CN113527697B - 一种用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物及其应用 - Google Patents
一种用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物及其应用 Download PDFInfo
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Abstract
一种用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属‑有机配合物,该配合物的分子式如下:[Co3(4‑H2dpye)(MnMo9O32)(H2O)10]·H2O;[Co3(4‑H2dpyb)(MnMo9O32)(H2O)12]·4H2O;其中,4‑H2dpye为N,N'‑双(4‑嘧啶甲酰胺基)‑1,2‑乙烷,4‑H2dpyb为N,N'‑双(4‑嘧啶甲酰胺基)‑1,4‑丁烷。将钴的氯化物、柔性双嘧啶双酰胺有机配体和Waugh型多酸加入水中,利用溶剂热法合成,得到配合物。优点是:合成方法简单、合成时间短、合成产率好;可作为硫醚的选择性氧化的催化剂使用,容易从反应介质中分离,且不会污染反应产物。
Description
技术领域
本发明属于有机催化及合成方法领域,特别涉及一种用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物及其应用。
背景技术
硫醚是工业原油中的一种含硫杂质,随着脱硫技术的发展,汽油柴油中的硫醚含量虽然大幅降低,但仍未彻底解决汽油柴油含有硫化物的问题。酸雨的主要来源可能来自燃料油中硫化物的燃烧,它不仅造成严重的环境污染,而且危害人体健康。而硫化物氧化会生成亚砜和砜,可用于化学工业、生物学和医学化学,因此,硫化物选择性氧化成相应的亚砜是极其重要的。到目前为止,包括萃取脱硫、吸附脱硫、氧化脱硫和生物脱硫等方法被用于硫醚选择性氧化。在上述方法中,氧化脱硫是一种高效、温和的深度脱硫方法。在氧化脱硫反应中,需要活性氧化剂如:过氧化氢、分子氧和叔丁基过氧化氢(TBHP)的帮助。此外,催化剂可使含硫物种迅速氧化为相应的亚砜和砜。在这方面,合成高效催化剂是必不可少的,也是非常必要的。
多金属氧酸盐(POMs)是一类具有独特物理和化学性质的多核金属-氧簇化合物。由于其具有纳米尺寸、强酸性、可变氧化态、电荷分布和多电子变换等特点,多金属氧酸盐被广泛用作高效、条件温和的催化剂并可以促使各种化学转化发生。然而,大多数多酸具有高溶解性导致其作为均相催化剂不容易从反应介质中分离出来,无法实现再循环使用,且残留的催化剂可能会污染反应产物。
Waugh型杂多阴离子[MnMo9O32]6-是一种典型的手性杂多阴离子,结构呈D3对称性,具有左旋和左旋两种构型。有望成为对硫醚的选择性氧化催化剂的研究新方向。
发明内容
本发明要解决的技术问题是提供一种合成方法简单、合成时间短、合成产率好的用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物及其应用,可作为硫醚的选择性氧化的催化剂使用,容易从反应介质中分离,且不会污染反应产物。
本发明的技术解决方案是:
一种用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物,该配合物的分子式如下:
[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O
[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O
其中,4-H2dpye为N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷,4-H2dpyb为N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷。
进一步的,所述配合物为[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O,其具体合成步骤是:
将钴的氯化物、柔性双嘧啶双酰胺有机配体和Waugh型多酸H6[MnMo9O32]加入水中,所述柔性双嘧啶双酰胺有机配体是N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷,其中,柔性双嘧啶双酰胺有机配体和H6[MnMo9O32]的摩尔比为7:4,柔性双嘧啶双酰胺有机配体与钴的氯化物的摩尔比为3:1,加入到螺口透明玻璃瓶中并拧紧瓶盖,升温至90℃,溶剂热条件下保温24h-48h,弃去上清液,将获得的块状晶体清洗,得到配合物。
进一步的,所述配合物为[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O,其具体合成步骤是:
将钴的氯化物、柔性双嘧啶双酰胺有机配体和Waugh型多酸H6[MnMo9O32]加入水中,所述柔性双嘧啶双酰胺有机配体是N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷,其中,柔性双嘧啶双酰胺有机配体和H6[MnMo9O32]的摩尔比为3:2,柔性双嘧啶双酰胺有机配体与钴的氯化物的摩尔比为3:7,倒入螺口透明玻璃瓶中并拧紧瓶盖,升温至90℃,水热条件下保温4h~6h,弃去上清液,将获得的块状晶体清洗,得到配合物。
进一步的,钴的氯化物为CoCl2·6H2O。
进一步的,所述钴的氯化物与水的摩尔体积比为21:0.8~21:1mmol/L。
进一步的,块状晶体清洗时,用去离子水清洗2次~4次。
进一步的,升温时,升温速率为5℃/h~15℃/h;
进一步的,反应物倒入螺口透明玻璃瓶中,其反应物加入量以溶剂水的加入量为计量,所述去离子水的加入量占螺口透明玻璃瓶体积的40%~60%。
一种用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物在作为对硫醚选择性氧化的催化剂中的应用。
本发明以Waugh型多酸为无机单元,以氯化钴为过渡金属,通过使用不同的含氮中性有机配体:N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷和N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷作为含氮中性有机配体,通过水热合成了两个不同结构的基于Waugh型多酸的钴配合物。该配合物中Waugh型多酸阴离子是主要的催化中心。合成的配合物[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O(1)是包含左旋[MnMo9O32]6-基金属-有机链和右旋[MnMo9O32]6-基金属-有机链交替连接组成的二维层状结构。合成的配合物[[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O(2)是一维金属-有机链状结构,其中[MnMo9O32]6-多氧阴离子是游离的。此外,这两种配合物均可通过氢键相互作用形成3D超分子框架结构。其有益效果是:
(1)合成方法简单、合成周期短、合成产率好。采用柔性双嘧啶双酰胺配体中的酰胺基团是极性基团,具有很好的亲水性,加快了合成Waugh型多酸基钴配合物时的结晶过程,缩短了合成周期,特别是[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O配合物合成时间仅需6h,从而降低了合成成本。
(2)合成的Waugh型多金属氧酸盐基金属-有机配合物是具有高结晶度且结构明确的晶体,很容易地从反应介质中分离出来,并在接下来的循环中重复使用,且可以保持较高的催化效率。
(3)合成的两种不同结构的配合物[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O配合物和[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O配合物可作为硫醚选择性氧化的催化剂使用,这两种催化剂不仅可以作为茴香硫醚的选择性氧化,还可用作四氯茴香硫醚、四氧甲基茴香硫醚、苯硫醚和2氯乙基乙基硫醚等底物的选择性氧化催化剂,且均具备良好的催化能力。
(4)合成的配合物[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O用作茴香硫醚选择性氧化的催化剂时,其转化率和选择性分别为97%和95%;配合物[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O用作茴香硫醚选择性氧化的催化剂时,其转化率和选择性分别为100%和96%。
附图说明
图1是本发明合成的[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O(1)的晶体结构图;
图2是本发明合成的[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O(2)的晶体结构图;
图3是本发明合成的[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O(1)的PXRD衍射图;
图4是本发明合成的[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O(2)的PXRD衍射图;
图5是本发明合成的[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O(1)的红外光谱图;
图6是本发明合成的[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O(2)的红外光谱图。
具体实施方式
