CN110548545B - 钛基金属有机骨架材料在光催化固氮中的应用 - Google Patents
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Abstract
本发明提供了一种钛基金属有机骨架材料在光催化固氮中的应用,所述光催化固氮反应的具体步骤为:以钛基金属有机骨架材料作为催化剂,所述催化剂与水以质量体积比为20‑30mg:100mL加入至光反应装置中,并在搅拌下通入氮气40‑70min,以300‑330W氙灯作为光源,反应时间10‑13h,每隔2‑3h取样,随后测定产物氨的含量。本发明提供的光催化固氮反应,是一种在温和条件下实现固氮的方式,且耗能低,可操作性强,具有广阔的引用前景。
Description
技术领域
本发明属于光催化技术领域,具体涉及一种钛基金属有机骨架材料在光催化固氮中的应用。
背景技术
氨气是一种生产化肥的必备原料,同时也是一种无碳的能量载体。尽管用于合成氨气的氮气分子作为空气的主要成分(78%)用之不尽,但因为破坏氮氮三键需要巨大的活化能势垒(941kJ/mol),使得人工固氮异常困难。基于以上事实,传统人工固氮依赖于Haber-Bosh过程,需要高温高压条件下才能将氮气和氢气转化为氨气,但同时伴随着大量氢气和能源的消耗以及温室气体二氧化碳的释放。因此,温和条件下的人工固氮在科学和工业领域均有重要意义。
金属有机骨架材料(MOFs)作为一种新型多孔材料,具有光敏中心和催化活性中心为一体的优势,其多孔性也具有增强反应物和产物的传质作用并暴露更多固氮中心的特点,有望成为一个光催化固氮平台,利用取之不尽的太阳能,在吸光的同时将光生电子转移给固氮中心,将氮气还原为氨气,但至今尚未报道。此项工作将开辟一类光催化固氮的新材料,同时也为MOFs基材料的应用开辟新方向。
发明内容
为了实现上述目的,本发明旨在提供一种钛基金属有机骨架材料在光催化固氮中的应用。
本发明提供如下技术方案:一种钛基金属有机骨架材料在光催化固氮中的应用,所述钛基金属有机骨架材料在光催化固氮反应中作为催化剂。
进一步,所述光催化固氮反应的具体步骤为:以钛基金属有机骨架材料作为催化剂,所述催化剂与水以质量体积比为20-30mg:100mL加入至光反应装置中,并在搅拌下通入氮气40-70min,以300-350W氙灯作为光源,反应时间10-13h,每隔2-3h取样,随后测定产物氨的含量。
进一步,所述催化剂为MIL-125(Ti)、NH2-MIL-125(Ti)、OH-MIL-125(Ti)或CH3-MIL-125(Ti)。
进一步,所述催化剂与水的加入质量体积比为25mg:100mL。
进一步,通入氮气60min,以带有400nm截止滤光片的300W氙灯作为光源,反应时间12h,每隔3h取样一次。
进一步,采用离子色谱法测定产物氨的含量。
与现有技术相比,本发明具有如下有益效果:
1、本发明采用的催化剂为钛基金属有机骨架材料,该类材料为介孔材料,其多孔性具有增强反应物和产物的传质作用并暴露更多固氮中心的特点;且该类材料集吸光单元与催化中心为一体,具有高效光催化固定性能;同时,该类材料的组成部分容易调控,可随意修饰有机配体,从而调节吸光性能。
2、本发明采用的催化剂为一类全新的固氮催化剂,可以通过改变配体,合成多种光催化固氮催化剂,其中催化剂NH2-MIL-125(Ti)的光催化性能最佳,产物氨的含量为12.25μmol/g/h。
3、本发明提供的光催化固氮反应,是一种在温和条件下实现固氮的方式,且耗能低,可操作性强,具有广阔的应用前景。
附图说明
图1为实施例1制备的MIL-125(Ti)和NH2-MIL-125(Ti)的场发射扫描电镜图;
图2为为实施例1制备的MIL-125(Ti)和NH2-MIL-125(Ti)的粉末X射线衍射图;
图3为实施例1制备的OH-MIL-125(Ti)和CH3-MIL-125(Ti)的粉末X射线衍射图;
图4为实施例1制备NH2-MIL-125(Ti)的氮气吸附等温线;
图5为实施例1制备的催化剂对光催化固氮活性图。
具体实施方式
下面结合具体实施例和附图,对本发明方法进行详细说明。
一、钛基金属有机骨架材料的制备
实施例1
(1)MIL-125(Ti)的制备:将18mL超干DMF溶剂、2mL超干甲醇溶剂、1g对苯二羧酸配体和0.52mL正四丁基钛混合均匀后,移入高压反应釜中,并在150摄氏度下保温20小时。反应结束后,产物经离心分离得到后,用DMF和甲醇洗涤数次,真空干燥箱干燥得产物。
(2)NH2-MIL-125(Ti)的制备:将18mL超干DMF溶剂、2mL超干甲醇溶剂、1g 2-氨基对苯二羧酸配体和0.52mL正四丁基钛混合均匀后,移入高压反应釜中,并在150摄氏度下保温20小时。反应结束,产物经离心分离得到后,用DMF和甲醇洗涤数次,真空干燥箱干燥得产物。
