CN108285149A - 一种银型锰钾矿八面体分子筛的制备方法 - Google Patents
一种银型锰钾矿八面体分子筛的制备方法 Download PDFInfo
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 31
- 239000004332 silver Substances 0.000 title claims abstract description 30
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- 238000005273 aeration Methods 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
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- 238000000034 method Methods 0.000 abstract description 14
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- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract description 2
- 238000002474 experimental method Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000011572 manganese Substances 0.000 description 5
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- 230000005540 biological transmission Effects 0.000 description 3
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- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HVCXHPPDIVVWOJ-UHFFFAOYSA-N [K].[Mn] Chemical compound [K].[Mn] HVCXHPPDIVVWOJ-UHFFFAOYSA-N 0.000 description 1
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- 229960004217 benzyl alcohol Drugs 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- ZWXOQTHCXRZUJP-UHFFFAOYSA-N manganese(2+);manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+3].[Mn+3] ZWXOQTHCXRZUJP-UHFFFAOYSA-N 0.000 description 1
- KNLQKHUBPCXPQD-UHFFFAOYSA-N manganese;sulfuric acid Chemical compound [Mn].OS(O)(=O)=O KNLQKHUBPCXPQD-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- XRRQZKOZJFDXON-UHFFFAOYSA-N nitric acid;silver Chemical compound [Ag].O[N+]([O-])=O XRRQZKOZJFDXON-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- BBQAGXHCESJTDM-UHFFFAOYSA-J potassium cerium(3+) tetrahydroxide Chemical compound [Ce+3].[K+].[OH-].[OH-].[OH-].[OH-] BBQAGXHCESJTDM-UHFFFAOYSA-J 0.000 description 1
- 150000003333 secondary alcohols Chemical class 0.000 description 1
- -1 silver ions Chemical class 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
