CN110052274A - 一种细菌纤维素可控合成多级孔金属氧化物催化剂的方法 - Google Patents
一种细菌纤维素可控合成多级孔金属氧化物催化剂的方法 Download PDFInfo
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- CN110052274A CN110052274A CN201810070948.2A CN201810070948A CN110052274A CN 110052274 A CN110052274 A CN 110052274A CN 201810070948 A CN201810070948 A CN 201810070948A CN 110052274 A CN110052274 A CN 110052274A
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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Abstract
本发明涉及一种细菌纤维素可控合成多级孔金属氧化物催化剂的方法,属于催化剂制备领域。该催化剂采用溶胶凝胶法,在混合金属盐溶液中加入细菌纤维素造孔剂,通过简单的改变细菌纤维素的投加比例以及糖分含量即可调控氧化物的孔径分布制备多级孔氧化物催化剂。采用生物造孔剂制备多级孔氧化物催化剂,合成工艺简单,步骤简明,可不用改性,直接经过焙烧产生多级孔结构,且孔径可调,有利于反应物及产物的传质扩散,具有较大的比表面积。本发明中通过简单的改变细菌纤维素的投加比例以及糖分含量即可调控多级孔氧化物的孔径分布,与传统的多种模版剂(微孔、介孔、大孔模板剂)同时使用调控多级孔相比,合成方法简单易行,原料来源广泛,成本低、能耗低、可大规模生产。
Description
技术领域
本发明涉及一种细菌纤维素可控合成多级孔金属氧化物催化剂的方法,属于催化剂制备领域。
背景技术
在多相催化反应过程中,催化剂的活性与其内部孔道结构密切相关。金属氧化物作为有效的多相催化反应的催化剂,其制备过程中的孔道结构设计一直是该类型催化剂的研发重点。
金属氧化物催化剂的孔道结构不受载体本身结构的限制,但制备方法却在很大程度上影响着金属氧化物催化剂的结构与活性。金属氧化物催化剂的孔道大小可分为微孔、介孔和大孔三类。微孔材料的孔道体系有助于内部晶体表面积的形成,并产生很多的吸附和催化活性位,但因其孔径较小,大分子扩散受限制,从而导致微孔材料的孔道利用率降低,其次微孔材料较快的积碳速率使催化剂的活性和稳定性较差,限制了其在催化领域的应用。而孔径相对较大的介孔、大孔材料能克服微孔材料对大体积分子传质扩散难的问题,但不利于活性位点的分布以及活性位点与底物的接触。为克服单一孔材料的缺点,调变孔道结构的多级孔材料应运而生。多级孔是兼具微孔、介孔和大孔中2种及以上类型的多孔体系。
多孔体系孔道和空腔的网状结构可以提高反应分子和产物分子的迁移和扩散,有利于催化反应的进行和分离过程。制备同时具有微孔、介孔和大孔的新型多级孔金属氧化物催化剂,对提高催化反应的效率是非常有益的,也是未来孔材料发展的主要方向。
