CN112808293A - 一种基于双配体mof前驱镍-氮化镍纳米复合材料的制备及应用 - Google Patents
一种基于双配体mof前驱镍-氮化镍纳米复合材料的制备及应用 Download PDFInfo
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Abstract
本发明属于固态复合材料合成及应用领域,具体涉及一种基于双配体MOF前驱镍‑氮化镍纳米复合材料的制备及应用,以不同温度氮气氛围下焙烧可制备出由碳层包覆保护、主体为纳米镍、而表面复合有组成可调氮化镍组分的纳米复合材料:其中碳包覆层为无定形和石墨化多孔碳复合层,镍纳米颗粒尺寸为10.0‑20.0nm,镍颗粒表面复合的氮化镍表面摩尔百分比可调控为10‑40%;以这种材料作为催化剂应用于液相加氢反应,对α,β不饱和醛酮选择性加氢及光催化硝基苯加氢制苯胺皆显示出值得关注的催化效果。该体系在于可以方便获得高分散、结构稳定、被碳层保护的镍‑氮化镍纳米复合材料,并实现了对样品表面结构组成特别是氮化镍组成的有效调控。
Description
技术领域
本发明属于固态复合材料合成及应用领域,具体涉及一种基于双配体MOF前驱镍-氮化镍纳米复合材料的制备及应用。
背景技术
对一些不饱和化合物如α,β不饱和醛酮、硝基苯类化合物进行高效加氢或还原催化转化是制备有机化工原料和精细化工中间体的重要过程,在染料、农药、医药、橡胶助剂和异氰酸酯等生产领域都有重要应用。实现这类转化通常都依赖金属催化剂,其中镍基催化剂由于其价格低廉、活性良好而备受关注,但也存在选择性差、稳定性不佳等难以克服的问题。解决这一问题的根本途径是对镍基催化剂的结构特别是表面结构及组成进行有效调控,特别是形成组成可调的复合结构很可能是获取高性能、稳定镍基催化剂的根本技术手段。据此,国内外相关科研、技术人员已开展了众多改进或发明工作,发现若能在镍基催化剂表面引入其它元素形成特定组成的复合结构可有效改善其催化性能和应用稳定性,如引入氮、磷等元素形成氮化镍或磷化镍,相对常见的镍氧化物皆有更显著的催化效果,但从目前技术实现角度看,由通常高温氮气氛围下对含镍基体进行的氮化过程所得到的氮化镍很难在镍基体上形成紧密复合结构,且氮化镍与镍的对比组成也很难进行调控,再加上分散度差、结构不明确、稳定性差等问题造成了这类材料难以进行控制合成以及实际应用。
针对这一难题,本发明设计了一种由含氮配体和无氮配体双配体构建出镍基MOF材料,再由此材料作为前驱体进行镍-氮化镍纳米复合材料制备的方法,并以α,β不饱和醛酮、硝基苯类化合物液相加氢反应展示了所制备复合材料的催化应用效果。结果发现,由于在双配体镍基MOF结构中存在紧密的氮镍配位结构,在以较低温度焙烧时就可在纳米镍基体上形成氮化镍表面复合层,改变焙烧温度可进一步实现氮化镍表面复合比例的调控,再加上来自配体有机结构焙烧后残留形成的碳包覆层,所得由碳层包覆保护的镍-氮化镍纳米复合材料显示出了值得关注的催化应用效果,表明本发明提供了一种实用可控构建高性能镍-氮化镍纳米复合材料的新方法,其所具备的应用潜力值得深入探究。
发明内容
本发明目的在于利用双配体MOF结构内金属、非金属元素可调配特性构建金属与金属配位化合物比例可调的固态复合材料,所制备材料能在包括催化反应而不仅限于催化反应如光电分析检测、有机物吸附转化及光降解等领域中发挥作用。
为实现上述目的,本发明提供一种基于双配体MOF前驱镍-氮化镍纳米复合材料的制备,所述纳米复合材料的制备包括以下步骤:
(1)双配体镍基MOF前驱材料的合成
