CN114805832A - 含过渡金属的手性共价有机框架光催化剂及其制备方法 - Google Patents
含过渡金属的手性共价有机框架光催化剂及其制备方法 Download PDFInfo
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- CN114805832A CN114805832A CN202210370193.4A CN202210370193A CN114805832A CN 114805832 A CN114805832 A CN 114805832A CN 202210370193 A CN202210370193 A CN 202210370193A CN 114805832 A CN114805832 A CN 114805832A
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Abstract
本发明属于功能材料技术领域,具体为含过渡金属的手性共价有机框架光催化剂及其制备方法。本发明制备方法包括:在溶剂热条件下,多氨基单体与多醛基单体在手性调节剂的存在下发生席夫碱反应,形成酮‑烯胺结构的连接键,合成具有良好结晶性和多孔性的手性共价有机框架材料;以酮‑烯胺结构作为络合位点,将过渡金属单原子负载在框架上,得到含有过渡金属单原子的手性共价有机框架材料。该手性共价有机框架材料作为光催化剂用于可见光分解水制氢,可显著提升析氢过程的效率。
Description
技术领域
本发明属于功能材料技术领域,具体涉及一种手性共价有机框架光催化剂及其制备方法。
背景技术
在碳中和大目标下,氢能作为一种高效的清洁能源备受瞩目。氢气在提供能量的同时,产生的副产物只有水,符合人们对于理想清洁能源的期望。在燃料电池领域,以氢气为燃料可以提供高效的电力。虽然氢气是低碳环保的下一代能源,但目前氢气的获取主要通过煤、石油、天然气的催化转化以及工业电解等高耗能途径,并不是严格意义上的绿色能源。此外,氢气高昂的价格也在一定程度上限制了其应用范围。
光催化产氢技术以太阳光为能源催化水分解产氢,是制备绿色氢气的有效途径。同时相较于其他氢气制备方法,以太阳能分解水产氢设备简单,成本较低,为输出廉价绿色能源提供了可能。目前析氢光催化剂普遍使用铂作为析氢助催化剂,贵金属的使用限制了光催化剂的大范围应用,提高了成本。
相较于无机光催化剂,有机光催化剂有着单元可调性强、吸光能力突出等优势。而相比于传统有机光催化材料,共价有机框架材料有序的堆叠结构和丰富的开放孔道使其具备了反应效率上的优势。在共价有机框架材料上进行金属络合,能够提升材料的催化反应效率和框架上的光激发电子空穴分离程度,进而带来光催化析氢效率的提高。
发明内容
本发明的目的在于提供一种能够高效催化水分解产氢的含过渡金属单原子的手性共价有机框架光催化剂及其制备方法。
本发明提供的含过渡金属单原子的手性共价有机框架催化剂,是以多醛基取代的功能单体、多氨基取代的功能单体、手性调节剂与过渡金属盐为原料,多步制备得到,具体步骤为:
步骤一,以多醛基取代的功能单体和多氨基取代的功能单体为原料,在手性调节剂存在的条件下,通过席夫碱反应形成可逆共价键,从而构筑手性共价有机框架材料;
步骤二,在温和的络合反应中,通过金属诱导使手性共价有机框架材料发生酮-烯醇结构异变,获得含酚基氧/亚胺氮的双齿配位点,从而合成出过渡金属络合的手性共价有机框架材料。
步骤一的具体操作流程为:将0.00001 ~ 6 mol多醛基单体、0.00001~12mol手性调节剂与0.00001 ~ 6 mol多氨基单体分别溶于0.1~5mL一定比例的混合溶剂,加入到耐热玻璃管中,并加0.01 ~ 1mL催化剂,于77K液氮中冷却,冻融脱气3次,密封后于70~180℃烘箱中反应1~7天;反应结束后过滤得到产物,使用四氢呋喃洗涤,得到手性共价有机框架材料;