金属氧化物的制备方法常用的有共沉淀法、水热法、硬模板法和溶胶凝胶法等。溶胶凝胶法因具有:(1)反应温度低,易控制;(2)操作流程简单,无需昂贵的设备,成本低;(3)化学计量准确,容易修饰改性,掺杂的范围广等优点,是目前较多采用的制备多孔氧化物的方法。溶胶凝胶法制备多孔金属氧化物催化剂时,造孔剂起着决定性的作用。为进一步改善溶胶-凝胶法制备多孔复合金属氧化物催化剂的性能和实现催化剂制备的绿色化,近年来,用新型生物基材料做造孔剂制备复合金属氧化物逐渐成为研究的热点,如酵母、活性炭纤维和棉花等均已经被用作制造多孔材料的原料。
作为新型的生物基材料,细菌纤维素(Bacterial cellulose,BC)由一些微生物经生物方法合成的,例如木醋杆菌。BC具有小的纤维结构和高的比表面积,很高的纤维纯度,高的抗张强度和弹性模量,有良好的透气、透水性能,极佳的形状维持能力和抗撕裂性,较高的结晶度和优异的化学稳定性,BC已广泛应用在食品加工、医药生产、纺织、造纸、化工和采油等行业。纯天然来源的BC有利于能源和环境的可持续发展,BC的表面羟基可以为催化剂前驱体提供键位,同时还就有锚定金属的作用,目前已有将BC用于催化领域的报道,尝试将 BC作为模板剂或载体去修饰改性催化剂的孔道结构。用BC膜为生物模板剂合成具有网状结构的介孔TiO2,与以蛋壳膜做模板剂制备出的超细纤维网状结构TiO2相比,其光催化活性明显提高[D Y Zhang,L M Qi.Synthesis of mesoporous titania networksconsisting of anatase nanowires by templating of bacterial cellulosemembranes.Chemical Communication,2005,(21): 2735-2737]。用BC作为模板剂来合成La2CuO4纳米晶体催化剂,该催化剂具有大的比表面积,在甲烷重整实验中呈现出优异的活性[J Z Yang,W H Tang,X L Liu,et al.Bacterial cellulose-assisted hydrothermalsynthesis and catalytic performance of La2CuO4 nanofiber for methanol steamreforming[J].International Journal of Hydrogen Energy,2013,38(25): 10813-10818]。由细菌纤维素得到的碳纳米纤维作为载体(CNF)合成的CoFe2O4/CNF催化剂,其电催化活性和热稳定性均较高[S S Liu,W N Yan,X C Cao,et al.Bacterial- cellulose-derived carbon nanofiber supported CoFe2O4as efficient electrocatalyst foroxygen reduction and evolution reactions[J].International journal of hydrogenenergy,2016,41(11):5351-5360]。
专利200910200345.0将细菌纤维素膜浸泡在贵金属盐溶液中制得金属纳米颗粒复合细菌纤维素,应用于光学、电学、催化以及化学性质在很多领域。然而在制备过程中,需要对金属纳米颗粒复合细菌纤维素在高温高压下进行处理,并在处理后用蒸馏水对该物质进行反复洗涤去除多余贵金属离子,这些操作过程不仅繁琐,而且造成试剂的浪费。专利201410047099.0提出在高温下将细菌纤维素碳化,原位生成碳模板剂,无需外加表面活性剂或介孔氧化硅模板剂,同时金属活性组分均匀分布在碳中。