),以ω扫描方式在293(2)K温度下收集衍射数据。单晶结构解析用SHELXTL程序完成。利用直接法确定金属原子位置,然后用差值函数法和最小二乘法求出全部非氢原子坐标,并且对非氢原子进行各向异性修正,得到该发明的配位聚合物光催化材料的结构为[Co(ox)(bpy)]。该配位聚合物荧光材料的主要晶体学数据和红外光谱图同实施例1。
Claims (8)
1.一种含混配体的Co(II)可见光响应光催化剂,分子式为[Co(ox)(bpy)],其结构特征在于:
1)以4,4'-联吡啶、1,2,4-偏三酸、水合肼、氯化钴、草酸为主反应物,一
步合成了1种新的含有混配体的Co(II)配位聚合物[Co(ox)(bpy)] (ox =
草酸根离子,bpy = 4,4'-联吡啶);
2)是bpy和ox连接Co2+形成的2D层状结构,其空间群为-I,其不对其不对称单元包含一个Co2+离子,一个bpy分子及一个ox分子,晶胞参数为:a = 5.4021(5) Å,b = 10.9756(11)Å,c = 11.3896(10) Å;
3)红外吸收峰(cm-1):3434 s, 2358 s, 1619 s, 1413 w, 1064 m, 808 m, 652 w,480 mm;
4)bpy和ox均采取了µ 2配位模式,首先,bpy配体利用其上的两个N原
子单齿连接两个Co2+中心沿c方向拓展为1D无限链结构,然后,利
用ox上的两个氧原子,以ox分子为桥,将1D链结构拓展为ac上的
2D层状结构。
2.如权利要求1所述的含混配体的Co(II)可见光响应催化剂的制备方法按照以下步骤进行:
1)混合搅拌:将4,4'-联吡啶、1,2,4-偏三酸、水合肼、氯化钴、草酸和水以一定的物质的量比混合,然后在室温下搅拌大约四小时;
2)调节pH值:将步骤1)得到的混合物用H2ox调至pH = 7;
3)加热:将步骤2)得到的混合物装入25 ml带有聚四氟乙烯内衬的不锈钢反应釜中,填充度为80%,密封,将其放入150~180°C烘箱内,在自生压力作用下,加热晶化4天,关闭烘箱电源,逐渐冷却至室温,打开反应釜即得到黄色的针状晶体;
4)洗涤及干燥:以步骤3)得到的黄色针状晶体用蒸馏水洗涤1-3次,然后在室温下干燥3-6 h,即可得到含有混配体的Co(II)配位聚合物光催化剂。
3.根据权利要求2所述的一种含4,4'-联吡啶(bpy)的混配体Co(II)可见光催化剂的制备方法,其特征在于所述步骤1)为将15 ml的蒸馏水加入到50 ml烧杯中,继续加入btca(1,2,4-偏三酸) (96 mg, 0.5 mmol),N2H4×H2O (0.13 mL),CoCl2·6H2O (119 mg, 0.5mmol),bpy (78 mg, 0.5 mmol),用H2ox (32 mg, 0.5 mmol)调pH = 7,然后在室温下搅拌4小时。
4.根据权利要求2所述的一种含混配体的Co(II)可见光催化剂的制备方法,其特征在于所述步骤2)为将步骤1)得到的混合物用H2ox (32 mg, 0.5 mmol)调pH = 7,然后在室温下搅拌4小时。
5.根据权利要求2所述的一种含混配体的Co(II)可见光催化剂的制备方法,其特征在于所述步骤3)为在温度为120 °C的烘箱中加热3天。
6.根据权利要求2所述的一种含混配体的Co(II)可见光催化剂的制备方法,其特征在于所述步骤3)为在温度为180°C的烘箱中加热5天。
7.根据权利要求2所述的一种含混配体的Co(II)可见光催化剂的制备方法,其特征在于所述步骤4)为温度为50 °C的烘箱中干燥3 h。
8.根据权利要求2所述的一种含混配体的Co(II)可见光催化剂的制备方法,其特征在于所述步骤4)为温度为170°C的烘箱中干燥5 h。
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