步骤二的具体操作流程为:将5mg~100mg手性共价有机框架材料分散于0.5 ~100mL 0.005~0.3mol/L过渡金属离子溶液中,在20~70℃下反应6~18h,反应结束后,过滤得到产物,并用去离子水和四氢呋喃洗涤产物,得到含过渡金属单原子的手性共价有机框架材料。
进一步地,步骤一优化的操作流程为:将0.01 ~4mol多醛基单体、0.01~8mol手性调节剂与0.01 ~ 4mol多氨基单体分别溶于1~3mL一定比例的混合溶剂,加入到耐热玻璃管中,并加0.1 ~ 1 mL催化剂,于77K液氮中冷却,冻融脱气3次,密封后于90~140℃烘箱中反应1~7天;反应结束后过滤得到产物,使用四氢呋喃洗涤,得到手性共价有机框架材料;
进一步地,步骤二优化的操作流程为:将20mg~70mg手性共价有机框架材料分散于10 ~60mL0.05~0.3mol/L过渡金属离子溶液中,在40~70℃下反应8~12h,反应结束后,过滤得到产物,并用去离子水和四氢呋喃洗涤产物,得到含过渡金属单原子的手性共价有机框架材料。
本发明中,所述的多醛基取代的功能单体选自如下结构式的功能单体:
本发明中,所述的多氨基取代的功能单体选自如下结构式的功能单体:
步骤一中,所述的混合溶剂为均三甲苯/二氧六环、正丁醇/二氧六环、正丁醇/邻二氯苯、均三甲苯/正丁醇之中的任意一种。
步骤一中,所述的混合溶剂包含两种溶液,这两种溶液的体积比为1:1~1:9。两种溶液优化的体积比为1:3~1:6。
步骤一中,所述的手性调节剂采用S/R-1-苯乙胺、S/R-叔丁基亚磺酰胺、S/R-2-甲基吡咯烷中的一种或几种。
步骤一中,所述的催化剂采用甲酸、乙酸、对甲苯磺酸、草酸、乳酸、盐酸、硫酸、吡咯烷中的一种或几种。
步骤二中,所述的过渡金属离子为Fe、Co、Ni、Cu、Zn、Mn中的一种或几种;所述金属盐为甲酸盐、乙酸盐、苯甲酸盐、草酸盐、硫酸盐、硝酸盐、磷酸盐或卤化物。
步骤二中,所述的含过渡金属离子溶液溶剂为水、甲醇、乙醇、四氢呋喃、丙酮中的一种或几种。
本发明制备采用两步法,避免了过渡金属对于手性框架合成的影响,同时络合过程温和简单,保持了共价有机框架的有序孔道和手性结构,并有效实现了金属络合。
本发明制备得到的光催化剂具备单原子分布过渡金属离子,同时金属单原子络合在手性共价有机框架的孔道壁上。在共价有机框架上的单位点金属络合,能够有效促进光催化氧化半反应,同时手性框架的有序堆叠优化了析氢反应的热力学过程,从而实现在无贵金属助催化条件下的高效光解水析氢。
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匹配自然太阳光的光吸收范围,不需要负载贵金属助催化剂即可实现可见光下的高效光解水析氢;同时高比表面积使其光催化反应的传质过程不受到阻碍;通过手性框架材料的有序堆叠,使得析氢过程的效率得到显著提升;
(2)本发明通过两步法合成络合过渡金属的手性共价有机框架材料;两步法构筑能够避免过渡金属对手性框架材料合成造成不利影响,同时温和的络合过程不破坏手性框架的结构,以酮烯胺结构作为金属络合位点能够实现金属单原子的大量负载;这种制备方法具备环境友好、操作简单、金属负载量大和单原子分布的特点,并且易于重复。
附图说明
图1为实施例1的结构示意图。
图2为实施例1光催化分解水析氢结果。
图3为实施例1光催化分解水气相产物的气相色谱检测图。
图4为实施例1的傅里叶红外光谱图。
图5为实施例1的圆二色光谱图。
图6为实施例1的粉末X射线衍射图谱。
图7为实施例1的等温N2吸脱附曲线。
图8为实施例1的球差校正透射电子显微镜照片。
