CN113426485B - 一种采用两步法提高有机金属框架材料光催化还原性能的方法 - Google Patents
一种采用两步法提高有机金属框架材料光催化还原性能的方法 Download PDFInfo
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Abstract
本发明提供一种两步法提高有机金属框架材料还原性能的方法,所述方法包括:1)将有机金属框架材料和光还原剂醇类化合物进行光反应,得到还原态的有机金属框架材料;2)向步骤1)得到的还原态的有机金属框架材料中加入有机胺和底物进行暗反应得到还原产物;其中,所述底物为CO2,或全卤代C6‑20芳烃。所述方法反应条件温和,反应效率高,有效地使用价廉低毒醇类化合物作为光还原剂还原全卤代C6‑20芳烃、光催化产氢原料和CO2得到其还原产物。
Description
技术领域
本发明属于光催化合成技术领域,具体涉及到一种采用两步法提高有机金属框架材料光催化还原性能的方法。
背景技术
有机金属框架材料是由金属离子与有机配体配位形成的有序多孔材料,由于其具有大比表面积,外露的金属反应位点,以及容易改性等优点,已经成为非常具有潜力的光催化剂。在已有的报道中,有机金属框架材料已经被广泛用于研究光催化还原CO2、光催化产氢和光催化还原多溴联苯醚等,但是当前有研究发现有机金属框架材料的还原性能弱于传统无机半导体,在以廉价低毒的醇类化合物,如甲醇等作为光还原剂的条件下,有机金属框架材料难以催化还原这些物质,表现出较差的还原性能。因此人们迫切需要一种能提高有机金属框架材料的还原性能并以廉价低毒的醇类化合物作为光还原剂的方法。
发明内容
为了解决上述技术的问题,本发明提供了一种利用两步法提高有机金属框架材料还原性能的方法,所述方法包括如下步骤:
1)将有机金属框架材料和光还原剂醇类化合物进行光反应,得到还原态的有机金属框架材料;
2)向步骤1)得到的还原态的有机金属框架材料中加入有机胺和底物进行暗反应得到还原产物;
其中,所述底物为CO2,光催化产氢原料或全卤代C6-20芳烃。
根据本发明的实施方式,步骤1)中所述有机金属框架材料包括但不限于钛基有机金属框架材料,如MIL-125(Ti),NH2-MIL-125(Ti),COK-69(Ti)等。
根据本发明的实施方式,步骤1)中所述醇类化合物包括但不限于如下化合物:甲醇,乙醇,异丙醇,苯甲醇等中的一种或多种。
根据本发明的实施方式,步骤1)中所述有机金属框架材料与醇类化合物的用量为10mg有机金属框架材料使用(1~20)mL醇类化合物,例如(1~15)mL醇类化合物,如(5~15)mL醇类化合物。
根据本发明的实施方式,步骤1)中所述光反应使用紫外光-可见光进行光照,光照使用的波长可以依据有机金属框架材料的紫外-可见漫反射光谱的吸收波长来确定。
根据本发明的实施方式,步骤1)中所述光反应使用紫外光-可见光的波长为500nm以下,例如340nm以下,如320以下。
根据本发明的实施方式,MIL-125(Ti)的吸收波长为340nm以下,因此当使用MIL-125(Ti)时,步骤1)中采用340nm以下的紫外光进行光照,例如采用340~320nm的紫外光光照;
根据本发明的实施方式,NH2-MIL-125(Ti)的吸收波长为500nm以下,因此当使用NH2-MIL-125(Ti)时,步骤1)中采用500nm以下的紫外光-可见光进行光照,例如采用500~420nm的可见光进行光照;
