CN106365199A - 以沸石分子筛为核、介孔层为壳的蛋黄‑蛋壳型结构材料及其制备方法 - Google Patents

以沸石分子筛为核、介孔层为壳的蛋黄‑蛋壳型结构材料及其制备方法 Download PDF

Info

Publication number
CN106365199A
CN106365199A CN201610907756.3A CN201610907756A CN106365199A CN 106365199 A CN106365199 A CN 106365199A CN 201610907756 A CN201610907756 A CN 201610907756A CN 106365199 A CN106365199 A CN 106365199A
Authority
CN
China
Prior art keywords
layer
molecular sieve
mesoporous
yolk
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610907756.3A
Other languages
English (en)
Inventor
程晓维
黄文峰
邓勇辉
陈晋阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fudan University
University of Shanghai for Science and Technology
Original Assignee
Fudan University
University of Shanghai for Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fudan University, University of Shanghai for Science and Technology filed Critical Fudan University
Priority to CN201610907756.3A priority Critical patent/CN106365199A/zh
Publication of CN106365199A publication Critical patent/CN106365199A/zh
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
    • B01J20/16—Alumino-silicates
    • B01J20/18—Synthetic zeolitic molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28057—Surface area, e.g. B.E.T specific surface area
    • B01J20/28064—Surface area, e.g. B.E.T specific surface area being in the range 500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/12—Noble metals
    • B01J29/126—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
    • B01J29/14—Iron group metals or copper
    • B01J29/146—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/46—Iron group metals or copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/74—Noble metals
    • B01J29/7415—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
    • B01J29/76—Iron group metals or copper
    • B01J29/7615—Zeolite Beta
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/396—Distribution of the active metal ingredient
    • B01J35/397—Egg shell like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G3/00—Compounds of copper
    • C01G3/02—Oxides; Hydroxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Nanotechnology (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

本发明属于纳米材料技术领域，具体为以沸石分子筛为核、介孔层为壳的蛋黄‑蛋壳型结构材料及其制备方法。本发明以沸石分子筛为核层，先在沸石外表面包覆酚醛树脂层；再在酚醛树脂表面负载金属或金属氧化物作为活性组分；然后在酚醛树脂表面包覆介孔层；最后在空气中焙烧除去模板剂和酚醛树脂层，得到结构完美的核壳或蛋黄‑蛋壳结构材料。该材料介孔层孔道垂直开放，空腔大小均匀，活性组分分散均匀且不堵塞沸石分子筛和介孔分子筛的孔道，克服了反应过程中流失问题，材料稳定性好、寿命长。本发明所得材料兼具沸石分子筛、介孔分子筛以及可调变的活性组分等多种功能，制备方法简便，作为吸附剂、催化剂或功能材料等具有广泛的应用前景。

