CN106563484A - 一种介孔型中空掺氮碳包铜纳米催化剂的制备方法 - Google Patents
一种介孔型中空掺氮碳包铜纳米催化剂的制备方法 Download PDFInfo
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Abstract
本发明属于碳基复合材料制备领域，具体是一种介孔型中空掺氮碳包铜纳米催化剂的制备方法，以聚吡咯为碳源、氮源，硫酸铜为活性组分前驱体，PS微球为模板，在适当的表面活性剂下，经多层顺序包裹后高温炭化，经活化后制得形貌大小可控的介孔型掺氮碳包铜催化剂，在甲醇制备DMC反应中体现了较高的催化活性及较好的稳定性。所制备的催化剂对于避免活性组分的团聚和剥离以及提高反应催化活性具有显著地效果。实验数据精确翔实，成本低，原料易得，产物为黑色粉体，粉体颗粒直径小于400 nm，产物纯度达98.9%，反应中DMC时空收率可达到1251 mg/g∙h，选择性高达99.99%。
Description
技术领域
本发明属于碳基复合材料制备领域，具体是一种介孔型中空掺氮碳包铜纳米催化剂的制备方法，该催化剂可用于催化甲醇氧化羰基化制备碳酸二甲酯。
背景技术
碳酸二甲酯(DMC)为甲醇的下游产品，用途极为广泛。多种制备方法相比较下，甲醇氧化羰基化方法因其生产成本低、选择性高、对设备腐蚀性小，而成为近些年研究的热点。
在甲醇氧化羰基化反应的催化剂研究中，我们提出的空心碳球包覆铜纳米粒子的复合材料，一方面利用了碳层的阻隔作用限制活性组分的团聚，另一方面可提供适于反应的特定微环境。
空心碳球包覆铜纳米催化剂稳定性高，铜纳米粒子不易发生大规模的团聚现象，但由于碳层的过于致密，阻碍了反应物的进出，大大地限制了催化活性。相关报道中以挥发性聚合物(如聚苯乙烯球等)为核制备的碳球通过热解可得到较好的介孔结构。其次，将碳壳进行杂原子掺杂可有效改善其物理、化学性能，例如在碳层中进行氮掺杂，氮原子提供的孤对电子可改变碳材料的局部电荷分布，增强载体与金属之间的作用力，显著地提高了金属颗粒在碳材料表面的分散度。所以，设计、制备一种介孔型中空掺氮碳包铜催化剂提供了解决这一问题的新方法，目前仍处于研究之中。
发明内容
为了优化催化剂在甲醇氧化羰基化制DMC中的催化性能，本发明提供了一种介孔型中空掺氮碳包铜纳米催化剂的制备方法。
本发明是通过以下技术方案实现的：一种介孔型中空掺氮碳包铜纳米催化剂的制备方法，包括如下步骤：
⑴硫酸铜溶液中滴入氨水，使出现沉淀后又刚好消失，然后加入PVP以及CTAB，加热搅拌，加入水合肼，使得C=0.06 M，颜色由蓝变为红色或紫红色，持续搅拌，制备铜纳米胶体；
⑵在铜纳米胶体中加入苯乙烯以及AIBN，超声分散、搅拌、加热，干燥获得CuNPs/PS；
⑶CuNPs/PS分散到无水乙醇中，加入PVP，搅拌、离心，然后将产物分散在去离子水中，加入吡咯、K2S2O8，搅拌、离心、洗涤、干燥，获得CuNPs/PS@PPy；
⑷将CuNPs/PS@PPy进行高温碳化处理，获得介孔型碳包铜纳米催化剂。
本发明的催化剂结构利用介孔型中空的屏障作用可使得内核组分免受外界环境因素的影响。利用特殊的限域结构体系，可有效防止金属纳米核在反应中的聚集、长大，最大程度的保证了金属纳米粒子的组成和结构的完整性。其次，通过原位合成法进行掺氮，有效的将氮元素引入碳骨架，在反应过程中可充分发挥氮元素的化学作用，增加催化剂的稳定性。因此，本发明所述催化剂无论在结构上还是性能上都能够解决活性组分易团聚的问题。