根据本发明的实施方式,COK-69(Ti)的吸收波长在350nm及以下,因此当使用COK-69(Ti)时,步骤1)中采用350nm以下的紫外光进行光照,例如采用350~320nm的紫外光进行光照。
根据本发明的实施方式,步骤1)中将有机金属框架材料、光还原剂醇类化合物混合后进行超声,然后进行光反应。
根据本发明的实施方式,步骤1)和步骤2)中所述反应可以在溶剂中进行,所述溶剂包括但不限于乙腈,苯,四氢呋喃等。亦可以不需额外加入溶剂,直接在醇类化合物中反应。
根据本发明的实施方式,步骤1)所述光反应时间为0.5~24h,例如1~5h。
根据本发明的实施方式,步骤2)中所述有机胺包括但不限于如下化合物:伯胺类:乙醇胺,乙基胺,丙基胺等;仲胺类:二乙醇胺,二乙胺,二丙基胺等;叔胺类:三乙醇胺,三乙胺,三丙胺,三戊胺等。
根据本发明的实施方式,步骤2)中所述有机胺的浓度可以在0.1mol/L以上,例如0.1mol/L~5mol/L,如0.1mol/L、0.5mol/L、1mol/L等。
根据本发明的实施方式,步骤2)中所述底物全卤代C6-20芳烃表示具有6~20个碳原子的芳香性或部分芳香性的单环、双环或三环烃环,且其芳环上除非卤素取代基外(若含有取代基)所有的氢原子均被卤素(F、C、Br、I)取代,优选“全卤代C6-14芳环”。所述“全卤代C6-14芳环”为具有6、7、8、9、10、11、12、13或14个碳原子的芳香性或部分芳香性的单环、双环或三环烃环,且其芳环上除非卤素取代基外所有的氢原子均被卤素(F、C、Br、I)取代。所述芳环还可以选自联苯,四氢化萘、二氢萘、萘、芴、或蒽。
根据本发明的实施方式,步骤2)中所述底物包括但不限于如下化合物:二氧化碳,十溴联苯醚,六溴苯,十溴联苯,或十溴联苯酮等。
根据本发明的实施方式,步骤2)中所述底物与有机金属框架材料的摩尔比为(1~3):1,例如1.4:1。
根据本发明的实施方式,所述步骤1)和步骤2)反应的温度可以为0-100℃,例如5-80℃,如10-60℃。
根据本发明的实施方式,步骤1)和步骤2)中所述反应在密封条件下进行。
根据本发明的实施方式,步骤1)和步骤2)中所述反应在无氧的环境中进行,例如在惰性气体(例如氩气)填充的手套箱中进行。
根据本发明的实施方式,所述无氧的环境的氧气浓度为0.1ppm。
根据本发明的实施方式,步骤1)和步骤2)中所述反应在搅拌的条件下进行。
根据本发明的实施方式,步骤2)中所述底物预先溶解于醚类溶剂如四氢呋喃等有机溶剂中的一种、两种或更多种。
有益效果
本发明采用两步法提高有机金属框架材料光催化还原性能。其技术核心是将有机金属框架材料光催化过程分为两步进行,第一步有机金属框架材料与醇类化合物进行光反应,第二步加入有机胺与底物进行暗反应。通过两步法,有机胺助剂作用显著提高了有机金属框架材料在以醇类化合物作为光还原剂条件下的光催化还原性能。所述方法反应条件温和,反应效率高,有效地使用价廉低毒醇类化合物作为光还原剂还原全卤代C6-20芳烃,光催化产氢原料和CO2得到其还原产物。
附图说明
图1为实施例1MIL-125(Ti)还原十溴联苯醚的动力学曲线;
图2为实施例1MIL-125(Ti)还原十溴联苯醚的HPLC检测图;
图3为实施例2MIL-125(Ti)还原六溴苯的动力学曲线;
图4为实施例2MIL-125(Ti)还原六溴苯的HPLC检测图;
图5为对比例1MIL-125(Ti)还原十溴联苯醚的动力学曲线。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明,以下实施例中使用的原料和试剂均为市售商品,或者可以通过已知方法制备。