Description

以沸石分子筛为核、介孔层为壳的蛋黄-蛋壳型结构材料及其 制备方法
技术领域
本发明属于纳米材料技术领域，具体涉及一种核壳（core-shell）或蛋黄-蛋壳（yolk-shell）型结构材料及其制备方法。
背景技术
沸石分子筛是一种无机硅铝酸盐或磷酸盐晶体，骨架中含有规则且有序排列的分子尺寸的孔道或笼（ca. 0.3-1.5nm）。沸石分子筛由于其特有的结构和性能，已成为一门独立的学科，应用已遍及石油化工、环保、生物工程、食品工业、医药化工等领域。由于其具有择形催化、离子交换以及分子筛分等作用，被广泛应用于工业催化，吸附分离和离子交换等。介孔分子筛不仅具有高度有序和均匀分布的孔道结构, 孔径尺寸改变范围较宽（2-50nm）, 比表面高, 而且其骨架组分具有多样性，因此在催化、生物固定、吸附、分离和制备纳米材料等很多领域有良好的应用前景, 已成为孔材料研究领域新的热点（宋艳，李永红等，化学进展，2007，5，659-663）。
近年来，为了实现集多功能于一体的复合型材料，科学工作者着力于把不同的材料结合起来，合成出新型的蛋黄-蛋白型（core-shell）或者蛋黄-蛋壳型（yolk-shell）核壳结构，从而发挥两种或多种不同材料各自的优越性。核壳材料一般包括无机/有机，无机/无机，有机/有机，以及空心球、微胶囊等。制备方法通常包括溶胶-凝胶法、晶种法、界面生长法等。核壳材料的壳层不仅可以调节纳米粒子的表面特性，改变其表面电荷密度、表面活性、官能团、反应性、生物相容性、稳定性及分散性，同时还可以通过特殊梯度结构，将外壳粒子特有的超疏水性能、催化性能、光电性能、生物性能等赋予内核微粒，从而实现材料的多功能化。刘丽等用反胶束法将SiO2纳米粒子与感光聚酰亚胺溶液混合，制得核壳结构的纳米复合感光材料。还利用溶胶-凝胶法制备了纳米TiO2粒子与聚酰亚胺复合的材料。该类核壳结构的纳米复合材料中的感光聚酰亚胺可作为通信产业中光波导、光联接等装置的材料。
本发明获得一种新型的双功能蛋黄-蛋壳型结构材料，即先合成不同拓扑结构且形貌规整、尺寸均一、分散均匀的沸石分子筛。然后在一定条件下通过聚合反应在沸石外表面包覆合适厚度的高分子聚合物层，再以湿法浸渍的方法在其表面负载一定量的金属盐类（如铜、银、铂、金等）。最后再包覆一层介孔SiO2或者TiO2层作为保护层，并在空气中焙烧除去模板剂以及高分子聚合物层等，把金属盐类转化为相应的金属氧化物，从而得到结构完美的yolk-shell结构材料。介孔结构外壳具有良好的扩散性能，允许空腔内外的反应物或产物分子自由进出；自由移动的内核及负载在其外表面的活性组分作为催化剂增进；外壳作为保护层能有效防止活性组分或内核从空腔内流失；空腔的存在易于控制反应温度和停留时间，提供均一的反应环境。该材料兼具沸石分子筛、介孔分子筛以及可调变的活性组分等多种功能，制备方法简便，作为吸附剂、催化剂或功能材料等具有广泛的应用前景。
发明内容
本发明的目的在于提供一种以沸石分子筛为内核、介孔层为外壳的功能化蛋黄-蛋壳（yolk-shell）型结构材料及其制备方法。该材料的自由移动的内核可以充当催化剂，并且可以均匀分散金属氧化物；空腔均匀，外壳介孔孔道垂直开放，对空腔内金属氧化物起到保护作用，减少其在反应过程中流失。
本发明提供的功能化蛋黄-蛋壳型结构材料的制备方法，具体步骤为：
（1）首先，合成不同拓扑结构且形貌规整、尺寸均一、分散均匀的沸石分子筛；
（2）然后，通过聚合反应在沸石分子筛外表面包覆合适厚度的高分子聚合物层；
（3）然后，以湿法浸渍的方法在其表面负载一定量的金属盐类（所述金属如铜、银、铂或金等）；
（4）最后，再包覆一层介孔SiO2或者介孔TiO2层作为保护层，并在空气中焙烧除去模板剂以及高分子聚合物层等，形成空腔结构，并且金属盐类转化为相应的金属氧化物，从而得到结构完美的yolk-shell结构材料。
本发明中，所用的沸石分子筛，是以四丙基氢氧化铵（TPAOH）为模板，以正硅酸乙酯（TEOS）为硅源，异丙醇铝为铝源，通过水热法合成获得。
本发明中，所述的空腔结构，由空气中焙烧除去模板剂以及高分子聚合物层等而形成；具体来说，是在沸石分子筛表面通过间苯二酚与甲醛或者苯酚与甲醛在碱性条件下的聚合反应包覆一定厚度的酚醛树脂层（RF），最后在空气中焙烧脱除该有机碳层而获得。