图9为实施例1的X射线光电子谱图。
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1,一种含过渡金属单原子的手性共价有机框架材料的制备方法和其光催化水分解产氢应用。
含过渡金属单原子的手性共价有机框架材料的制备方法如下:
步骤一,含有酮烯胺结构的手性共价有机框架材料的制备
将0.075mmol 三羟基均三苯甲醛,0.025mmol R-1-苯乙胺,0.112 mmol对苯二胺分别溶于0.75ml 三甲苯和二氧六环混合溶剂(v/v=1:1),然后将上述溶液加入耐热玻璃管,并加入0.3mL6 mol/L醋酸溶液。玻璃管于77K液氮中冷却,冻融脱气三次后密封,然后置于120℃的烘箱中反应3天;反应结束后过滤得到产物I,并用四氢呋喃洗涤产物,从而得到手性共价有机框架材料产物I。
步骤二,络合过渡金属的手性共价有机框架材料的制备
将10mg产物I分散于1mL 0.15 mol/L 醋酸铜水溶液中,在50℃下反应12h。反应结束后,过滤得到产物II,并用水和四氢呋喃洗涤产物II。产物II即为一种络合有过渡金属的手性共价有机框架材料催化剂。
将所制备的络合有过渡金属的手性共价有机框架材料催化剂取0.01g,放入盛有0.1 mol/L 半胱氨酸水溶液的光催化反应器中,以可见光为光源,气相色谱测试光催化的气体产物,分析析氢活性。以下结合附图说明本实施例的含过渡金属单原子的手性共价有机框架材料光催化剂的性能。
图1是本发明实施例中共价有机框架材料的分子结构示意图。
如图1所示,该含过渡金属单原子的手性共价有机框架材料的分子结构中具有酮-烯胺连接键,同时以酮-烯胺结构作为金属络合位点络合金属离子。
发明人对实施例中的含过渡金属的手性共价有机框架材料进行了表征测试,包括光催化析氢测试、傅里叶红外光谱测试、圆二色谱测试、粉末X射线衍射测试、氮气吸脱附测试、球差校正透射电子显微镜测试、X射线光电子谱测试。
图2是本发明的实施例中,含过渡金属手性共价有机框架材料在可见光照射下的析氢曲线。图3是对应气相产物的气相色谱分析结果。
光催化析氢性能测试结果如图2、3所示,从图中可以看出,含过渡金属单原子的手性共价有机框架材料光催化剂,在可见光照射下能够迅速稳定地分解水产生氢气,析氢速度达到了15.6 mmol/(g·h),说明该催化剂能够有效地将光能转化为氢能,在太阳能利用领域具有潜在的应用前景。
图4是本发明实施例中含过渡金属单原子的手性共价有机框架材料的傅里叶红外光谱图。 图5是本发明实施例中含过渡金属单原子的手性共价有机框架材料的圆二色光谱图。
如图4所示,傅里叶红外谱图中有明显的C=O键振动峰与C-N键振动峰,说明本实施例中得到了具有酮-烯胺连接键的共价有机框架材料。如图5所示,本实施例中的含过渡金属单原子的共价有机框架材料在可见光波段具有旋光性,即具有手性。
图6是本发明实施例中含过渡金属单原子的手性共价有机框架材料的粉末X射线衍射图谱。图7是本发明实施例中含过渡金属单原子的手性共价有机框架材料的氮气吸脱附曲线。
如图6所示,粉末X射线衍射图谱显示,本实施例中的含过渡金属的手性共价有机框架材料具有典型的二维共价有机框架X-射线衍射峰,说明了有序的周期性结构、结晶性良好。如图7所示,本实施例中的含过渡金属的手性共价有机框架材料的氮气吸脱附曲线属于典型的I型曲线,说明该材料具有微孔结构和较高的比表面积。
图8是本发明实施例中含过渡金属单原子的手性共价有机框架材料的球差校正透射电子显微镜照片。图9是本发明实施例中含过渡金属单原子的手性共价有机框架材料的X射线光电子谱。
如图8所示,高倍下拍摄的球差校正透射电子显微镜照片显示,本实施例中的含过渡金属单原子的手性共价有机框架材料具有原子级分散的铜原子。如图9所示,本实施例得到的材料中的二价铜原子处于络合态。