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- 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
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Abstract
本发明公布了一种银型锰钾矿八面体分子筛的制备方法,首先利用MnSO4与碱液反应生成Mn(OH)2沉淀,并在低温环境中迅速氧化成水钠锰矿前驱物,然后在Ag离子的参与下采用水热法将水钠锰矿相转化为银型锰钾矿相,得到银型锰钾矿八面体分子筛。本发明不以K型锰钾矿为模板,而是以层状水钠锰矿为模板,拓展了银等阳离子掺杂锰钾矿的制备途径,该方法操作简易,所制备的银型锰钾矿活性高,具有纳米针状的晶形,宽度约为15纳米左右,长度从几百纳米到几微米不等。
Description
技术领域
本发明涉及一种银型锰钾矿八面体分子筛的制备方法,属于纳米材料、催化材料和电容材料领域。
背景技术
锰钾矿是一种具有隧道结构的八面体分子筛,是由[MnO6]八面体以共棱边和共顶角组成的2×2型隧道结构,晶格中存在着Mn2+、Mn3+和Mn4+,孔径大小约为0.46nm×0.46nm,K+、Ba2+等阳离子位于隧道结构中保持电化学平衡。因此锰钾矿具有良好的氧化还原性、吸附性和表面酸性,已被证明在离子交换、电池材料、吸附剂、分子筛、环境修复材料、催化剂、核废料固定等领域具有重要的应用前景。
金属阳离子已被证明易于负载或掺杂到锰氧八面体骨架或进入孔径内,常见掺杂的金属元素包括Ag、Pd、Zr、Ce、V、Ti、Pt、Sn、Fe、Cu、Co等,掺杂后锰钾矿的性能有大幅度提高。其中Ag掺杂后的锰钾矿在催化苯甲醇、仲醇、辛醇等转化上相对其他催化剂具有明显优势,能够有效低温吸附CO、NO、SO2气体并催化其氧化,并且是一种有潜力的电容材料。
目前国内外制备Ag型锰钾矿八面体分子筛的方法主要包括两种:一种是间接法,通过水热法或溶胶凝胶法合成K型锰钾矿后,采用Ag离子交换K离子制备;另一种是直接法,采用AgMnO4在酸性介质(硝酸、硫酸等)中直接水热氧化Mn2+制备,或者AgMnO4与Ag2O高温固相反应制备而得。
发明内容
本发明的目的是提供一种银型锰钾矿八面体分子筛的制备方法,从而提供作为催化剂等应用的银型锰钾矿材料。
本发明的技术方案如下:
一种银型锰钾矿八面体分子筛的制备方法,包括以下几个步骤:
(1)将MnSO4溶液与过量碱液的混合液在低温环境中曝气搅拌反应,过滤,反复洗涤至pH7~8,干燥,研磨,得到水钠锰矿前驱物粉末;
(2)取上述粉末加入计量的硝酸银溶液,置于高温高压反应釜300~500℃温度下反应,过滤,洗涤,干燥后制得银型锰钾矿八面体分子筛。
所述方法步骤1)中,过量碱液使用KOH和/或NaOH溶液均可,推荐所述混合液中MnSO4与OH-的摩尔浓度比值为1:7.5~1:14。
所述方法步骤1)中,低温环境、大曝气量和快速搅拌均有利于产物的纯度,推荐10℃以下水浴环境、30L/min以上空气曝气量、100-150r/min的振荡速度。
所述方法步骤1)中,曝气反应时间为5小时以上。
所述方法步骤2)中,所述硝酸银溶液的浓度为0.08~0.1摩尔/升,优选每克粉末样品加入20mL 0.08~0.1摩尔/升的硝酸银溶液;高温高压釜的填装率在40%以下。
所述方法步骤2)中,高温水热反应时间为3.5~12小时。
本发明通过制备水钠锰矿前驱物后,在Ag离子的参与下采用水热法将水钠锰矿相转化为银型锰钾矿相,该制备方法尚未见报道,其主要机理是:利用MnSO4与碱液反应生成Mn(OH)2沉淀,并在低温环境中迅速氧化成水钠锰矿;之后在银离子溶液中,Ag离子与水钠锰矿层间的K或Na离子交换,并在高温水热环境中以Ag离子为模板,层状水钠锰矿结构调整成为隧道结构的银型锰钾矿八面体分子筛。本发明方法制备出的银型锰钾矿具有纳米针状的晶形,宽度约为15纳米左右,长度从几百纳米到几微米不等。本发明方法不以K型锰钾矿为模板,而是以层状水钠锰矿为模板,拓展了银等阳离子掺杂锰钾矿的制备途径,该方法操作简易,产品活性高。
附图说明
图1是本发明实施例2中制备的银型锰钾矿八面体分子筛的X射线粉晶衍射图。
图2是本发明实施例2中制备的银型锰钾矿八面体分子筛的高分辨透射电镜形貌图。
具体实施方式
下面结合附图,通过实例说明利用本发明的方法合成银型锰钾矿型八面体分子筛的最佳实验条件。