本发明中，所述的介孔SiO2层，是在酚醛树脂层的外表面，利用TEOS在碱性条件下以十六烷基三甲基溴化铵（CTAB）为模板剂水解，然后通过在空气中焙烧除去模板剂获得；所述的介孔TiO2层，是在酚醛树脂层的外表面，在酸性水溶液中以十六烷基三甲基溴化铵为结构导向剂，以硫酸钛（Ti(SO4)2）为钛源合成获得。
上述方法中，在沸石分子筛合成过程中，需有一定温度下诱导反应过程，通过水热反应后，最后离心洗涤得到纯相沸石分子筛。
上述方法中，有机碳层的合成在乙醇和水（乙醇和水的体积比可为1-3）的混合体系中进行，20℃-35℃温度下，碱性条件下用间苯二酚与甲醛的聚合反应得到间苯二酚甲醛树脂，或者在酸性条件下苯酚与甲醛聚合得到苯酚甲醛树脂。
上述方法中，介孔层的合成在乙醇和水（乙醇和水的体积比可为1-2）的混合体系里，20℃-35℃温度下，以CTAB为模板剂，通过TEOS在碱性环境下的水解后离心水洗得到介孔SiO2，或者通过Ti(SO4)2在酸性环境下水解后离心水洗得到介孔TiO2。
上述方法中，负载的金属氧化物，是通过上述材料与相应的金属盐类湿法浸渍后焙烧形成。其中，金属负载的浓度即金属盐类的摩尔浓度为0.01-0.2，优选摩尔浓度为0.05-0.15；固液比即投入的固体（如zeolite@C）与溶剂的质量比，为1:5-1:30，优选为1:10-1:20；金属盐的湿法浸渍次数为2-5。
上述方法中，最后在空气中焙烧除去介孔层中模板剂和有机碳层得到介孔和空腔，是在马弗炉中以（1-5）℃/min速率升温至350℃-600℃，恒温保持2 h -4h，然后降至室温。
本发明制备的得到的yolk-shell结构材料，其比表面积500-800 m2/g，微孔容积为0.061-0.433 m3/g。
本发明制备的得到的yolk-shell结构材料，其介孔结构外壳具有良好的扩散性能，允许空腔内外的反应物或产物分子自由进出；自由移动的内核及负载在其外表面的活性组分作为催化剂增进；外壳作为保护层能有效防止活性组分或内核从空腔内流失；空腔的存在易于控制反应温度和停留时间，提供均一的反应环境。该材料兼具沸石分子筛、介孔分子筛以及可调变的活性组分等多种功能，制备方法简便，作为吸附剂、催化剂或功能材料等具有广泛的应用前景。
本发明所提供的结构材料，以ZSM-5@void/CuO@mSiO2为例，其特征可用如下方法进行表征：
1. 粉末X-射线衍射（XRD）。在粉末X-射线衍射中，参照标准MFI图谱，以确定在逐步合成过程中并未破坏ZSM-5沸石核的结构；
2. 透射电子显微镜（TEM）和扫描电子显微镜（SEM）。用于表征ZSM-5沸石颗粒的大小、形貌、均一性、分散性；过渡材料RF层包覆均匀程度、厚度、分散性；ZSM-5@Void@mSiO2中mSiO2层的均匀程度、厚度、分散性等；
3. 低温氮吸附。由BJH方法计算产物比表面积和孔容积。
附图说明
图1分别为（a）ZSM-5、(b)ZSM-5@RF、(c)ZSM-5@void/CuO@mSiO2的XRD谱图。从中可以看出，合成的ZSM-5沸石，在外面包覆一层有机碳层，以及再在外面包覆一层介孔二氧化硅层后经600℃空气中焙烧经处理后的产物中内核ZSM-5结构均保持完美。
图2为ZSM-5的TEM图及对应的SEM图。
图3为ZSM-5@RF的TEM图及对应的SEM图。
图4为ZSM-5@void/CuO@mSiO2的TEM图及对应的SEM图。从图中可以看出，合成出来的ZSM-5沸石颗粒分散均匀，尺寸均一，形貌规则。ZSM-5@RF样品有机碳层包覆得十分均匀，厚度适宜。ZSM-5@void/CuO@mSiO2样品介孔SiO2层包覆得十分均匀，厚度合适，获得yolk-shell结构材料。
图5分别为(a)ZSM-5、(b)ZSM-5@RF、(c)ZSM-5@void/CuO@mSiO2的低温氮吸附谱图。三者均呈现典型的I型吸附曲线。其中ZSM-5比表面积和微孔容积分别为384 m2/g和0.030 cm3/g，这说明其结构完美且孔道开放；ZSM-5@RF比表面积和微孔容积分别为16m2/g和0.056 cm3/g，说明其孔道基本上完全被堵塞，ZSM-5表面被有机碳层完全包覆；ZSM-5@void/CuO@mSiO2比表面积和微孔容积分别为577 m2/g和0.433 cm3/g，说明有机碳层和模板剂CTAB完全去除，而且根据曲线类型可以看出介孔层完美呈现。
具体实施方式
实施例
本发明实施例通过以下表格中原料及配比实现。