通过高温热处理除去模板剂碳,得到纳米介孔氧化物;或者除去碳模板剂后,通过高温还原得到纳米介孔金属材料。该制备过程需要对物质进行多步热处理(在不同的气体气氛),步骤繁琐,能耗比较大。将商品细菌纤维素作为造孔剂,通过调节细菌纤维素中糖分的多少可以有效调控微孔。而将细菌纤维素不经过改性直接作为造孔剂,通过改变细菌纤维素的组成来调控孔道结构的多级孔催化剂的制备方法尚未见报道。因此,利用细菌纤维素研发可控多孔金属氧化物的简易制备方法,既能有效调控多级孔结构,又能控制高活性晶面的暴露比例,从而获得高效多孔催化剂,可以用于任何催化反应中,比如挥发性有机物的催化氧化、NOX的选择性催化还原、CO氧化、 CO加氢和石油的催化裂化等。
发明内容
本发明的目的是借助细菌纤维素的特殊结构制备多级孔氧化物催化剂。其原料成本低廉,制备过程工艺简单,操作步骤简明、绿色无害,制备出的催化剂具有多级孔结构,孔径可调,是一种环境友好、高效、高稳定性的催化剂。
为了实现上述目的,本发明采取了如下技术方案。
本发明提供了多级孔氧化物催化剂的绿色合成方法,以金属盐为原料,以细菌纤维素为造孔剂,利用溶胶-凝胶法制备多级孔氧化物,通过调节细菌纤维素和金属盐比例、糖类含量来调控催化剂孔径分布,制备步骤如下:
(1)将不同金属盐按一定的摩尔比溶解在40~70mL溶剂中,溶解温度在50~80℃之间;
(2)将细菌纤维素在10~40MPa下均质,得到均匀的细菌纤维素粘稠状液体;
(3)待(1)中金属盐完全溶解后加入一定比例的(2)细菌纤维素(不同糖类比例)造孔剂,形成溶胶,在60~90℃下加热并搅拌2~5h,形成凝胶;
(4)将(3)中粘凝胶在室温下老化0~48h后于80~110℃下在烘箱中干燥0~12h,并在空气流中于350~550℃下煅烧2~8h。
所述的金属为铜、钴、铁、锌、锰、铬、镍、钒、锶、铈、锆、钇和钐等过渡金属以及钠、钾等主族金属。
所述的金属盐为金属乙酸盐和金属硝酸盐。
所述的溶剂为去离子水或无水乙醇。
所述的细菌纤维素造孔剂为培养或商品木醋杆菌、无色杆菌、气杆菌、土壤杆菌、产碱杆菌、产醋杆菌、醋化杆菌、巴氏醋杆菌、葡萄糖杆菌、农杆菌、根瘤菌、假单胞杆菌、八叠球菌、动胶菌或空肠弯曲菌中等属的微生物合成的细菌纤维素或细菌纤维素混合造孔剂。
所述的细菌纤维素混合造孔剂为细菌纤维素与草酸、柠檬酸,及另一种或多种有机溶液的混合溶液。
所述的造孔剂中另一种或多种有机溶液是乙醇、或乙醇与乙二醇、环己烷、石油醚、正己烷等其中一种或多种有机溶剂的混合溶液。
所述的其他糖分比例为细菌纤维素与其他糖类的比例为0~25%。
所述的外加糖类为葡萄糖、果糖、蔗糖、乳糖、麦芽糖、淀粉和糊精中的一种或多种糖类的混合。
本发明具有以下有益效果:
(1)本发明所用的细菌纤维素和糖类来源广泛,廉价易得,焙烧分解产生二氧化碳和水,生产过程无污染,是环境友好型的造孔剂,可大规模生产。
(2)本发明采用细菌纤维素及其糖分含量调控多级孔氧化物催化剂的孔径分布,利用细菌纤维素的亲水性,以及普通化学类造孔剂没有的超精细纤维网状结构,更大的比表面积,能更好得使金属盐分布均匀,而且焙烧之后,可产生微孔、介孔或大孔结构,糖类在高温下先碳化形成碳球,可用作微孔造孔剂,持续升温,产生微孔结构。
(3)本发明合成的催化剂具有多级孔结构,且孔径可调,有利于反应物及产物的传质扩散,具有较大的比表面积。
(4)本发明采用生物造孔剂制备多级孔氧化物催化剂,合成工艺简单,步骤简明,可不用改性,直接经过焙烧产生多级孔结构。所使用的制备设备简单,可在多个催化领域进行应用。
