CN111921559A - 一种单位点过渡金属共价有机框架光催化剂及其制备方法 - Google Patents
一种单位点过渡金属共价有机框架光催化剂及其制备方法 Download PDFInfo
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- QEIRCDAYPQFYBI-UHFFFAOYSA-N 6-(5-aminopyridin-2-yl)pyridin-3-amine Chemical group N1=CC(N)=CC=C1C1=CC=C(N)C=N1 QEIRCDAYPQFYBI-UHFFFAOYSA-N 0.000 claims abstract description 12
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- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
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Abstract
本发明属于功能材料技术领域,具体为一种单位点过渡金属共价有机框架光催化剂及其制备方法。本发明采用溶剂热条件下的一锅法制备策略,以5,5'‑二氨基‑2,2'‑联吡啶、多醛基功能化单体和过渡金属盐类为反应原料,在过渡金属与2,2'‑联吡啶配位的同时,通过醛胺缩合反应将其聚合成为高度有序的共价有机框架结构。该方法制备得到的光催化剂,可使共价有机框架的光吸收范围拓展到近红外区间,提高了全光谱范围的光子捕获能力,降低了光生电子/空穴的复合几率,显著提高了光催化转换的效率。本发明方法操作简单、过程可控,所制备的材料结构明确,利用太阳能催化分解水产生氢气的效率高,使再生资源转换为清洁能源,具有良好的应用前景。
Description
技术领域
本发明属于功能材料技术领域,具体涉及一种单位点过渡金属共价有机框架光催化剂及其制备方法。
背景技术
自蒸汽机发明以来,工业化进程快速发展,化石能源的使用不断扩大,带来了一系列问题,例如:环境污染、温室效应等。利用高效的清洁能源,不仅是人类社会可持续发展的要求,而且也高度切合我们国家的战略发展愿景。氢气是一种高效清洁能源,燃烧后产物为水,但是目前氢气主要通过煤炭气化、重油及天然气水蒸气催化转化、电解水等方法制备,这些方案虽然已经工业化,但仍面临大量消耗化石能源的问题。
光催化产氢技术是利用清洁的太阳能催化分解水制备氢气,相比于其他产氢技术,设备简单,投资成本低,为廉价绿色制备氢气提供了可能。目前已有许多无机半导体材料,如TiO2、CdS、KNbO3等被应用于光催化产氢技术的研究,但是无机材料普遍面临太阳能利用效率低,光吸收范围窄,光生电子/空穴易复合等问题。
利用半导体性质的共价有机框架作为光催化剂,引起了人们的广泛关注。相比于传统的无机半导体材料,共价有机框架具有可调控的构建基元和功能性,高的比表面积、孔隙率,以及显著的结晶性。在共价有机框架上实现单位点的金属配位,可有效拓宽光吸收的范围,增加太阳光利用率,缩短电子传输距离,使光生载流子有效分离和转移,从而提高分解水产氢的效率。
发明内容
本发明的目的在于提供一种能够有效提高分解水产氢效率的单位点过渡金属共价有机框架光催化剂及其制备方法。
本发明提供的单位点过渡金属共价有机框架催化剂,是将5,5'-二氨基-2,2'-联吡啶、多醛基取代的功能单体与过渡金属盐为原料,采用溶剂热条件下的一锅法制备得到,制备的具体步骤为:
以5,5'-二氨基-2,2'-联吡啶、多醛基取代的功能单体和过渡金属盐为原料,在一定条件下,过渡金属离子与2,2'-联吡啶上的N原子络合形成催化单位点,得到金属络合物;同时该金属络合物通过醛胺缩合反应,可逆共价键连接构筑单位点的过渡金属联吡啶共价有机框架,记为Bp(M)-COFs:M代表过渡金属离子Ni、Co、Mn、Fe、Zn中的一种或者几种。
本发明提供的单位点过渡金属共价有机框架催化剂制备方法,具体操作流程如下:
(1)将0.00001 ~ 6 mol 5,5'-二氨基-2,2'-联吡啶 与0.00001 ~ 6 mol多醛基单体加入到耐热玻璃管中;再加0.05~100mL,0.01~10 mol/L 酸溶液;加入0.01-2 mol/L过渡金属离子源的溶液0.05~100mL;加入0.1~10000mL的有机溶剂;
(2)冻融脱气,采用常用油泵抽气,去除反应体系的空气,密闭后将玻璃管放入到45~150℃的烘箱中,静置1-7天;
(3)取出玻璃管待其降到室温后,将产物取出,过滤,采用四氢呋喃洗涤,抽干后得到固体粉末;
(4)然后放到索氏提取装置中,加热至80-100℃,待提取溶液为无色透明时,将产物取出;放入真空烘箱中40-100℃烘干,即得到Bp(M)-COF。
本发明中,所述的5,5'-二氨基-2,2'-联吡啶的分子结构式如下:
本发明中,所述的多醛基取代的功能单体自选如下结构式的功能单体:
本发明中,所述的过渡金属离子为Ni、Co、Mn、Fe、Zn中的一种或几种;所述金属盐为乙酸盐、草酸盐、卤化物或硫酸盐。
本发明中,所述的酸溶液采用甲酸、乙酸、乳酸、盐酸、硫酸中的一种或几种。
本发明中,所述的有机溶剂采用甲醇、乙醇、二氧六环、正丁醇、甲苯中的一种或几种。
本发明制备方法采用一锅法,避免了后修饰过程中出现的过渡金属聚集、配位点集中于材料表面的问题,并保持了金属化共价有机框架的高比表面积和一维开放孔通道。
本发明制备得到的光催化剂具备单位点均匀分布的过渡金属离子,并固定在共价有机框架的一维孔道壁上,一方面在反应动力学中,可充分接触助催化剂和水分子,另一方面在光物理性质中,拓展了共价有机框架的光吸收范围(拓展到近红外区间),提高了全光谱范围的光子捕获能力;并通过金属离子的极化作用降低光生电子/空穴的复合速率,从而在分解水产氢反应中显著提高光催化利用效率。
本发明较现有技术的显著优点在于:
(1)本发明所得光催化剂具有较宽的光吸收范围,高的比表面积,均匀的孔径,能使光生电子/空穴有效分离,从而可显著提高其光催化反应效率;
(2)本发明在功能基元络合过渡金属离子的同时参与共价有机框架的构筑,该一锅法制备的光催化剂,可使过渡金属在共价有机框架上形成单位点和均匀的孔道壁上分布,结构明确,操作简单,方法可控易于重复。
附图说明
图1为实施例1 紫外可见光吸收范围曲线。
图2为实施例1等温吸附脱附曲线。
图3为实施例2等温吸附脱附曲线。
图4为实施例3 镍的结合能数据。
图5为实施例3 元素的分布图。
图6为实施例3的红外谱图数据。
图7为实施例4的X射线衍射数据。
图8为实施例4气相色谱检测氢气的数据。
具体实施方式
为了使本发明所述的内容更加便于理解,下面结合具体实施方式对本发明所述的技术方案做进一步的说明,但是本发明不仅限于此。
实施例1,Bp(Mn)-COF的制备:
将0.03mmol 5,5'-二氨基-2,2'-联吡啶,0.022 mmol三羟基均三苯甲醛,加入到耐热玻璃管中,加0.05ml 0.2 mol/L盐酸溶液,加入0.1mol/L氯化锰溶液 0.1 ml,加入2 ml的甲醇,采用常用油泵抽气,去除反应体系的空气,密闭后将玻璃管放入到60℃的烘箱中静置4天;取出玻璃管待其降到室温后,将产物取出过滤,采用四氢呋喃洗涤,抽干后得到固体粉末,然后放到索氏提取装置中,加热到85℃,待提取溶液为无色透明即可将产物取出。放入真空烘箱中50℃烘干即得到Bp(Mn)-COF。
实施例2,Bp(Zn)-COF的制备:
将0.31 mmol 5,5'-二氨基-2,2'-联吡啶 与0.02 mmol 4-[3,5-二(4-甲酰基苯基)苯基]苯甲醛,0.2 mmol 2-羟基-1,3,5-苯三甲醛 加入到耐热玻璃管中,加0.4ml 0.2 mol/L盐酸溶液,加入0.4 mol/L乙酸锌溶液 0.5 ml,加入20 ml的乙醇,冻融脱气,采用常用油泵抽气,去除反应体系的空气,密闭后将玻璃管放入到80℃的烘箱中静置3天;取出玻璃管待其降到室温后,将产物取出过滤,采用四氢呋喃洗涤,抽干后得到固体粉末,然后放到索氏提取装置中,加热到90℃,待提取溶液为无色透明即可将产物取出。放入真空烘箱中40℃烘干即得到Bp(Zn)-COF。