具体实施时，所述高温碳化处理的步骤为：将CuNPs/PS@PPy置于惰性气体环境下升温至700 ℃±5 ℃，处理时间为3 h。
本发明与背景技术相比之下具有明显的先进性，以聚吡咯为碳源、氮源，硫酸铜为活性组分前驱体，PS微球为模板，在适当的表面活性剂下，经多层顺序包裹后高温炭化，经活化后制得形貌大小可控的介孔型掺氮碳包铜催化剂，在甲醇制备DMC反应中体现了较高的催化活性及较好的稳定性。所制备的催化剂对于避免活性组分的团聚和剥离以及提高反应催化活性具有显著地效果。实验数据精确翔实，成本低，原料易得，产物为黑色粉体，粉体颗粒直径小于400 nm，产物纯度达98.9%，反应中DMC时空收率可达到1251 mg/g∙h，选择性高达99.99%。相比较于结构简易的碳包铜催化剂，在防止活性组分团聚的前提下有效地提高了催化活性，是一种先进的制备介孔型掺氮中空碳包铜催化剂的方法。
附图说明
图1为介孔型中空掺氮碳包铜纳米催化剂形貌图。由图1可以看出，制备得到的催化剂是核壳型粉体，形貌规整，大小均一。
图2为介孔型中空掺氮碳包铜纳米催化剂的内部结构图。图中可清晰地看出催化剂的中空结构及铜纳米颗粒。
图3为介孔型中空掺氮碳包铜纳米催化剂的X射线衍射图谱。图中：纵坐标为衍射强度，横坐标为衍射角2θ，图中43.31º、50.43º、74.13º为零价铜的衍射峰，36.42º为一价亚铜的衍射峰。由图可得出结论，衍射峰峰型尖锐，可表明单质铜结晶度高。
图4为介孔型中空掺氮碳包铜纳米催化剂的物理吸脱附曲线。
图5为介孔型中空掺氮碳包铜纳米催化剂的孔径分布图。由图4和图5可以看出：出现明显的回滞坏，测得的载体比表面为611.49 m2/g，最可几孔径为2.68 nm。由图可得到结论，本发明制备的掺氮中空碳球的孔为介孔。
具体实施方式
本发明使用的化学物质材料为：去离子水、氨水、硫酸铜、十六烷基三甲基溴化铵（CTAB）、聚乙烯吡咯烷酮(PVP)、吡咯、苯乙烯、偶氮二异丁腈(AIBN)、过硫酸钾、水合肼、高纯氮气、高纯氢气，其准备用量如下：以克、毫升、厘米3为计量单位
去离子水:H2O 液体 3000 ml±50 ml
氨水:NH3•H2O 液体 6 ml±0.1 ml
吡咯:C4H5N 液体 3 ml±0.1 ml
苯乙烯:C8H8 液体 9 ml±0.1 ml
水合肼:H6N2O 液体 280 µl±0.1 µl
偶氮二异丁腈:C8H12N4 固体 1 g±0.001 g
过硫酸钾:K2S2O8 固体 1 g±0.001 g
硫酸铜:CuSO4•5H2O 固体 2 g±0.001 g
十六烷基三甲基溴化铵:C19H42BrN 固体 1 g±0.001 g
聚乙烯吡咯烷酮:(C6H9NO)n 固体 4 g±0.001 g
氮气：N2 气体 100000 cm3±100 cm3
氢气：H2 气体 100000 cm3±100 cm3
介孔型中空掺氮碳包铜纳米催化剂的制备方法如下：
(1) 纳米铜胶体的制备：
①称取2 g±0.001 g的CuSO4•5H2O溶于10 ml±0.1 ml去离子水中，待其完全溶解后向烧杯中逐滴滴入氨水，使出现沉淀，后又刚好消失；
②加入3 g±0.001 gPVP、1 g±0.001 gCTAB，超声分散30 min；
③将烧杯放于50 ℃水浴中持续搅拌2 h；