(5)本发明通过简单的改变细菌纤维素的投加比例以及糖分含量即可调控多级孔氧化物的孔径分布,与传统的多种模版剂(微孔、介孔、大孔模板剂)同时使用调控多级孔相比,合成方法简单易行,成本低、能耗低、可大规模生产。
附图说明
图1为实施例1中以细菌纤维素为造孔剂和实施例2中以含糖细菌纤维素为造孔剂合成的复合氧化物催化剂CuCe0.75Zr0.25Oy的N2吸脱附(A)及孔径分布曲线(B)(由细菌纤维素为造孔剂(a)与细菌纤维和蔗糖(b)为造孔剂所制备的CuCe0.75Zr0.25Oy催化剂的N2吸脱附曲线(A)及孔径分布曲线(B))。
图2为实施例1中以细菌纤维素为造孔剂和实施例2中以含糖细菌纤维素造孔剂合成的复合氧化物催化剂CuCe0.75Zr0.25Oy催化降解甲苯的转化率曲线(A)及CO2选择性曲线(B)(由细菌纤维素为造孔剂(a)与细菌纤维和蔗糖(b)为造孔剂所制备的CuCe0.75Zr0.25Oy催化剂催化降解甲苯的转化率(A)及CO2的选择性(B))。
具体实施方式
下面列举实例,说明本发明涉及的以细菌纤维素作为造孔剂的多孔金属氧化物催化剂的制备方法。
实施例1:7.986g乙酸铜、10.742g乙酸铈和12.27g乙酸锆在50℃下溶解在70mL的无水乙醇中,称取固液比为3.6%的培养木醋杆菌纤维素100g加入上述金属乙酸盐溶液中形成胶状物,将溶胶在80℃下均匀搅拌加热3h,在空气气氛下老化12h形成凝胶,然后置于烘箱在105℃下中干燥8h形成催化剂前驱体,再在马弗炉里于空气气氛下在550℃下煅烧2h。
实施例2:用实施例1相同的操作,不同之处在于:一定量的硝酸铜、硝酸铈和硝酸锆在50℃下溶解在70mL的无水乙醇中,称取固液比为3.6%的培养木醋杆菌纤维素100g和含25%蔗糖溶液,加入上述金属硝酸盐溶液中形成胶状物。
实施例3:用实施例1相同的操作,不同之处在于:一定量的乙酸锰、乙酸铈和乙酸锆在65℃溶解在70ml的无水乙醇中,称取固液比为3.6%的培养木醋杆菌纤维素100g加入上述金属乙酸盐溶液中形成胶状物,将溶胶在60℃下均匀搅拌加热2h。
实施例4:用实施例1相同的操作,不同之处在于:将溶胶在90℃下均匀搅拌加热4h,在空气气氛下老化48h。
实施例5:用实施例1相同的操作,不同之处在于:使用商品用椰果肉(商品木醋杆菌纤维素),在40MPa的均质机上进行均质,之后称取固液比为3.6%的商品木醋杆菌纤维素100g和含20%葡萄溶液,加入到上述硝酸铜、硝酸铈和硝酸锆溶液中形成溶胶。
实施例6:用实施例1相同的操作,不同之处在于:将溶胶置于烘箱在95℃下中干燥3 h形成催化剂前驱体,在马弗炉里于空气气氛下于450℃下煅烧5h。
实施例7:用实施例1相同的操作,不同之处在于:使用商品用椰果肉(商品木醋杆菌纤维素),在30MPa的均质机上进行均质,之后称取固液比为3.6%的商品木醋杆菌纤维素100g和含5%葡萄糖溶液,加入到上述金属乙酸盐溶液中形成溶胶。
实施例8:用实施例1相同的操作,不同之处在于:一定量的乙酸铁、乙酸铈和乙酸锆在50℃下溶解在55ml的去离子水中。
实施例9:用实施例1相同的操作,不同之处在于:一定量的硝酸钾、硝酸铈和硝酸铬在80℃下溶解在40ml的去离子水中,称取固液比为1.2%的培养木醋杆菌纤维素100g和含10%蔗糖溶液,加入上述金属硝酸盐溶液。