图1为催化剂MIL-125(Ti)和催化剂NH2-MIL-125(Ti)的SEM图,从图中可知,NH2修饰前后的MIL-125(Ti)的形貌一致,均为八面体结构,且都拥有尺寸大小较为相同的晶体。图2为催化剂MIL-125(Ti)和催化剂NH2-MIL-125(Ti)的XRD衍射图谱(横坐标为:角度;纵坐标为:衍射强度),从图中可知,合成的MIL-125(Ti)和NH2-MIL-125(Ti)的XRD衍射峰的位置相吻合,可见NH2的引入并未改变衍射峰的出峰位置,且合成的MIL-125(Ti)与模拟的MIL-125(Ti)结果相吻合,证明本申请已成功合成出了MIL-125(Ti)和NH2-MIL-125(Ti)。图4为NH2-MIL-125(Ti)的氮气吸附等温线(横坐标为:相对压力;纵坐标为:氮气吸附量),从图中可知,催化剂NH2-MIL-125(Ti)存在滞后环,根据介孔材料曲线的特点可知,催化剂NH2-MIL-125(Ti)为介孔材料,这有利于反应物及产物的扩散,从而提高催化剂的催化活性。
(3)OH-MIL-125(Ti)的制备:将291.4mg 2-羟基对苯二羧酸溶解在18mL超干DMF溶剂和2mL超干甲醇溶剂的混合溶剂中,随后加入105mg MIL-125(Ti),随后将混合液转移到高压反应釜中,并在150摄氏度下保温24小时。反应结束后,离心得到产物,并经DMF和甲醇洗涤数次,真空干燥箱干燥得产物。
(4)CH3-MIL-125(Ti)的制备:将288mg 2-甲基对苯二羧酸溶解在18mL超干DMF溶剂和2mL超干甲醇溶剂的混合溶剂中,随后加入105mg MIL-125(Ti),随后将混合液转移到高压反应釜中,并在150摄氏度下保温24小时。反应结束后,离心得到产物,并经DMF和甲醇洗涤数次,真空干燥箱干燥得产物。图3为催化剂OH-MIL-125(Ti)和CH3-MIL-125(Ti)的XRD衍射图谱(横坐标为:角度;纵坐标为:衍射强度),从图中可知,改变有机配体,并不会影响MIL-125(Ti)XRD衍射峰的出峰位置。
二、光催化固氮反应
实施例2
将25mg催化剂和100mL水加入到光反应装置中,并在搅拌下通氮气60min,随后用带有400nm截止滤光片的300W氙灯照射,反应12h,每隔3h取一次样品,采用离子色谱法测定产物氨的含量。
实施例3
将20mg催化剂和100mL水加入到光反应装置中,并在搅拌下通氮气40min,随后用带有400nm截止滤光片的320W氙灯照射,反应10h,每隔2h取一次样品,采用离子色谱法测定产物氨的含量。
实施例4
将30mg催化剂和100mL水加入到光反应装置中,并在搅拌下通氮气70min,随后用带有400nm截止滤光片的330W氙灯照射,反应13h,每隔3h取一次样品,采用离子色谱法测定产物氨的含量。
上述实施例2-4中催化剂可以为MIL-125(Ti)、NH2-MIL-125(Ti)、OH-MIL-125(Ti)或CH3-MIL-125(Ti)。对上述实施例2-4反应后的产物进行测定,测定产物氨含量的结果如图5(横坐标为:不同种类的催化剂;纵坐标为:氨的含量)所示,图5给出了催化剂为MIL-125(Ti)、NH2-MIL-125(Ti)、OH-MIL-125(Ti)或CH3-MIL-125(Ti)时,产物氨的含量。从图中可知,MIL-125(Ti)、NH2-MIL-125(Ti)、OH-MIL-125(Ti)和CH3-MIL-125(Ti)这四种催化剂均可用于光催化固氮,其中,催化剂NH2-MIL-125(Ti)的光催化性能最佳,产物氨的含量为12.25μmol/g/h。
最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。
Claims (4)
1.一种光催化固氮的方法,其特征在于,具体步骤为:以钛基金属有机骨架材料作为催化剂,所述催化剂与水以质量体积比为20-30 mg:100 mL加入至光反应装置中,并在搅拌下通入氮气40-70 min,以300-330 W氙灯作为光源,反应时间10-13 h,每隔2-3 h取样,随后测定产物氨的含量;所述催化剂为MIL-125(Ti)、NH2-MIL-125(Ti)、OH-MIL-125(Ti)或CH3-MIL-125(Ti)。
2.根据权利要求1所述的光催化固氮的方法,其特征在于:所述催化剂与水的加入质量体积比为25 mg:100 mL。
3.根据权利要求1所述光催化固氮的方法,其特征在于:通入氮气60 min,以带有400nm截止滤光片的300 W氙灯作为光源,反应时间12 h,每隔3 h取样一次。
4.根据权利要求1所述光催化固氮的方法,其特征在于:采用离子色谱法测定产物氨的含量。
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