Claims (10)

1.一种以沸石分子筛为核、介孔层为壳的蛋黄-蛋壳型结构材料的制备方法，其特征在于，具体步骤为：
（1）首先，合成不同拓扑结构且形貌规整、尺寸均一、分散均匀的沸石分子筛；
（2）然后，通过聚合反应在沸石分子筛外表面包覆合适厚度的高分子聚合物层；
（3）然后，以湿法浸渍的方法在步骤（2）得到的材料表面负载一定量的金属盐类；
（4）最后，再包覆一层介孔SiO2或者介孔TiO2层作为保护层，并在空气中焙烧除去模板剂以及高分子聚合物层，形成空腔结构，同时把金属盐类转化为相应的金属氧化物，从而得到蛋黄-蛋壳型结构材料。
2.根据权利要求1所述的制备方法，其特征在于，所述的沸石分子筛，是以四丙基氢氧化铵为模板，以正硅酸乙酯为硅源，异丙醇铝为铝源，通过水热法合成获得。
3.根据权利要求1所述的制备方法，其特征在于，所述金属为铜、银、铂或金。
4.根据权利要求1、2或3所述的制备方法，其特征在于，所述的空腔结构，是在沸石分子筛表面通过间苯二酚与甲醛或者苯酚与甲醛在碱性条件下的聚合反应包覆一定厚度的有机碳层即酚醛树脂层，最后在空气中焙烧脱除该有机碳层而获得。
5.根据权利要求4所述的制备方法，其特征在于，所述的介孔SiO2层，是在酚醛树脂层的外表面，利用TEOS在碱性条件下以十六烷基三甲基溴化铵为模板剂水解，然后在空气中焙烧除去模板剂获得；所述的介孔TiO2层，是在酚醛树脂层的外表面，在酸性水溶液中以十六烷基三甲基溴化铵为结构导向剂，以硫酸钛为钛源合成获得。
6.根据权利要求4所述的制备方法，其特征在于，所述的有机碳层的合成在乙醇和水的混合体系中进行，20℃-35℃温度下，碱性条件下用间苯二酚与甲醛的聚合反应得到间苯二酚甲醛树脂，或者在酸性条件下苯酚与甲醛聚合得到苯酚甲醛树脂。
7.根据权利要求4所述的制备方法，其特征在于，所述的介孔层的合成在乙醇和水的混合体系里，20℃-35℃温度下，以CTAB为模板剂，通过TEOS在碱性环境下的水解后离心水洗得到介孔SiO2，或者通过Ti(SO4)2在酸性环境下水解后离心水洗得到介孔TiO2。
8. 根据权利要求4所述的制备方法，其特征在于，在空气中焙烧除去介孔层中模板剂和有机碳层得到介孔和空腔，是在马弗炉中以（1-5）℃/min速率升温至350℃-600℃，恒温保持2h -4h，然后降至室温。
9. 一种由权利要求1-8之一所述制备方法得到的以沸石分子筛为核、介孔层为壳的蛋黄-蛋壳型结构材料，其比表面积500-800 m2/g，微孔容积为0.061-0.433 m3/g。
10.如权利要求9所述的以沸石分子筛为核、介孔层为壳的蛋黄-蛋壳型结构材料，作为吸附剂、催化剂或功能材料的应用。
CN201610907756.3A 2016-10-19 2016-10-19 以沸石分子筛为核、介孔层为壳的蛋黄‑蛋壳型结构材料及其制备方法 Pending CN106365199A (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610907756.3A CN106365199A (zh) 2016-10-19 2016-10-19 以沸石分子筛为核、介孔层为壳的蛋黄‑蛋壳型结构材料及其制备方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610907756.3A CN106365199A (zh) 2016-10-19 2016-10-19 以沸石分子筛为核、介孔层为壳的蛋黄‑蛋壳型结构材料及其制备方法

Publications (1)

Publication Number Publication Date
CN106365199A true CN106365199A (zh) 2017-02-01

Family

ID=57895472

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610907756.3A Pending CN106365199A (zh) 2016-10-19 2016-10-19 以沸石分子筛为核、介孔层为壳的蛋黄‑蛋壳型结构材料及其制备方法

Country Status (1)