实验所用化学原料有:分析纯硫酸锰,分析纯氢氧化钾或氢氧化钠,分析纯硝酸银。实验所用的仪器主要有:SHA-2A型冷冻水浴恒温振荡器、鼓气机、高温高压反应釜。实验样品物相表征用RIGAKA-RA X射线粉晶衍射仪分析,形貌用高分辨透射电镜(JEOL JEM-2010)观察。
实施例1、前驱物水钠锰矿类型的影响
本实验在500mL的反应体系中用0.2M MnSO4与2.75M的NaOH或KOH在1℃水浴中,通空气量为60L/min,振荡搅拌转速为150r/min的条件下反应5小时,然后过滤洗涤至pH=7~8,干燥后,破碎至小于200目,得到前驱物粉末;取1g上述前驱物粉末与20mL 0.1M AgNO3溶液置于密封的高温高压反应釜中,在300℃反应9小时,洗涤,干燥。采用NaOH和KOH碱液形成的Na型和K型水钠锰矿,都可以作为前驱物使用进一步转化成为银型锰钾矿。
实施例2、水热反应温度的影响
本实验在500mL的反应体系中用0.2M MnSO4与2.75M的KOH在1℃水浴中,通空气量为60L/min,振荡搅拌转速为150r/min的条件下反应5小时,然后过滤洗涤至pH=7~8,干燥后,破碎至小于200目,得到水钠锰矿前驱物粉末;取1g水钠锰矿前驱物粉末与20mL0.1MAgNO3溶液置于密封的高温高压反应釜中,分别在室温、150℃、200℃、250℃、300℃、400℃、500℃温度下反应9小时,洗涤,干燥。其中400℃所制银型锰钾矿八面体分子筛的X射线衍射图如图1所示,具有纯的银型锰钾矿物相;其高分辨透射电镜图如图2所示,可以看出发育一维针状的纳米晶形,宽度在十几纳米,长度从几十纳米到几微米不等。中低温环境中即便在银模板作用下水钠锰矿也无法转变成为隧道结构的银型锰钾矿,只有在300℃以上才有银型锰钾矿相的生成。
实施例3、银离子浓度的影响
本实验在500mL的反应体系中用0.2M MnSO4与2.75M的KOH在7℃,通空气量为60L/min,振荡搅拌转速为150r/min的条件下反应5小时,然后过滤洗涤至pH=7~8,干燥后,破碎至小于200目,得到水钠锰矿前驱物粉末;取1g水钠锰矿前驱物粉末,分别与20mL 0.01M,0.04M,0.06M、0.08M和0.1M AgNO3溶液置于密封的高温高压反应釜中,在300℃下反应9小时,洗涤,干燥。采用0.08M浓度以下AgNO3溶液不足以使全部水钠锰矿前驱物转化成银锰钾矿,部分会形成方铁锰矿和黑锰矿,因此每克水钠锰矿前驱物需采用在0.08~0.1M浓度银溶液才能形成银型锰钾矿。
实施例4、水热反应时间的影响
本实验在500mL的反应体系中用0.2M MnSO4与2.75M的NaOH或KOH在1℃水浴中,通空气量为60L/min,振荡搅拌转速为150r/min的条件下反应5小时,然后过滤洗涤至pH=7~8,干燥后,破碎至小于200目,得到水钠锰矿前驱物粉末;取1g水钠锰矿前驱物粉末与20mL0.1M AgNO3溶液置于密封的高温高压反应釜中,在300℃下分别反应2小时、3.5小时、5小时、7小时、9小时、12小时,洗涤,干燥。较短的时间水钠锰矿会部分转化成方铁锰矿和黑锰矿,随着反应时间的推进进一步转化成为银型锰钾矿,需要3.5小时以上的时间才能更好地完成反应。
Claims (9)
1.一种银型锰钾矿八面体分子筛的制备方法,包括以下步骤:
1)将MnSO4溶液与过量碱液的混合液在低温环境中曝气搅拌反应,过滤,反复洗涤至pH7~8,干燥,研磨,得到水钠锰矿前驱物粉末;
2)取步骤1)制备的粉末加入计量的硝酸银溶液,置于高温高压反应釜300~500℃温度下反应,过滤,洗涤,干燥,制得银型锰钾矿八面体分子筛。
2.如权利要求1所述的制备方法,其特征在于,步骤1)中所述碱液是KOH溶液和/或NaOH溶液。
3.如权利要求1所述的制备方法,其特征在于,步骤1)所述混合液中MnSO4与OH-的摩尔浓度比值为1:7.5~1:14。
4.如权利要求1所述的制备方法,其特征在于,步骤1)的反应在10℃以下水浴环境,30L/min以上空气曝气量,100~150r/min的振荡速度下进行。
5.如权利要求1所述的制备方法,其特征在于,步骤1)曝气反应5小时以上。
6.如权利要求1所述的制备方法,其特征在于,步骤2)中所述硝酸银溶液的浓度为0.08~0.1摩尔/升。
7.如权利要求6所述的制备方法,其特征在于,步骤2)中每克粉末样品加入20mL 0.08~0.1摩尔/升的硝酸银溶液。
8.如权利要求1所述的制备方法,其特征在于,步骤2)高温高压釜的填装率在40%以下。
9.如权利要求1所述的制备方法,其特征在于,步骤2)高温水热反应时间为3.5~12小时。
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