因此,上述测试结果表明,实施例1得到的含过渡金属的手性共价有机框架材料含有酮-烯胺的连接结构和旋光性,具有原子级分散的络合铜,并拥有良好的结晶性、微孔结构以及高比表面积等特征,同时具有高效的光催化分解水产氢的能力,在能源领域具有潜在的应用前景。
实施例2,一种含过渡金属单原子的手性共价有机框架材料的制备方法,具体步骤为:
步骤一,含有酮烯胺结构的手性共价有机框架材料的制备
将0.01mmol 三羟基均三苯甲醛,0.03mmolS-1-苯乙胺,0 .015mmol水合肼分别溶于0.5ml 正丁醇和二氧六环混合溶剂(v/v=1:3),然后将上述溶液加入耐热玻璃管,并加入0.03mL 吡咯烷。玻璃管于77K液氮中冷却,冻融脱气三次后密封,然后置于70℃的烘箱中反应7天;反应结束后过滤得到产物I,并用四氢呋喃洗涤产物,从而得到手性共价有机框架材料产物I。
步骤二,络合过渡金属的手性共价有机框架材料的制备
将5mg产物I分散于2mL 0.06mol/L 硝酸镍甲醇溶液中,在20℃下反应18h。反应结束后,过滤得到产物II,并用水和四氢呋喃洗涤产物II。产物II即为一种络合有过渡金属的手性共价有机框架材料催化剂。
实施例3,一种含过渡金属单原子的手性共价有机框架材料的制备方法,具体步骤为:
步骤一,含有酮烯胺结构的手性共价有机框架材料的制备
将0.05mmol 二羟基均三苯甲醛,0.1mmolR-叔丁基亚磺酰胺,0.075mmol4,4’-二氨基联苯分别溶于1ml 均三甲苯和正丁醇混合溶剂(v/v=1:1),然后将上述溶液加入耐热玻璃管,并加入0.1mL 3mol/L的草酸溶液。玻璃管于77K液氮中冷却,冻融脱气三次后密封,然后置于70℃的烘箱中反应7天;反应结束后过滤得到产物I,并用四氢呋喃洗涤产物,从而得到手性共价有机框架材料产物I。
步骤二,络合过渡金属的手性共价有机框架材料的制备
将10mg产物I分散于20mL 0.01mol/L 氯化锌乙醇溶液中,在60℃下反应6h。反应结束后,过滤得到产物II,并用水和四氢呋喃洗涤产物II。产物II即为一种络合有过渡金属的手性共价有机框架材料催化剂。
实施例4,一种含过渡金属单原子的手性共价有机框架材料的制备方法,具体步骤为:
步骤一,含有酮烯胺结构的手性共价有机框架材料的制备
将0.2mmol 单羟基均三苯甲醛,0.1mmolR-2-甲基吡咯烷,0.2mmol2,4,6-三(4-氨基苯基)-1,3,5-三嗪分别溶于3ml 邻二氯苯和二氧六环混合溶剂(v/v=3:1),然后将上述溶液加入耐热玻璃管,并加入0.3mmol对甲苯磺酸。玻璃管于77K液氮中冷却,冻融脱气三次后密封,然后置于100℃的烘箱中反应5天;反应结束后过滤得到产物I,并用四氢呋喃洗涤产物,从而得到手性共价有机框架材料产物I。
步骤二,络合过渡金属的手性共价有机框架材料的制备
将20mg产物I分散于1.5mL 0.04mol/L 苯甲酸钴的四氢呋喃溶液中,在30℃下反应15h。反应结束后,过滤得到产物II,并用水和四氢呋喃洗涤产物II。产物II即为一种络合有过渡金属的手性共价有机框架材料催化剂。
对实施例2~实施例4制备方法得到的含过渡金属单原子的手性共价有机框架材料,同样进行了一系列表征测试,包含光催化析氢测试、傅里叶红外光谱测试、圆二色谱测试、粉末X射线衍射测试、氮气吸脱附测试、透射电子显微镜测试、X射线光电子谱测试,结果表明,通过实施例2~实施例4得到的含过渡金属单原子的手性共价有机框架材料,具有与实施例1制备的材料相似的性能;都含有酮-烯胺的键连形式和络合态的金属单原子,同时具有旋光性、高结晶性、微孔结构和高比表面积等特性;在可见光下具有较好的分解水析氢速率,能够实现太阳能到氢能的转化,在清洁能源领域具有潜在的应用前景。