将0.21mmol CoCl2·6H2O、0.07mmol N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷、0.04mmol H6[MnMo9O32]和10.0mL H2O依次加入到20毫升螺口透明玻璃瓶中,拧紧瓶盖,以10℃/h速率升温至90℃件下恒温48h,得到橙色块状晶体,用去离子水冲洗2次,室温下自然晾干,得[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O,产率为42%。配位环境图如图1(a)所示,其一维左旋链结构如图1(b)所示,一维左旋链结构如图1(b)所示,二维层状结构如图1(d)所示,三维层状结构如图1(e)所示其PXRD衍射图谱如图3所示,热分析如图5所示。
实施例2合成[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O,其中,4-H2dpye为N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷。
将0.21mmol CoCl2·6H2O、0.07mmol N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷、0.04mmol H6[MnMo9O32]和8.0mL H2O依次加入到20毫升螺口透明玻璃瓶中,拧紧瓶盖,以10℃/h速率升温至90℃件下恒温48h,得到橙色块状晶体,用去离子水冲洗2次,室温下自然晾干,得[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O,产率为38%。配位环境图如图1(a)所示,其一维左旋链结构如图1(b)所示,一维左旋链结构如图1(b)所示,二维层状结构如图1(d)所示,三维层状结构如图1(e)所示其PXRD衍射图谱如图3所示,热分析如图5所示。
实施例3合成[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O,其中,4-H2dpye为N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷。
将0.21mmol CoCl2·6H2O、0.07mmol N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷、0.04mmol H6[MnMo9O32]和8.0mL H2O依次加入到20毫升螺口透明玻璃瓶中,拧紧瓶盖,以10℃/h速率升温至90℃件下恒温24h,得到橙色块状晶体,用去离子水冲洗2次,室温下自然晾干,得[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O,产率为34%。配位环境图如图1(a)所示,其一维左旋链结构如图1(b)所示,一维左旋链结构如图1(b)所示,二维层状结构如图1(d)所示,三维层状结构如图1(e)所示其PXRD衍射图谱如图3所示,热分析如图5所示。
将0.21mmol CoCl2·6H2O、0.06mmol N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷、0.04mmol H6[MnMo9O32]和10.0mL H2O依次加入到20毫升螺口透明玻璃瓶中,拧紧瓶盖,以10℃/h速率升温至90℃件下恒温6h,得到橙色块状晶体,用去离子水和无水乙醇交替冲洗2次,室温下自然晾干,得[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O,产率为62%。配位环境图如图2(a)所示,一维金属-有机链如图2(b)所示,其三维超分子结构如图2(c-d)所示,其PXRD衍射图谱如图4所示,热分析如图6所示。
实施例5合成[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O,其中,4-H2dpyb为N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷。
将0.21mmol CoCl2·6H2O、0.06mmol N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷、0.04mmol H6[MnMo9O32]和12.0mL H2O依次加入到20毫升螺口透明玻璃瓶中,拧紧瓶盖,以10℃/h速率升温至90℃件下恒温4h,得到橙色块状晶体,用去离子水和无水乙醇交替冲洗2次,室温下自然晾干,得[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O,产率为56%。配位环境图如图2(a)所示,一维金属-有机链如图2(b)所示,其三维超分子结构如图2(c-d)所示,其PXRD衍射图谱如图4所示,热分析如图6所示。
实施例6合成[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O,其中,4-H2dpyb为N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷。