实施例3, Bp(Ni)-COF的制备:
将0.305 mol 5,5'-二氨基-2,2'-联吡啶 与0.1mol 2-羟基-1,3,5-苯三甲醛,0.1mol均苯三甲醛 加入到耐热玻璃管中,加50ml 0.2 mol/L醋酸溶液,加入0.4 mol/L氯化镍溶液 20 ml,加入0.5 L的二氧六环,0.5L 甲苯。冻融脱气,采用常用油泵抽气,去除反应体系的空气,密闭后将玻璃管放入到95℃的烘箱中静置6天;取出玻璃管待其降到室温后,将产物取出过滤,采用四氢呋喃洗涤,抽干后得到固体粉末,然后放到索氏提取装置中,加热到85℃,待提取溶液为无色透明即可将产物取出。放入真空烘箱中70℃烘干即得到Bp(Ni)-COF。
实施例4,Bp(Co,Zn)-COF的制备:
将4 mol 5,5'-二氨基-2,2'-联吡啶 与2.01 mol 1,3,6,8-四(4-甲醛基苯基)芘加入到耐热玻璃管中,加90 ml 4 mol/L醋酸溶液,加入1 mol/L硫酸钴溶液 20 ml,0.5 mol/L草酸锌溶液 20 ml,加入8L的正丁醇。冻融脱气,采用常用油泵抽气,去除反应体系的空气,密闭后将玻璃管放入到100℃的烘箱中静置2天;取出玻璃管待其降到室温后,将产物取出过滤,采用四氢呋喃洗涤,抽干后得到固体粉末,然后放到索氏提取装置中,加热到90 ℃,待提取溶液为无色透明即可将产物取出。放入真空烘箱中40℃烘干即得到Bp(Co,Zn)-COF。
将上述实施例1~4中所制备的过渡金属共价有机框架催化剂取0.01g,放入装有0.1 mol/L 抗坏血酸混合水溶液的光催化反应器中,加入 1 wt % 氯铂酸,以自然光为光源,在转速为300r/min的条件下用气相色谱测试光催化产氢活性,结果见表1。
表1 本发明实施例所制备过渡金属共价有机框架光催化剂的催化活性
以上所述仅为本发明的较佳实施例,凡依本发明申请专利范围所做的均等变化与修饰,皆应属本发明的涵盖范围。
Claims (9)
1.一种单位点过渡金属共价有机框架光催化剂的制备方法,其特征在于,采用溶剂热条件下的一锅法,具体步骤如下:以5,5'-二氨基-2,2'-联吡啶、多醛基取代的功能单体和过渡金属盐为原料,在一定条件下,过渡金属离子与2,2'-联吡啶上的N原子络合形成催化单位点,得到金属络合物;同时该金属络合物通过醛胺缩合反应,可逆共价键连接构筑单位点的过渡金属联吡啶共价有机框架,记为Bp(M)-COFs,其中M代表过渡金属离子Ni、Co、Mn、Fe、Zn中的一种或者几种。
2.根据权利要求1所述的制备方法,其特征在于,具体操作流程如下:
(1)将0.00001 ~ 6 mol 5,5'-二氨基-2,2'-联吡啶 与0.00001 ~ 6 mol多醛基单体加入到耐热玻璃管中;再加0.05~100mL,0.01~10 mol/L 酸溶液;加入0.01-2 mol/L过渡金属离子源的溶液0.05~100mL;加入0.1~10000mL的有机溶剂;
(2)冻融脱气,采用常用油泵抽气,去除反应体系的空气,密闭后将玻璃管放入到45~150℃的烘箱中,静置1-7天;
(3)取出玻璃管待其降到室温后,将产物取出,过滤,采用四氢呋喃洗涤,抽干后得到固体粉末;
(4)然后放到索氏提取装置中,加热至80-100℃,待提取溶液为无色透明时,将产物取出;放入真空烘箱中40-100℃烘干,即得到Bp(M)-COF。
5.根据权利要求2所述的制备方法,其特征在于,所述的过渡金属离子为Ni、Co、Mn、Fe、Zn中的一种或几种;所述过渡金属盐为乙酸盐、草酸盐、卤化物或硫酸盐。
6.根据权利要求2所述的制备方法,其特征在于,所述的酸溶液采用甲酸、乙酸、乳酸、盐酸、硫酸中的一种或几种。
7.根据权利要求2所述的制备方法,其特征在于,所述的有机溶剂采用甲醇、乙醇、二氧六环、正丁醇、甲苯中的一种或几种。
8.一种如权利要求1-7之一所述制备方法制得的单位点过渡金属共价有机框架光催化剂。
9.如权利要求8所述的单位点过渡金属共价有机框架光催化剂在分解水产氢中的应用。
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