实施例10:用实施例1相同的操作,不同之处在于:将溶胶在80℃下均匀搅拌加热6h,在空气气氛下老化24h,然后置于烘箱在80℃下干燥2h。
Claims (10)
1.一种细菌纤维素可控合成多级孔金属氧化物催化剂的方法,其特征在于采用溶胶凝胶法,在混合金属盐溶液中加入细菌纤维素造孔剂,通过简单的改变细菌纤维素的投加比例以及糖分含量即可调控氧化物的孔径分布制备多级孔氧化物催化剂,属于催化剂制备领域。
2.根据权利要求1所述可控合成多级孔金属氧化物催化剂的方法,其特征在于采取如下步骤:
(1)将不同金属盐按一定的摩尔比溶解在40~70mL溶剂中,溶解温度在50~80℃之间;
(2)将细菌纤维素在30~40MPa下均质,得到均匀的细菌纤维素粘稠状液体;
(3)待(1)中金属盐完全溶解后加入一定比例的(2)细菌纤维素(不同糖类比例)造孔剂,形成溶胶,在60~90℃下加热并搅拌2~5h,形成粘稠状胶体;
(4)将(3)中粘稠状胶体在室温下老化0~48h后于80~110℃下在烘箱中干燥0~12h,并在空气流中于350~550℃下煅烧2~8h。
3.根据权利要求1所述的细菌纤维素,其特征在于,所述的细菌纤维素造孔剂为培养或商品木醋杆菌、无色杆菌、气杆菌、土壤杆菌、产碱杆菌、产醋杆菌、醋化杆菌、巴氏醋杆菌、葡萄糖杆菌、农杆菌、根瘤菌、假单胞杆菌、八叠球菌、动胶菌或空肠弯曲菌中等属的微生物合成的细菌纤维素,或者细菌纤维素与草酸、柠檬酸,及另一种或多种有机溶液的混合溶液。
4.根据权利要求1所述的造孔剂,其特征在于,所用的细菌纤维素和糖类来源广泛,廉价易得,焙烧分解产生二氧化碳和水,生产过程无污染,是环境友好型的造孔剂,可大规模生产。
5.根据权利要求1所述的细菌纤维素为造孔剂,其特征在于,使用细菌纤维素做造孔剂时,不需要修饰,直接加入金属盐溶液中搅拌形成溶胶,而均质后本身的溶胶性质使得溶胶凝胶的制备方法更为简便。
6.根据权利要求1所述的混合金属盐溶液,其特征在于,所述的金属盐溶液为铜、钴、铁、锌、锰、铬、镍、钒、锶、铈、锆、钇和钐等过渡金属以及钠、钾等主族金属的乙酸盐或硝酸盐溶解到溶剂所形成的溶液中。
7.根据权利要求1所述的细菌纤维素的投加比例以及糖分含量,其特征在于,所述的外加糖类为葡萄糖、果糖、蔗糖、乳糖、麦芽糖、淀粉和糊精中的一种或多种糖类的混合,其他糖分比例为其他糖类与细菌纤维素的比例(0~25%)。
8.根据权利要求1所述的可控合成多级孔金属氧化物催化剂的方法,其特征在于,采用细菌纤维素及其糖分含量调控多级孔氧化物催化剂的孔径分布,利用细菌纤维素的亲水性,以及普通化学类造孔剂没有的超精细纤维网状结构,更大的比表面积,能更好得使金属盐分布均匀,而且焙烧之后,可产生微孔、介孔或大孔结构,糖类在高温下先碳化形成碳球,可用作微孔造孔剂,持续升温,产生微孔结构。
9.根据权利要求1所述的一种多孔氧化物催化剂的制备方法,其特征在于,采用生物造孔剂制备多级孔氧化物催化剂,合成工艺简单,步骤简明,可不用改性,直接经过焙烧产生多级孔结构,且孔径可调,有利于反应物及产物的传质扩散,具有较大的比表面积。
10.根据权利要求1所述的一种多孔氧化物催化剂的制备方法,其特征在于,通过简单的改变细菌纤维素的投加比例以及糖分含量即可调控多级孔氧化物的孔径分布,与传统的多种模版剂(微孔、介孔、大孔模板剂)同时使用调控多级孔相比,合成方法简单易行,原料来源广泛,成本低、能耗低、可大规模生产。
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