将0.21mmol CoCl2·6H2O、0.06mmol N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷、0.04mmol H6[MnMo9O32]和8.0mL H2O依次加入到20毫升螺口透明玻璃瓶中,拧紧瓶盖,以10℃/h速率升温至90℃件下恒温4h,得到橙色块状晶体,用去离子水和无水乙醇交替冲洗2次,室温下自然晾干,得[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O,产率为58%。配位环境图如图2(a)所示,一维金属-有机链如图2(b)所示,其三维超分子结构如图2(c-d)所示,其PXRD衍射图谱如图4所示,热分析如图6所示。
一、基于双嘧啶双酰胺有机配体和H6[MnMo9O32]的钴配合物的表征:
(1)、晶体结构测定
用显微镜选取合适大小的单晶,室温下采用Bruker SMART APEX II衍射仪(石墨单色器,Mo-Ka,)收集衍射数据。扫描方式衍射数据使用SADABS程序进行吸收校正。使用Olex2,通过SHELXT结构解决方案程序使用本征相来解决结构问题,并使用SHELXL优化包使用最小二乘最小化对结构进行优化。本发明配合物1[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O和配合物2[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O晶体学衍射点数据收集与结构精修的部分参数如表1所示:
表1
(2)、粉末衍射表征相纯度
在Rigaku D/Max-2500衍射仪上收集完成粉末衍射数据,操作电流为100mA,电压为40kV。采用铜靶X射线。固定扫描,接收狭缝宽为0.1mm。密度数据收集使用2θ/θ扫描模式,扫描范围5°到50°,扫描速度为5°/s,跨度为0.02°/次。数据拟合使用Cerius2程序,单晶结构粉末衍射谱模拟转化使用Mercury 1.4.1。
如图3~图4所示,基于双嘧啶双酰胺有机配体和Waugh型多酸的钴配合物的粉末X射线衍射谱图与拟合的XRD谱图基本吻合,表明配合物均为纯相。
(3)、红外光谱表征配合物1-2的化学键及官能团
傅里叶红外光谱在Varian 640-IR光谱仪上进行(KBr压片)。对于配合物1-2,在1250-1650cm-1处的特征谱带可归因于4-H2dpye和4-H2dpyb配体中C=O和N-H的特征峰,3400cm-1附近的较宽谱带可归因于配位水和游离水分子特征峰。配合物1在941和906m-1处和配合物2在938和906cm-1处的特征谱带归因于Mo=O伸缩振动峰。配合物1在683、590、540和498cm-1处和配合物2在686、596、538和497cm-1处的特征谱带归因于O-Mo-O弯曲振动峰。
二、配合物1和配合物2在作为对含硫化合物选择性氧化的催化剂中应用的研究
(1)配合物1和配合物2对茴香硫醚氧化的催化活性评价
我们建立了以甲基苯硫醚为底物的典型模态反应,以评价上述配合物1、配合物2的催化活性。
为了研究最佳条件,以0.5mmol甲基苯硫醚为底物,以配合物1(表2)或配合物2(表3)为催化剂,叔丁基过氧化氢为氧化剂,以萘为内标,进行了一系列探索。由气相色谱仪监控反应:
表2
a反应条件:甲基苯硫醚(0.5mmol);溶剂甲醇(3mL);叔丁基过氧化氢;配合物1(3μmol).溶剂:b乙醇;c乙腈;d二氯甲烷。
表3
a反应条件:甲基苯硫醚(0.5mmol);溶剂:甲醇(3mL);叔丁基过氧化氢;配合物2(3μmol).溶剂:b乙醇;c乙腈;d二氯甲烷;氧化剂:e过氧化氢。
(2)配合物1(表4)和配合物2(表5)作为催化剂的多功能性
其中,以0.5mmol含硫化合物为底物,以上述配合物1或配合物2为催化剂,叔丁基过氧化氢为氧化剂,以萘为内标,进行了一系列探索。含硫化合物包括:芳族硫基化合物和脂族硫基化合物被用作底物以研究其催化性能。
表4
a反应条件:底物(0.5mmol);甲醇(3mL);叔丁基过氧化氢(0.75mmol);配合物1(3μmol);60℃.b乙醇(3mL);叔丁基过氧化氢(0.5mmol);50℃。
表5
a反应条件:底物(0.5mmol);甲醇(3mL);叔丁基过氧化氢(0.75mmol);配合物2(3μmol);60℃.b乙醇;TBHP(0.5mmol);50℃。
表4和表5结果表明,配合物1和配合物2可用作大多数含硫化合物催化氧化反应的有效的催化剂,其用途广泛。
(3)硫醚氧化不同催化剂比较
以0.5mmol甲基苯硫醚为底物,以不同为催化剂,叔丁基过氧化氢为氧化剂,以萘为内标,对不同催化剂比较催化效果比较,具体反应条件和反应结果如表6所示:
表6
条目 | 催化剂 | 体系 | 时间(min) | 转化率(%) |
1 | 配合物1 | 非均相 | 30 | 97 |
2 | 配合物2 | 非均相 | 30 | 100 |
