CN111978538A - 一种硫掺杂共价三嗪框架聚合物及其制备方法与在制备苯酚中的应用 - Google Patents
一种硫掺杂共价三嗪框架聚合物及其制备方法与在制备苯酚中的应用 Download PDFInfo
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Abstract
本发明公开了一种硫掺杂共价三嗪框架聚合物及其制备方法与在制备苯酚中的应用。硫掺杂共价三嗪框架(NP‑CTFS)通过三氟甲磺酸(TfOH)催化氰基化合物的三聚反应而成,其具有宽可见光吸收、高热稳定性、高化学稳定性和更负的导带电位,在室温、空气氛围和可见光照射下,能够高效和高选择性地光催化芳香硼酸羟基化制备苯酚,具有反应条件温和、催化效果好、底物适用范围宽、苯酚选择性高和催化剂可回收优点。
Description
技术领域
本发明涉及一种光催化材料的制备及其应用,具体涉及一种硫掺杂共价三嗪框架(NP-CTFS)的制备及其在光催化芳香硼酸羟基化制备苯酚的应用。
背景技术
苯酚类化合物作为多用途有机中间体被广泛应用于天然产物、材料、生物和药物化合物的合成。工业上,苯酚类化合物主要通过卤代芳烃的亲核取代或金属催化羟基化制备。近些年,芳香硼酸羟基化制备苯酚受到越来越多的重视,常用的氧化剂包括双氧水、叔丁基过氧化氢、间氯过氧苯甲酸、臭氧、过硼酸钠等。但这些氧化剂通常需要化学计量、不稳定、易爆炸等缺点,不符合绿色化学发展潮流。
近年来,以氧气(或空气)为氧化剂光催化芳香硼酸羟基化制备苯酚受到越来越多的青睐,常见的光催化剂主要包括有机染料和过渡金属化合物。但这些光催化剂存在一些固有缺陷,包括催化剂不易回收、易分解、高成本、金属污染等缺点。因此,开发高效、无金属、多相光催化剂仍然是一项迫切的需求。
共价三嗪框架(CTF)作为一类新型的无金属共轭聚合物,通过氰基化合物的三聚反应聚合而成,具有高稳定性、宽可见光吸收、能带易调等优势。并且,非金属化学原子比如硫、卤素和磷的掺杂有助于进一步优化共价三嗪框架的电子结构,进而增强其光催化活性。2016年,Bi课题组通过将硫磺与已制备的共价三嗪框架混合并退火热处理,首次制备了硫掺杂的共价三嗪框架光催化剂,并成功应用于光催化分解水产氢。于此相比,本专利报道的硫掺杂共价三嗪框架 (NP-CTFS)通过更简易的一步法制备,在这里三氟甲磺酸(TfOH) 既是三聚反应的催化剂,也是硫掺杂的来源。作为无金属多相光催化剂,硫掺杂共价三嗪框架(NP-CTFS)具有易回收和可重复使用的优势,有利于催化剂成本的降低和产物苯酚化合物的分离提纯。
发明内容
本发明的目的在于克服现有技术的不足,提供一种硫掺杂共价三嗪框架聚合物及其制备方法与在制备苯酚中的应用,硫掺杂共价三嗪框架聚合物能高效和高选择性地光催化芳香硼酸羟基化制备苯酚。
为了实现上述目的,本发明采用如下技术方案:
一种硫掺杂共价三嗪框架聚合物,其特征在于具有式(I)结构:
作为优选的,在上述的聚合物中,所述的聚合物是红褐色粉末,光吸收范围200-1200nm,导带电位-2.18V(vs.RHE)。
上述聚合物的制备方法,包括如下步骤:由单体3,7-双(4-氰基苯基)-2-萘-10-吩嗪(CNP)在三氟甲磺酸(TfOH)催化剂、100℃、真空下发生三聚反应得到,如下所示:
作为优选的,在上述的制备方法中,3,7-双(4-氰基苯基)-2-萘-10- 吩嗪(CNP)和三氟甲磺酸(TfOH)的摩尔比例是1:45;三氟甲磺酸(TfOH)作为催化剂和溶剂,在真空和100℃下反应的时间24h。
上述硫掺杂共价三嗪框架聚合物在光催化芳香硼酸羟基化制备苯酚中的应用。
利用硫掺杂共价三嗪框架聚合物光催化芳香硼酸羟基化制备苯酚的方法,包括如下步骤:
将芳香硼酸、内标物正十二烷、硫掺杂共价三嗪框架(NP-CTFS) 和电子给体超声分散在有机溶剂中,安装冷指回流冷凝器,在25℃、空气氛围和白光LED下照射反应7~48h,乙醇稀释,过滤回收催化剂,得到的有机相经气相色谱(GC)进行定量分析。
作为优选的,在上述的方法中,所述光催化芳香硼酸羟基化制备苯酚以空气为氧化剂、以硫掺杂共价三嗪框架聚合物(NP-CTFS)为催化剂,以N,N-二异丙基乙胺为电子给体,以正十二烷为内标物,以乙腈为溶剂,以白光LED(波长400-800nm)为光源,以芳香硼酸为反应底物。
所述芳香硼酸选自苯硼酸、4-三氟甲基苯硼酸、4-溴基苯硼酸、 4-甲氧基苯硼酸、2-三氟甲基苯硼酸、3-三氟甲基苯硼酸、2-萘硼酸中的一种或多种。
与现有技术相比,本发明具有如下有益效果:
本发明基于一种硫掺杂共价三嗪框架聚合物(NP-CTFS),具有高稳定性、宽可见光响应和更负的导带电位。在可见光照射下温和地光催化芳香硼酸羟基化制备苯酚,苯酚收率达到75~99%。而且作为无金属催化的多相催化剂,易于分离和回收,具有重复使用的优势,产物苯酚易纯化。因此,本发明设计的硫掺杂共价三嗪框架(NP-CTFS) 对光催化芳香硼酸羟基化制备苯酚具有广泛的应用前景。
附图说明
图1为硫掺杂共价三嗪框架聚合物(NP-CTFS)的红外光谱图;
图2为硫掺杂共价三嗪框架聚合物(NP-CTFS)的固体核磁13C波谱图;
图3为硫掺杂共价三嗪框架聚合物(NP-CTFS)的硫(S)2p的X射线光电子能谱(XPS);
图4为硫掺杂共价三嗪框架聚合物(NP-CTFS)的碳(C)1s XPS图。
图5为回收的光催化剂用红外光谱进行表征图;
图6为回收的光催化剂用固体核磁13C谱进行表征图。
具体实施方式
下面将结合本发明实施例,对本发明实施例中的技术方案进行清楚、完整地描述,显然,所描述的实施例仅仅是本发明实施例的一部分,而不是全部的实施例。基于本发明中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本发明保护的范围。
实施例1:硫掺杂共价三嗪框架聚合物的制备:
在一个10mLPyrex耐压管中加入0.5mmol3,7-双(4-氰基苯基)-2- 萘-10-吩嗪(CNP),然后再将22.5mmol三氟甲磺酸(TfOH)加入。随后通过液氮迅速将混合物冷冻并抽真空,并在真空条件下通过火焰密封。随后将反应管放入100℃油浴中反应24h。反应完成后,冷却至室温后,用氨水除去剩余的三氟甲磺酸(TfOH),并依次用去离子水、乙醇、二氯甲烷洗涤滤饼,干燥后用研钵研成粉末,再用二氯甲烷为溶剂索氏提取24h,100℃下真空干燥过夜,得到红褐色粉末(产率:95%)。
红外光谱(图1)揭示2224cm-1处的氰基振动峰在硫掺杂共价三嗪框架(NP-CTFS)中明显地减弱,并且在NP-CTFS中出现三嗪结构的特征峰(1484,1360和804cm-1)。固体核磁13C波谱(图2) 显示在NP-CTFS中出现三嗪结构中碳原子的特征峰170ppm,而其它峰143,133,127和113ppm则归属于单体骨架上的碳原子。综合红外光谱和固体核磁13C波谱结果,我们认为单体3,7-双(4-氰基苯基)-2-萘-10-吩嗪(CNP)成功地发生三聚反应,得到三嗪结构单元。硫(S)2p的X射线光电子能谱(XPS)(图3)揭示了三嗪结构中 C-S键的特征峰(163.8和165.0eV),而168.3eV则归属于NP-CTFS 表面残余的SO4 2-物种。碳(C)1s XPS图(图4)中的288.9和286.5 eV分别归属于三嗪结构单元中N-C=N键和C-S键的C原子,而286.0 和284.8eV则归属于苯环和萘上的C原子。S和C的XPS光谱表明 S原子成功地合并入三嗪结构单元,得到硫掺杂的共价三嗪框架。
本发明进行的光催化芳香硼酸羟基化制备苯酚主要利用硫掺杂共价三嗪框架催化剂(NP-CTFS),将芳香硼酸、电子给体和内标物溶解于有机溶剂,在25℃、空气氛围和可见光照射下进行多相催化反应。
实施例和对比例中的试剂均为市售的分析纯试剂。
实施例和对比例中所用的硫掺杂共价三嗪框架催化剂是按现有技术所描述的方法制得。
实施例2
以0.5mmol苯硼酸为原料,加入25mg硫掺杂共价三嗪框架聚合物(NP-CTFS),2.5mmolN,N-二异丙基乙胺电子给体,0.5mmol 正十二烷内标物,10mL乙腈为溶剂,超声分散10min。在25℃、空气氛围和白光LED照射下搅拌进行催化反应7h。过滤除去催化剂,乙醇稀释,取样GC定量分析,相应苯酚收率98%。
实施例3
以0.5mmol4-三氟甲基苯硼酸为原料,加入25mg硫掺杂共价三嗪框架聚合物(NP-CTFS),2.5mmolN,N-二异丙基乙胺电子给体, 0.5mmol正十二烷内标物,10mL乙腈为溶剂,超声分散10min。在 25℃、空气氛围和白光LED照射下搅拌进行催化反应16h。过滤除去催化剂,乙醇稀释,取样GC定量分析,相应苯酚收率98%。
实施例4
以0.5mmol4-溴基苯硼酸为原料,加入25mg硫掺杂共价三嗪框架聚合物(NP-CTFS),2.5mmolN,N-二异丙基乙胺电子给体,0.5 mmol正十二烷内标物,10mL乙腈为溶剂,超声分散10min。在25 ℃、空气氛围和白光LED照射下搅拌进行催化反应16h。过滤除去催化剂,乙醇稀释,取样GC定量分析,相应苯酚收率84%。
实施例5