如下实施例1-4及对比例中的三乙醇胺或三乙胺的浓度相对于反应液而言。
如下实施例1-4及对比例中的反应底物浓度相对于反应液而言。
如下实施例1-4中转化率的计算公式为:
转化率=(C0-C1)/C0
其中C0底物的初始,C1为反应60min后底物的浓度。
如下实施例及对比例中的反应均在室温下操作。
实施例1
将10mg有机金属框架材料MIL-125(Ti)与10mL甲醇混合于光化学反应器并密封,然后超声10min,之后用高纯氩气进行除氧操作。除氧完毕后,紫外光(340~320nm)光照2h,之后将光反应器移至氩气填充的手套箱中,向其中加入134μL三乙醇胺(反应溶液中浓度为0.1mol/L)和溶于四氢呋喃的十溴联苯醚母液(纯度为97%,其中含有少量九溴联苯醚),底物初始反应浓度为10-3mol/L,然后进行暗反应。每间隔15min进行取点。
HPLC检测十溴联苯醚的还原动力学曲线,如图1所示,从图1中可以看出,随着反应时间的进行(图1中的时间为反应进行的时间),十溴联苯醚的浓度逐渐降低。通过HPLC谱图(图2所示)可以看出,十溴联苯醚逐渐被还原为低溴代联苯醚(八溴联苯醚和九溴联苯醚),经计算反应60min后十溴联苯醚的转化率为65.8%。
实施例2
将10mg有机金属框架材料MIL-125(Ti)与10mL的苯甲醇和乙腈的混合溶液(两者体积比为v/v=1:10)混合于光化学反应器并密封,然后超声10min,之后用高纯氩气进行除氧操作。除氧完毕后,紫外光(340~320nm)光照2h,之后将光反应器移至氩气填充的手套箱中,向其中加入三乙醇胺(反应液中的浓度为0.1mol/L)和溶于四氢呋喃的六溴苯母液,底物初始反应浓度为10-3mol/L,然后进行暗反应。每间隔15min进行取点。
HPLC检测六溴苯的还原动力学曲线,如图3所示,从图3中可以看出,随着反应时间的进行,六溴苯的浓度逐渐降低。通过液相色谱图(图4所示)可知,六溴苯逐渐被还原为低溴代苯(五溴苯),经计算反应60min后六溴苯的转化率为87.1%。
实施例3
将10mg有机金属框架材料MIL-125(Ti)与10mL甲醇混合于光化学反应器并密封,然后超声10min,之后用高纯氩气进行除氧操作。除氧完毕后,紫外光(340~320nm)光照2h,之后将光反应器移至氩气填充的手套箱中,向其中加入122μL的三乙胺(反应溶液中浓度为0.1mol/L)和溶于四氢呋喃的十溴联苯醚母液,底物初始反应浓度为10-3mol/L,进行暗反应。每间隔15min取点。经HPLC检测,反应60min后,十溴联苯醚被还原为低溴代联苯醚,经计算十溴联苯醚的转化率为81.4%。
实施例4
将10mg有机金属框架材料NH2-MIL-125(Ti)与5mL的苯甲醇混合于光化学反应器并密封,然后超声10min,之后用高纯氩气进行除氧操作。除氧完毕后,可见光(500~420nm)光照12h,之后将光反应器移至氩气填充的手套箱中,加入5mL浓度为0.2mol/L三乙醇胺乙腈溶液和溶于四氢呋喃的十溴联苯醚母液,底物初始反应浓度为10-3mol/L,然后进行暗反应。每间隔15min取点。经HPLC检测十溴联苯醚的浓度逐渐降低,其被还原为低溴代联苯醚,反应60min时十溴联苯醚的转化率为43.3%。
实施例5
50mg MIL-125(Ti)和10mL甲醇加入到光化学反应器中并密封,然后超声10min,之后用高纯氩气进行除氧操作。除氧完毕后,用紫外光(340~320nm)光照5h后,将催化剂转移至手套箱中,在无氧的条件下加入1mL的三乙醇胺。然后向反应器中持续5min通入CO2,待搅拌并反应4h后用离子色谱测得生成甲酸的量为4.6μmol。