④将水浴温度升至70 ℃，加入水合肼，使得C=0.06 M，颜色由蓝变为红色(或紫红色)，持续搅拌2 h，得铜纳米胶体，封存备用。
(2) 制备CuNPs/PS:
①取1.5 g±0.001 g溶胶分散于20 ml去离子水中，加入9 ml±0.1 ml苯乙烯，后加入适量AIBN，使得其质量占混合溶液总质量的2.0%，随后超声分散10 min，快速搅拌30 min；
②将水浴温度升至85 ℃，匀速搅拌7 h，干燥得CuNPs/PS。
(3) 制备CuNPs/PS@PPy：
①CuNPs/PS分散到无水乙醇中，加入称取的1 g±0.001 gPVP，持续室温搅拌12 h，离心分离；
②将①中产物分散在去离子水中，得30ml混合溶液；
③在②混合溶液中加入30 ml±0.1 ml去离子水、3 ml±0.1 ml吡咯，室温搅拌30min，加入1 g±0.001 gK2S2O8，持续搅拌8 h，离心洗涤后50 ℃干燥，收集产物CuNPs/PS@PPy。
(4) 高温炭化后制得催化剂：将CuNPs/PS@PPy置于管式炉中，通入氮气，将流速设为100 cm3/min。升温速率为3 ℃/min，处理温度为700 ℃±5℃，处理时间为3 h，得介孔型碳包铜纳米催化剂。
(5)研磨、过筛
将所得催化剂用玛瑙研钵研磨，后用650目筛网过筛。
(6)产物储存
将制备的催化剂储存于氮气气氛下的样品袋中，干燥密闭储存。
(7)活性评价
催化剂活性评价在25 ml容积的微型高压反应釜中进行。称取0.1 g催化剂加入反应釜釜体内，加入10 mL甲醇，密闭釜体后，通入反应气CO至压力为2.0 MPa、O2至总压力为3.0MPa。设置搅拌速率为900 r/min，温度为110 ℃下反应90 min后停止加热，降至室温，离心后取上层清液，再用气相色谱进行产物分析。
(8)检测、分析、表征
对制备的催化剂进行表面形貌、内部结构、化学物理性能进行检测、分析和表征；
用扫描电子显微镜SEM观察样品表面形貌；
用透射电子显微镜TEM观察样品内部结构及内部空腔尺寸；
用X-射线粉末衍射仪进行晶相分析；
用氮气吸附-脱附仪进行比表面测量及孔径分析；
结论：介孔型碳包铜纳米催化剂为黑色粉体，粉体颗粒直径小于400nm，碳层厚度小于30nm，产物纯度达98.9%，催化活性好，反应中DMC时空收率可达到1251mg/g∙h，选择性高达99.99%。
Claims (2)
1.一种介孔型中空掺氮碳包铜纳米催化剂的制备方法，其特征在于，包括如下步骤：
⑴硫酸铜溶液中滴入氨水，使出现沉淀后又刚好消失，然后加入PVP以及CTAB，加热搅拌，加入水合肼，使得C=0.06 M，颜色由蓝变为红色或紫红色，持续搅拌，制备铜纳米胶体；
⑵在铜纳米胶体中加入苯乙烯以及AIBN，超声分散、搅拌、加热，干燥获得CuNPs/PS；
⑶CuNPs/PS分散到无水乙醇中，加入PVP，搅拌、离心，然后将产物分散在去离子水中，加入吡咯、K2S2O8，搅拌、离心、洗涤、干燥，获得CuNPs/PS@PPy；
⑷将CuNPs/PS@PPy进行高温碳化处理，获得介孔型碳包铜纳米催化剂。
2.根据权利要求1所述的一种介孔型中空掺氮碳包铜纳米催化剂的制备方法，其特征在于，所述高温碳化处理的步骤为：将CuNPs/PS@PPy置于惰性气体环境下升温至700 ℃±5℃，处理时间为 3h。
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