以0.5mmol4-甲氧基苯硼酸为原料,加入25mg硫掺杂共价三嗪框架聚合物(NP-CTFS),2.5mmolN,N-二异丙基乙胺电子给体,0.5 mmol正十二烷内标物,10mL乙腈为溶剂,超声分散10min。在25 ℃、空气氛围和白光LED照射下搅拌进行催化反应48h。过滤除去催化剂,乙醇稀释,取样GC定量分析,相应苯酚收率88%。
实施例6
以0.5mmol2-三氟甲基苯硼酸为原料,加入25mg硫掺杂共价三嗪框架聚合物(NP-CTFS),2.5mmolN,N-二异丙基乙胺电子给体, 0.5mmol正十二烷内标物,10mL乙腈为溶剂,超声分散10min。在 25℃、空气氛围和白光LED照射下搅拌进行催化反应16h。过滤除去催化剂,乙醇稀释,取样GC定量分析,相应苯酚收率99%。
实施例7
以0.5mmol3-三氟甲基苯硼酸为原料,加入25mg硫掺杂共价三嗪框架聚合物(NP-CTFS),2.5mmolN,N-二异丙基乙胺电子给体, 0.5mmol正十二烷内标物,10mL乙腈为溶剂,超声分散10min。在 25℃、空气氛围和白光LED照射下搅拌进行催化反应16h。过滤除去催化剂,乙醇稀释,取样GC定量分析,相应苯酚收率99%。
实施例8
以0.5mmol2-萘硼酸为原料,加入25mg硫掺杂共价三嗪框架聚合物(NP-CTFS),2.5mmolN,N-二异丙基乙胺电子给体,0.5mmol 正十二烷内标物,10mL乙腈为溶剂,超声分散10min。在25℃、空气氛围和白光LED照射下搅拌进行催化反应32h。过滤除去催化剂,乙醇稀释,取样GC定量分析,相应苯酚收率75%。
分别取实施例1-7中制备得到的苯酚样品,采用气相色谱GC通过内标法进行定量分析,结果如下表1所示:
表1
反应时间(h) | 苯酚收率(%) | |
实施例2 | 7 | 98 |
实施例3 | 16 | 98 |
实施例4 | 16 | 84 |
实施例5 | 48 | 88 |
实施例6 | 16 | 99 |
实施例7 | 16 | 99 |
实施例8 | 32 | 75 |
从上表1可以看到,通过本发明所述的硫掺杂共价三嗪框架催化剂光催化芳香硼酸制备苯酚的方法,其苯酚收率达到75~99%,选择性好,效率高。
对比例1
取实施例2中催化剂通过过滤和干燥进行回收,重新用于光催化芳香硼酸制备苯酚的反应中,反应条件与实施例2相一致。
反应完成后,通过气相色谱法进行分析,结果显示,相应苯酚的收率为96%。
进一步地,将上述反应完成后的催化剂通过过滤和干燥再次回收,重新用于光催化芳香硼酸制备苯酚的反应中,反应条件与实施例2相一致。
反应完成后,通过气相色谱法进行分析,结果显示,相应苯酚的收率为97%。
回收的光催化剂用红外光谱和固体核磁13C谱进行表征,正如图 5和图6所示,回收的光催化剂和新鲜的光催化剂没有明显的变化,这表明硫掺杂共价三嗪框架(NP-CTFS)光催化剂具有优秀的化学稳定性。
由此可见,通过本发明所述的方法,可以实现催化剂的多次回收和重复利用,同时能够保证反应的效率和选择性,大大降低反应的成本和能耗,且反应条件温和,安全性显著提高。
以上具体实施方式部分对本发明所涉及的分析方法进行了具体的介绍。应当注意的是,上述介绍仅是为了帮助本领域技术人员更好地理解本发明的方法及思路,而不是对相关内容的限制。在不脱离本发明原理的情况下,本领域技术人员还可以对本发明进行适当的调整或修改,上述调整和修改也应当属于本发明的保护范围。
Claims (8)
2.根据权利要求1所述的聚合物,其特征在于,所述的聚合物是红褐色粉末,光吸收范围200-1200nm,导带电位-2.18V(vs.RHE)。
4.根据权利要求3所述的制备方法,其特征在于,3,7-双(4-氰基苯基)-2-萘-10-吩嗪(CNP)和三氟甲磺酸(TfOH)的摩尔比例是1:45;三氟甲磺酸(TfOH)作为催化剂和溶剂,在真空和100℃下反应的时间24h。
5.权利要求1所述硫掺杂共价三嗪框架聚合物在光催化芳香硼酸羟基化制备苯酚中的应用。
6.利用权利要求1所述硫掺杂共价三嗪框架聚合物光催化芳香硼酸羟基化制备苯酚的方法,其特征在于包括如下步骤:
将芳香硼酸、内标物正十二烷、硫掺杂共价三嗪框架(NP-CTFS)和电子给体超声分散在有机溶剂中,安装冷指回流冷凝器,在25℃、空气氛围和白光LED下照射反应7~48h,乙醇稀释,过滤回收催化剂,得到的有机相经气相色谱(GC)进行定量分析。
7.根据权利要求6所述的方法,其特征在于,所述光催化芳香硼酸羟基化制备苯酚以空气为氧化剂、以硫掺杂共价三嗪框架聚合物(NP-CTFS)为催化剂,以N,N-二异丙基乙胺为电子给体,以正十二烷为内标物,以乙腈为溶剂,以白光LED(波长400-800nm)为光源,以芳香硼酸为反应底物。