对比例1
将10mg MIL-125(Ti)和10mL甲醇添加于光化学反应器,然后超声10min,之后用高纯氩气进行除氧操作。除氧完毕后,紫外-可见光(340~320nm)光照2h,之后将光反应器移至氩气填充的手套箱中,加入溶于四氢呋喃的十溴联苯醚母液,初始底物反应浓度为10- 3mol/L,然后进行暗反应。每间隔15min取点,结果如图5所示,由图5可知在60min内十溴联苯醚未被还原。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (14)
1.一种利用两步法提高有机金属框架材料还原性能的方法,其特征在于,所述方法包括如下步骤:
1)将有机金属框架材料和光还原剂醇类化合物进行光反应,得到还原态的有机金属框架材料;
2)向步骤1)得到的还原态的有机金属框架材料中加入有机胺和底物进行暗反应得到还原产物;
其中,所述底物为CO2,光催化产氢原料或全卤代C6-20芳烃;
所述有机金属框架材料选自钛基有机金属框架材料;
所述醇类化合物选自甲醇,乙醇,异丙醇,苯甲醇中的一种或多种;
所述光反应使用紫外光-可见光的波长为500nm以下。
2.根据权利要求1所述的方法,其特征在于,步骤1)中所述有机金属框架材料选自MIL-125(Ti),NH2-MIL-125(Ti),COK-69(Ti)。
3.根据权利要求1或2所述的方法,其特征在于,步骤1)中所述有机金属框架材料与醇类化合物的用量为10mg有机金属框架材料使用(1~20)mL醇类化合物。
4.根据权利要求1所述的方法,其特征在于,步骤1)中当使用MIL-125(Ti)时,步骤1)中采用340 nm以下的紫外光-可见光进行光照。
5.根据权利要求1所述的方法,其特征在于,步骤1)中当使用NH2-MIL-125(Ti)时,步骤1)中采用500 nm以下的紫外光-可见光进行光照。
6.根据权利要求1所述的方法,其特征在于,步骤1)中当使用COK-69(Ti)时,步骤1)中采用350nm以下的紫外-可见光进行光照。
7.根据权利要求1所述的方法,其特征在于,步骤2)中所述有机胺选自如下中的至少一种:乙醇胺,乙基胺,丙基胺,二乙醇胺,二乙胺,二丙基胺,三乙醇胺,三乙胺,三丙胺,三戊胺。
8.根据权利要求1所述的方法,其特征在于,步骤2)中所述有机胺的浓度在0.1 mol/L以上。
9.根据权利要求1所述的方法,其特征在于,步骤2)中所述底物全卤代C6-20芳烃表示具有6~20个碳原子的芳香性或部分芳香性的单环、双环或三环烃环,且其芳环上若含有取代基,除非卤素取代基外所有的氢原子均被卤素取代。
10.根据权利要求9所述的方法,其特征在于,步骤2)中所述全卤代C6-20芳烃为具有6、7、8、9、10、11、12、13或14个碳原子的芳香性或部分芳香性的单环、双环或三环烃环,且其芳环上除非卤素取代基外所有的氢原子均被卤素取代。
11.根据权利要求10所述的方法,其特征在于,步骤2)中所述底物选自如下化合物:二氧化碳,十溴联苯醚,六溴苯,十溴联苯,或十溴联苯酮。
12.根据权利要求1所述的方法,其特征在于,步骤2)中所述底物与有机金属框架材料的摩尔比为(1~3):1。
13.根据权利要求1所述的方法,其特征在于,步骤1)和步骤2)反应的温度为0-100 oC。
14.根据权利要求1所述的方法,其特征在于,步骤1)和步骤2)中所述反应在无氧的环境中进行。
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