Country Link
CN (1) CN106365199A (zh)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107934984A (zh) * 2017-12-13 2018-04-20 重庆中烟工业有限责任公司 一种微介孔蛋黄‑壳复合分子筛及其制备方法以及一种卷烟
CN107934983A (zh) * 2017-12-13 2018-04-20 重庆中烟工业有限责任公司 一种负载金属的微介孔蛋黄‑壳复合分子筛及其制备方法以及一种卷烟
CN108033458A (zh) * 2017-12-13 2018-05-15 重庆中烟工业有限责任公司 一种负载金属的微介孔蛋黄-壳复合分子筛及其制备方法以及一种卷烟
CN108033457A (zh) * 2017-12-13 2018-05-15 重庆中烟工业有限责任公司 一种微介孔蛋黄-壳复合分子筛及其制备方法以及一种卷烟
CN108033456A (zh) * 2017-12-12 2018-05-15 国家地质实验测试中心 一种具纳米二氧化硅介孔包覆结构的改性沸石及其制备和应用
CN108069438A (zh) * 2017-12-13 2018-05-25 重庆中烟工业有限责任公司 一种负载金属的微介孔蛋黄-壳复合分子筛及其制备方法以及一种卷烟
CN108125274A (zh) * 2017-12-13 2018-06-08 重庆中烟工业有限责任公司 一种微介孔蛋黄-壳复合分子筛及其制备方法以及一种卷烟
CN109824110A (zh) * 2019-02-28 2019-05-31 长沙埃比林环保科技有限公司 一种重金属污水吸附材料的制备方法
CN111167505A (zh) * 2020-01-03 2020-05-19 万华化学集团股份有限公司 一种高稳定性钌基催化剂及其制备方法和应用
CN112920464A (zh) * 2021-04-06 2021-06-08 江苏科技大学 一种具有低介电常数的填料、环氧基复合材料及其制备方法
CN113206236A (zh) * 2021-05-06 2021-08-03 合肥国轩高科动力能源有限公司 Yolk-shell结构的NCM三元正极材料的制备方法、制得的材料
CN114497892A (zh) * 2021-12-30 2022-05-13 苏州大学 介孔氧化硅/聚合物复合锂离子电池隔膜及其制备
CN114749207A (zh) * 2022-05-11 2022-07-15 东南大学 一种分子筛封装的核壳催化剂及其制备方法
CN115138346A (zh) * 2022-07-22 2022-10-04 扬州工业职业技术学院 磁性沸石复合材料、其制备方法及处理印染废水的应用

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103714929A (zh) * 2013-12-25 2014-04-09 复旦大学 具有Yolk-Shell结构的磁性介孔氧化硅复合微球及其制备方法
CN103894223A (zh) * 2014-03-26 2014-07-02 复旦大学 蛋黄-蛋壳结构的沸石分子筛-介孔氧化钛复合材料及其制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103714929A (zh) * 2013-12-25 2014-04-09 复旦大学 具有Yolk-Shell结构的磁性介孔氧化硅复合微球及其制备方法
CN103894223A (zh) * 2014-03-26 2014-07-02 复旦大学 蛋黄-蛋壳结构的沸石分子筛-介孔氧化钛复合材料及其制备方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
张晓芳等: ""双介孔SiO2的制备及表征"", 《材料导报B：研究篇》 *
邹菲等: ""反应温度对介孔二氧化钛前驱体的影响"", 《第十一届全国X射线衍射学术大会暨国际衍射数据中心（ICDD）研讨会会议论文集》 *