8.根据权利要求7所述的方法,其特征在于,所述芳香硼酸选自苯硼酸、4-三氟甲基苯硼酸、4-溴基苯硼酸、4-甲氧基苯硼酸、2-三氟甲基苯硼酸、3-三氟甲基苯硼酸、2-萘硼酸中的一种或多种。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113754667A (zh) * | 2021-09-28 | 2021-12-07 | 西湖大学 | 一种快速、宏量制备高结晶半导体共价三嗪框架的方法 |
CN113845665A (zh) * | 2021-09-28 | 2021-12-28 | 天津大学 | 一种全共轭有机三嗪骨架材料及其制备方法和应用 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3932402A (en) * | 1974-06-24 | 1976-01-13 | Phillips Petroleum Company | Preparation of sym-triazines by trimerization of nitriles in trifluoromethanesulfonic acid |
CN105126908A (zh) * | 2015-08-24 | 2015-12-09 | 福州大学 | 硫掺杂共价三嗪有机聚合物可见光催化剂及其制备与应用 |
CN109776796A (zh) * | 2019-03-07 | 2019-05-21 | 中国科学技术大学 | 一种炔基功能化共价三嗪聚合物、其制备方法及应用 |
-
2020
- 2020-06-29 CN CN202010607339.3A patent/CN111978538A/zh active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3932402A (en) * | 1974-06-24 | 1976-01-13 | Phillips Petroleum Company | Preparation of sym-triazines by trimerization of nitriles in trifluoromethanesulfonic acid |
CN105126908A (zh) * | 2015-08-24 | 2015-12-09 | 福州大学 | 硫掺杂共价三嗪有机聚合物可见光催化剂及其制备与应用 |
CN109776796A (zh) * | 2019-03-07 | 2019-05-21 | 中国科学技术大学 | 一种炔基功能化共价三嗪聚合物、其制备方法及应用 |
Non-Patent Citations (2)
Title |
---|
BLAINE G. MCCARTHY ET AL.,: "Structure−Property Relationships for Tailoring Phenoxazines as Reducing Photoredox Catalysts", 《J. AM. CHEM. SOC》 * |
LIUYI LI ET AL.,: "Sulfur-doped covalent triazine-based frameworks for enhanced photocatalytic hydrogen evolution from water under visible light", 《J. MATER. CHEM. A》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN113754667A (zh) * | 2021-09-28 | 2021-12-07 | 西湖大学 | 一种快速、宏量制备高结晶半导体共价三嗪框架的方法 |
CN113845665A (zh) * | 2021-09-28 | 2021-12-28 | 天津大学 | 一种全共轭有机三嗪骨架材料及其制备方法和应用 |
CN113845665B (zh) * | 2021-09-28 | 2022-11-08 | 天津大学 | 一种全共轭有机三嗪骨架材料及其制备方法和应用 |
CN113754667B (zh) * | 2021-09-28 | 2023-01-10 | 西湖大学 | 一种快速、宏量制备高结晶半导体共价三嗪框架的方法 |
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