取不含氮的间苯二甲酸配体以及含氮配体3,6-双咪唑基哒嗪与镍盐水溶液混合置于聚四氟乙烯水热反应釜中,搅拌均匀后120℃反应72h,反应结束后,分离出固态物进行洗涤,经75℃真空干燥,得到双配体镍基MOF前驱材料;
(2)镍-氮化镍纳米复合材料的制备
取步骤(1)中制备的MOF前驱材料,在氮气氛围下,在600-900℃温度区间进行焙烧得到镍-氮化镍纳米复合材料。
优选的,所述步骤(1)中镍盐:间苯二甲酸:3,6-双咪唑基哒嗪的摩尔比例为2:1:1,其中镍盐为的六水合硝酸镍。
优选的,所述步骤(2)的焙烧条件为:氮气流速为30ml/min,升温速率5℃/min,在焙烧设定温度下焙烧4h。
优选的,所述镍-氮化镍纳米复合材料作为催化剂或主体材料应用于α,β不饱和醛酮选择性加氢及光催化硝基苯加氢制苯胺的催化。
优选的,所述应用于α,β不饱和醛酮选择性加氢催化是以乙醇或水为溶剂,加入α,β不饱和醛酮反应物如柠檬醛或肉桂醛,配制为反应物与溶剂体积比为0.01-0.1的溶液20-50mL,加入0.02-0.5g镍-氮化镍纳米复合材料作为催化剂,装入以聚四氟乙烯为内衬的高压反应釜装置中,高压釜密封后以氢气置换5次,以除去釜中的空气,预充氢气后加热至反应温度90-150℃后,保持氢气压力为2.0-4.0Mpa,进行反应,反应器内溶液搅拌速度600-800转/分,反应时间为90-240分钟,对α,β不饱和醛酮反应物的C=C加氢产物产率可达50-95%。
优选的,所述应用于光催化硝基苯加氢制苯胺催化是在150mL光照瓶中,加入100mL水、0.3-1.0mL硝基苯和0.01-0.05g镍-氮化镍纳米复合材料催化剂,并加入10mL三乙醇胺作为牺牲剂,充以氮气作为保护气,在氙灯下光照4-7h,苯胺的产率可达60-100%。
附图说明
图1为本发明合成的双配体MOF和模拟MOF的X射线衍射(XRD)对比图谱;
图2为Ni-600催化剂的X射线衍射(XRD)图谱;
图3为Ni-600催化剂的扫描电子显微镜(SEM)图;
图4为Ni-600催化剂中的氮元素X射线光电子能谱(XPS)图
图5为Ni-600催化剂中的镍元素的X射线光电子能谱(XPS)图;
图6为Ni-800催化剂的硝基苯加氢性能测试曲线。
具体实施方式
下面结合实例对本发明进行进一步的说明。
实施例1
双配体MOF的合成:Ni:IPA:BMP=2:1:1代表六水合硝酸镍,间苯二甲酸(IPA)和3,6-双咪唑基哒嗪的摩尔比为2:1:1。配制包含0.291g六水合硝酸镍,0.083g间苯二甲酸与0.106g,3,6-双咪唑基哒嗪。分别分散在0.5mL,2mL,2mL水溶液中。其中IPA的溶解需要另外加入0.042g氢氧化钠使其充分溶解在水中。将配制好的水溶液转移至10ml聚四氟乙烯水热反应釜中,在烘箱中120℃反应72h,反应结束后,分离出固态物进行洗涤,将多余的配体洗净,然后经真空75℃干燥即为双配体MOF。
催化剂Ni-600的合成:将干燥后的双配体MOF在氮气氛围600℃下热解。具体为以5℃/min的升温速率升温至600℃,而后保持4h,氮气流速为40ml/min,温度调控程序结束后,冷却至室温,将固体粉末移出记为Ni-600催化剂。
分析:通过X射线衍射(XRD)对合成的双配体MOF进行表征与模拟的XRD图进行对比。通过图1的XRD图可以表明MOF成功合成,然后将在氮气氛围中600℃热解的催化剂Ni-600样品用X射线衍射(XRD),扫描电子显微镜(SEM),与透射电子显微镜(XPS)对进行表征。通过XRD表征,由图2显示,Ni-600样品可观测到清晰的单质镍的衍射峰,说明催化剂里含有单质镍,而且还可以观察到由图2在大致2θ=26.3°的低宽峰归属于石墨化碳的峰,属于碳的(002)晶面,SEM照片显示样品呈现为维持一个整体块状,且表现无明显形貌变化。XPS表征(图3)对催化剂表面氮元素种类进行分析,通过分峰拟合得知,电子结合能位置为398.7eV,401eV,403.9eV,400eV,分别归属于吡啶氮,吡咯氮,石墨氮,和Ni-N。由XPS表征(图4),其中从催化剂Ni-800表面Ni2p1/2进行分峰拟合可以得知,Ni-600主要由两个峰组成,电子结合能位置为872.3eV,870eV,分别归属于Ni(0),Ni-N组分。