实施例的作用与效果
根据本发明实施例所涉及的含过渡金属单原子的手性共价有机框架材料的制备方法,由于该方法在多醛基单体与多氨基单体的席夫碱反应中加入手性助剂,使得结构手性传递到了酮-烯胺键连的材料上,从而合成具有良好结晶性、多孔性,并具有旋光性的共价有机框架材料;通过酮-烯胺结构的互变异构使金属离子络合在手性共价有机框架材料的框架上,从而实现金属在材料中的单原子分布。该制备方法操作简单,条件温和易实现,过程可控,可以得到具有高结晶性、高比表面积、含有金属单原子的手性共价有机框架材料。
根据本发明实施例制备方法得到的含过渡金属单原子的手性共价有机框架材料,在可见光下具有较高的分解水析氢速率,能够有效地将太阳能转变为氢能,在清洁能源领域具有潜在的应用前景。
以上所述仅为本发明的较佳实施例。由于本发明已经被具体示出,应当指出,对于本技术领域的其他技术人员,在不脱离本技术发明构思和精神的前提下,还可以对形式和细节做出若干修饰和改进,因此,这些改进和修饰也应视为本发明的保护范围之内。
Claims (10)
1.一种含过渡金属单原子的手性共价有机框架材料的制备方法,其特征在于,具体步骤为:
步骤一,以多醛基取代的功能单体和多氨基取代的功能单体为原料,在手性调节剂的存在的条件下,通过席夫碱反应形成可逆共价键,从而构筑手性共价有机框架材料;具体流程为:将0.00001 ~ 6 mol多醛基单体、0.00001~12mol手性调节剂与0.00001 ~ 6 mol多氨基单体分别溶于0.1~5mL一定比例的混合溶剂,加入到耐热玻璃管中,并加0 .05 ~ 1mL催化剂,于77K液氮中冷却,冻融脱气3次,密封后于70~180℃烘箱中反应1~7天,反应结束后过滤得到产物,使用四氢呋喃洗涤,得到手性共价有机框架材料;
步骤二,通过温和的络合反应,经过共价有机框架材料的酮-烯醇互变异构,得到过渡金属络合的手性共价有机框架材料;具体流程为:将5mg~100mg手性共价有机框架材料分散于0.5 ~ 100mL 0.005~0.3mol/L过渡金属离子溶液中,在20~70℃下反应6~18h,反应结束后,过滤得到产物,并用去离子水和四氢呋喃洗涤产物,得到含过渡金属单原子的手性共价有机框架材料。
4.根据权利要求1所述的含过渡金属的手性共价有机框架材料的制备方法,其特征在于,步骤一中所述的混合溶剂为均三甲苯/二氧六环、正丁醇/二氧六环、正丁醇/邻二氯苯、均三甲苯/正丁醇之中的任意一种;混合溶剂中,两种溶液的体积比为1:1~1:9。
5.根据权利要求1所述的含过渡金属的手性共价有机框架材料的制备方法,其特征在于,步骤一中所述的手性调节剂采用S/R-1-苯乙胺、S/R-叔丁基亚磺酰胺、S/R-2-甲基吡咯烷中的一种或几种。
6.根据权利要求1所述的含过渡金属的手性共价有机框架材料的制备方法,其特征在于,步骤一中所述的催化剂采用甲酸、乙酸、对甲苯磺酸、草酸、乳酸、盐酸、硫酸、吡咯烷中的一种或几种。
7.根据权利要求1所述的含过渡金属的手性共价有机框架材料的制备方法,其特征在于,步骤二中所述的过渡金属离子为Fe、Co、Ni、Cu、Zn、Mn中的一种或几种;所述金属盐为甲酸盐、乙酸盐、草酸盐、硫酸盐、硝酸盐、磷酸盐或卤化物。
8.根据权利要求1所述的含过渡金属的手性共价有机框架材料的制备方法,其特征在于,
步骤二中所述的含过渡金属离子溶液溶剂为水、甲醇、乙醇、四氢呋喃、丙酮中的一种或几种。
9.如权利要求1~8中任意一项所述的制备方法得到的含过渡金属的手性共价有机框架材料。
10.如权利要求9所述含过渡金属的手性共价有机框架材料作为光催化剂在可见光分解水制氢中的应用。
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