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108033456A (zh) * 2017-12-12 2018-05-15 国家地质实验测试中心 一种具纳米二氧化硅介孔包覆结构的改性沸石及其制备和应用
CN108033456B (zh) * 2017-12-12 2019-02-05 国家地质实验测试中心 一种具纳米二氧化硅介孔包覆结构的改性沸石及其制备和应用
CN107934984A (zh) * 2017-12-13 2018-04-20 重庆中烟工业有限责任公司 一种微介孔蛋黄‑壳复合分子筛及其制备方法以及一种卷烟
CN107934983A (zh) * 2017-12-13 2018-04-20 重庆中烟工业有限责任公司 一种负载金属的微介孔蛋黄‑壳复合分子筛及其制备方法以及一种卷烟
CN108033458A (zh) * 2017-12-13 2018-05-15 重庆中烟工业有限责任公司 一种负载金属的微介孔蛋黄-壳复合分子筛及其制备方法以及一种卷烟
CN108033457A (zh) * 2017-12-13 2018-05-15 重庆中烟工业有限责任公司 一种微介孔蛋黄-壳复合分子筛及其制备方法以及一种卷烟
CN108069438A (zh) * 2017-12-13 2018-05-25 重庆中烟工业有限责任公司 一种负载金属的微介孔蛋黄-壳复合分子筛及其制备方法以及一种卷烟
CN108125274A (zh) * 2017-12-13 2018-06-08 重庆中烟工业有限责任公司 一种微介孔蛋黄-壳复合分子筛及其制备方法以及一种卷烟
CN109824110A (zh) * 2019-02-28 2019-05-31 长沙埃比林环保科技有限公司 一种重金属污水吸附材料的制备方法
CN111167505A (zh) * 2020-01-03 2020-05-19 万华化学集团股份有限公司 一种高稳定性钌基催化剂及其制备方法和应用
CN111167505B (zh) * 2020-01-03 2022-09-20 万华化学集团股份有限公司 一种高稳定性钌基催化剂及其制备方法和应用
CN112920464A (zh) * 2021-04-06 2021-06-08 江苏科技大学 一种具有低介电常数的填料、环氧基复合材料及其制备方法
CN113206236A (zh) * 2021-05-06 2021-08-03 合肥国轩高科动力能源有限公司 Yolk-shell结构的NCM三元正极材料的制备方法、制得的材料
CN114497892A (zh) * 2021-12-30 2022-05-13 苏州大学 介孔氧化硅/聚合物复合锂离子电池隔膜及其制备
CN114749207A (zh) * 2022-05-11 2022-07-15 东南大学 一种分子筛封装的核壳催化剂及其制备方法
CN114749207B (zh) * 2022-05-11 2023-09-01 东南大学 一种分子筛封装的核壳催化剂及其制备方法
CN115138346A (zh) * 2022-07-22 2022-10-04 扬州工业职业技术学院 磁性沸石复合材料、其制备方法及处理印染废水的应用

Similar Documents

Publication Publication Date Title
CN106365199A (zh) 以沸石分子筛为核、介孔层为壳的蛋黄‑蛋壳型结构材料及其制备方法
CN107208355B (zh) 含二氧化硅气凝胶的毡的制备方法和使用该制备方法制备的含二氧化硅气凝胶的毡
CN104445215B (zh) 中空二氧化硅纳米材料的制备方法
CN108046277B (zh) 一种微米级中空磁性二氧化硅微球的制备方法
Nguyen et al. Black titania with nanoscale helicity
CN103318911B (zh) 一种多级孔道β沸石的制备方法
CN103359765A (zh) 一种形貌可控并具有介孔结构的微米γ氧化铝的制备方法
CN108339567B (zh) 一种制备封装二氧化钛的疏水沸石催化材料的方法
CN105271268B (zh) 一种单分散介孔二氧化硅微球粉及其制备方法
CN110422857B (zh) 一种Sn-beta分子筛纳米晶的制备方法
Liang et al. Mesostructured silica tubes and rods by templating porous membranes
CN107970878B (zh) 一种磷酸基团官能化中空介孔二氧化硅微球的制备方法
CN106622377A (zh) 一种球形含铝介孔复合材料和负载型催化剂及其制备方法和应用以及乙酸乙酯的制备方法
CN107457005B (zh) 球形硅藻土介孔复合材料和负载型催化剂及其制备方法和应用及油酸异丙酯制备方法
CN105170185A (zh) 一种zif-8@mcm-41分子筛及其制备方法
CN108380223A (zh) 一种基于TiO2/SiO2骨架的四元光子晶体材料及其制备方法
CN107262135B (zh) 球形含铝高岭土介孔复合材料和负载型催化剂及其制备方法和应用及油酸异丙酯的制备方法
CN102718412B (zh) 二维有序六方紧密堆积结构SiO2膜的制备方法
Giraldo et al. Spontaneous formation of inorganic helical fibers and rings
CN105948117A (zh) 一种以水热法制备HfO2纳米颗粒的方法
Wong et al. Subnanometer CdS clusters self-confined in MFI-type zeolite nanoparticles and thin films
CN107456992B (zh) 球形沸石介孔复合材料和负载型催化剂及其制备方法和应用及油酸异丙酯制备方法
CN103962171A (zh) 硅铝分子筛-氧化铝复合材料及其原位生长制备方法
CN107262136B (zh) 球形含铝伊利石介孔复合材料和负载型催化剂及其制备方法和应用及油酸异丙酯的制备方法
CN106268831B (zh) 一种模板法合成Cu2O@Zn(OH)2异质结结构的方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170201