3 | H<sub>6</sub>[MnMo<sub>9</sub>O<sub>32</sub>] | 均相 | 30 | 64 |
4 | CoCl<sub>2</sub>·6H<sub>2</sub>O | 均相 | 30 | 47 |
5 | 无催化剂 | - | 30 | 32 |
a反应条件:底物(0.5mmol);甲醇(3mL);叔丁基过氧化氢(0.75mmol);催化剂(3μmol);60℃。
配合物1或配合物2的H6[MnMo9O32]和CoCl2·6H2O作为催化剂对甲基苯硫醚的氧化结果表明,H6[MnMo9O32]是催化活性中心,Co2+和[MnMo9O32]6-阴离子在硫化物的氧化过程中具有一定的协同作用,可以促进催化作用。
由表6结果可知,配合物1和配合物2不同的催化活性可能由于它们具有不同的结构。其中,具有未配位的[MnMo9O32]6-阴离子的配合物2可能比配合物1暴露更多的活性位点,从而具有更加优良的催化性能。
以上仅为本发明的具体实施例而已,并不用于限制本发明,对于本领域的技术人员来说,本发明可以有各种更改和变化。凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (9)
1.一种用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物,其特征是:
该配合物的分子式如下:
[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O;
[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O;
其中,4-H2dpye为N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷,4-H2dpyb为N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷。
2.根据权利要求1所述的用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物,其特征是:
所述配合物为[Co3(4-H2dpye)(MnMo9O32)(H2O)10]·H2O,其具体合成步骤是:
将钴的氯化物、柔性双嘧啶双酰胺有机配体和Waugh型多酸H6[MnMo9O32]加入水中,所述柔性双嘧啶双酰胺有机配体是N,N'-双(4-嘧啶甲酰胺基)-1,2-乙烷,其中,柔性双嘧啶双酰胺有机配体和H6[MnMo9O32]的摩尔比为7:4,柔性双嘧啶双酰胺有机配体与钴的氯化物的摩尔比为3:1,加入到螺口透明玻璃瓶中并拧紧瓶盖,升温至90℃,溶剂热条件下保温24h~48h,弃去上清液,将获得的块状晶体清洗,得到配合物。
3.根据权利要求1所述的用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物,其特征是:
所述配合物为[Co3(4-H2dpyb)(MnMo9O32)(H2O)12]·4H2O,其具体合成步骤是:
将钴的氯化物、柔性双嘧啶双酰胺有机配体和Waugh型多酸H6[MnMo9O32]加入水中,所述柔性双嘧啶双酰胺有机配体是N,N'-双(4-嘧啶甲酰胺基)-1,4-丁烷,其中,柔性双嘧啶双酰胺有机配体和H6[MnMo9O32]的摩尔比为3:2,柔性双嘧啶双酰胺有机配体与钴的氯化物的摩尔比为3:7,倒入螺口透明玻璃瓶中并拧紧瓶盖,升温至90℃,水热条件下保温4h~6h,弃去上清液,将获得的块状晶体清洗,得到配合物。
4.根据权利要求2或3所述的用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物,其特征是:钴的氯化物为CoCl2·6H2O。
5.根据权利要求2或3所述的用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物,其特征是:所述钴的氯化物与水的摩尔体积比为21:0.8~21:1.2 mmol/L。
6.根据权利要求2或3所述的用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物,其特征是:块状晶体清洗时,用去离子水清洗2次~4次。
7.根据权利要求2或3所述的用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物,其特征是:升温时,升温速率为 5℃/h~15℃/h。
8.根据权利要求2或3所述的用于高效催化氧化脱硫的Waugh型多金属氧酸盐基金属-有机配合物,其特征是:反应物倒入螺口透明玻璃瓶中,其反应物加入量以溶剂水的加入量为计量,所述水的加入量占螺口透明玻璃瓶体积的40%~60%。
9.一种如权利要求1所述的Waugh型多金属氧酸盐基金属-有机配合物在作为对硫醚选择性氧化的催化剂中的应用。
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