实施例2
催化剂Ni-700(N2氛围700℃下热解)的制备:Ni:IPA:BMP=2:1:1代表六水合硝酸镍,间苯二甲酸和3,6-双咪唑基哒嗪的摩尔比为2:1:1。配制包含0.291g六水合硝酸镍,0.083g间苯二甲酸与0.106g,3,6-双咪唑基哒嗪。分别分散在0.5mL,2mL,2mL水溶液中。其中IPA的溶解需要另外加入0.042g氢氧化钠使其充分溶解在水中。将配制好的水溶液转移至10ml聚四氟乙烯水热反应釜中,在烘箱中120℃反应72h,反应结束后,分离出固态物进行洗涤,将多余的配体洗净,然后经75℃干燥,将干燥后的催化剂再氮气氛围700℃下热解。具体为以5℃/min的升温速率升温至700℃,而后保持4h,氮气流速为40ml/min,温度调控程序结束后,冷却至室温,将固体粉末移出即为Ni-700催化剂。
分析:样品结构相关附图与实例1相似,不赘附图
柠檬醛加氢活性测试:将300微升柠檬醛,0.03g Ni-700催化剂,15ml无水乙醇,装入高压反应装置聚四氟乙烯内衬釜中。高压釜密封后以氢气置换5次,以除去釜中的空气。预充氢气后加热至反应温度后,保持氢气压力恒定后,开始记录反应体系物质浓度变化。反应温度为90℃,氢气压力2.0Mpa,搅拌速度800转/分,反应时间为90min,柠檬醛转化率及对香茅醛(C=C加氢产物)的选择性及其最终的产率如表1所示当反应时间为90min时,转化率可达94%,香茅醛选择性接近90%,可得香茅醛的产率约为85%。
实施例3
催化剂Ni-900(N2氛围900℃下热解)的制备:Ni:IPA:BMP=2:1:1代表六水合硝酸镍,间苯二甲酸和3,6-双咪唑基哒嗪的摩尔比为2:1:1。配制包含0.291g六水合硝酸镍,0.083g间苯二甲酸与0.106g,3,6-双咪唑基哒嗪。分别分散在0.5mL,2mL,2mL水溶液中。其中IPA的溶解需要另外加入0.042g氢氧化钠使其充分溶解在水中。将配制好的水溶液转移至10ml聚四氟乙烯水热反应釜中,在烘箱中120℃反应72h,反应结束后,分离出固态物进行洗涤,将多余的配体洗净,然后经75℃干燥,将干燥后的催化剂再氮气氛围600℃下热解。具体为以5℃/min的升温速率升温至900℃,而后保持4h,氮气流速为40ml/min,温度调控程序结束后,冷却至室温,将固体粉末移出即为Ni-900催化剂。
分析:样品结构相关附图与实例1相似,不赘附图
肉桂醛加氢活性测试:将300微升肉桂醛,0.03g Ni-700催化剂,15ml无水乙醇,装入高压反应装置聚四氟乙烯内衬釜中。高压釜密封后以氢气置换5次,以除去釜中的空气。预充氢气后加热至反应温度后,保持氢气压力恒定后,开始记录反应体系物质浓度变化。当反应温度为100℃,氢气压力2.0Mpa,搅拌速度800转/分,反应时间为90min,肉桂醛转化率及苯基丙醛(C=C加氢产物)的选择性及其最终的产率如表1可见,转化率可达100%,苯丙醛选择性接近86%,可得香茅醛的产率约为86%。
实施例4
催化剂Ni-800(N2氛围600℃下热解)的制备:Ni:IPA:BMP=2:1:1代表六水合硝酸镍,间苯二甲酸和3,6-双咪唑基哒嗪的摩尔比为2:1:1。配制包含0.291g六水合硝酸镍,0.083g间苯二甲酸与0.106g,3,6-双咪唑基哒嗪。分别分散在0.5mL,2mL,2mL水溶液中。其中IPA的溶解需要另外加入0.042g氢氧化钠使其充分溶解在水中。将配制好的水溶液转移至10ml聚四氟乙烯水热反应釜中,在烘箱中120℃反应72h,反应结束后,分离出固态物进行洗涤,将多余的配体洗净,然后经75℃干燥,将干燥后的催化剂再氮气氛围800℃下热解。具体为以5℃/min的升温速率升温至800℃,而后保持4h,氮气流速为40ml/min,温度调控程序结束后,冷却至室温,将固体粉末移出即为Ni-800催化剂。
分析:样品结构相关附图与实例1相似,不赘附图
光催化硝基苯加氢活性测试:将305微升硝基苯,0.01g Ni-800催化剂,90ml去离子水,10ml三乙醇胺装入150ml光照瓶中,超声10min,然后用氮气将光照瓶中的空气置换出来,置换时间约30min。置换后将光照瓶放在300W的氙灯下光照,并在反应过程中取点检测苯胺的产率。图4为常温常压下,反应时间为0.5-5h区间内,硝基苯产率变化曲线。可见,当反应时间为5h时,硝基苯的产率接近100%。
表1两种α,β不饱和醛酮选择性加氢催化应用条件及效果
Claims (6)
1.一种基于双配体MOF前驱镍-氮化镍纳米复合材料的制备,其特征在于:所述纳米复合材料的制备包括以下步骤:
(1)双配体镍基MOF前驱材料的合成
取不含氮的间苯二甲酸配体以及含氮配体3,6-双咪唑基哒嗪与镍盐水溶液混合置于聚四氟乙烯水热反应釜中,搅拌均匀后120℃反应72h,反应结束后,分离出固态物进行洗涤,经75℃真空干燥,得到双配体镍基MOF前驱材料;
(2)镍-氮化镍纳米复合材料的制备
取步骤(1)中制备的MOF前驱材料,在氮气氛围下,在600-900℃温度区间进行焙烧得到镍-氮化镍纳米复合材料。
2.根据权利要求1所述纳米复合材料的制备,其特征在于:所述步骤(1)中镍盐:间苯二甲酸:3,6-双咪唑基哒嗪的摩尔比例为2:1:1,其中镍盐为的六水合硝酸镍。
3.根据权利要求1所述纳米复合材料的制备,其特征在于:所述步骤(2)的焙烧条件为:氮气流速为30ml/min,升温速率5℃/min,在焙烧设定温度下焙烧4h。
4.一种如权利要求1-3任一所述制备的镍-氮化镍纳米复合材料的应用,其特征在于:所述镍-氮化镍纳米复合材料作为催化剂或主体材料应用于α,β不饱和醛酮选择性加氢及光催化硝基苯加氢制苯胺的催化。
5.根据权利要求4所述镍-氮化镍纳米复合材料的应用,其特征在于:所述应用于α,β不饱和醛酮选择性加氢催化是以乙醇或水为溶剂,加入α,β不饱和醛酮反应物如柠檬醛或肉桂醛,配制为反应物与溶剂体积比为0.01-0.1的溶液20-50mL,加入0.02-0.5g镍-氮化镍纳米复合材料作为催化剂,装入以聚四氟乙烯为内衬的高压反应釜装置中,高压釜密封后以氢气置换5次,以除去釜中的空气,预充氢气后加热至反应温度90-150℃后,保持氢气压力为2.0-4.0Mpa,进行反应,反应器内溶液搅拌速度600-800转/分,反应时间为90-240分钟,对α,β不饱和醛酮反应物的C=C加氢产物产率可达50-95%。
6.根据权利要求4所述镍-氮化镍纳米复合材料的应用,其特征在于:所述应用于光催化硝基苯加氢制苯胺催化是在150mL光照瓶中,加入100mL水、0.3-1.0mL硝基苯和0.01-0.05g镍-氮化镍纳米复合材料催化剂,并加入10mL三乙醇胺作为牺牲剂,充以氮气作为保护气,在氙灯下光照4-7h,苯胺的产率可达60-100%。
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