CN106345455A - 一种薄片状纳米水钠锰矿的制备方法 - Google Patents

一种薄片状纳米水钠锰矿的制备方法 Download PDF

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CN106345455A
CN106345455A CN201610618913.9A CN201610618913A CN106345455A CN 106345455 A CN106345455 A CN 106345455A CN 201610618913 A CN201610618913 A CN 201610618913A CN 106345455 A CN106345455 A CN 106345455A
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邱国红
张腾飞
刘立虎
罗瑶
谭文峰
刘凡
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Abstract

本发明公开了一种薄片状纳米水钠锰矿的制备方法，它是将二价锰盐和硝酸盐或亚硝酸盐加入去离子水中，调节反应液pH，使反应体系的初始pH为3～8；然后将上述溶液分装到石英管中，用紫外光或可见光或太阳光照射，反应6～24h；最后将反应产物滤膜过滤或离心分离，干燥，即得。本发明生成薄片状纳米水钠锰矿，产物厚度低、粒径小，具有工艺简便、节约能源，原料丰富、价格低廉、产物纯度高、形貌可控等优点。

Description

一种薄片状纳米水钠锰矿的制备方法
技术领域
本发明涉及水钠锰矿的制备方法，具体涉及一种薄片状纳米水钠锰矿的制备方法。
背景技术
锰氧化物在自然界中分布广泛、含量丰富、且存在形式多样，因其在电化学、磁学、催化和吸附等领域表现出优异的理化特性而被广泛研究和应用。
锰氧化物晶体结构类型多，包括层状(如水钠锰矿、布塞尓矿和锂硬锰矿等)、隧道(如软锰矿、锰钾矿和钙锰矿等)和尖晶石结构等，水钠锰矿作为一种氧化度较高的层状结构氧化锰矿物备受关注。经典的用浓盐酸还原高锰酸钾制备水钠锰矿的方法应用广泛。是在100℃恒温水浴条件下将浓盐酸泵入高锰酸钾溶液中，将所得悬液于60℃老化12h，这种方法耗时较长，且制得水钠锰矿形貌为常规花球状。
形貌对锰氧化物的理化性质有显著影响。水钠锰矿的每个颗粒由单一片层随机堆叠而成，形成形貌、比表面积和活性位点不同的产物。目前研究中制备的水钠锰矿主要有线状、花瓣状和球状等。由于薄片状水钠锰矿具较大比表面积，在吸附、催化和电化学等领域具潜在的应用前景，逐渐受到关注。制备片状水钠锰矿的方法有微生物氧化法、阳离子交换法和模板法等。Omomo等将制备的水钠锰矿和TBA+溶液混合，平衡10天后得到二维片状水钠锰矿(J.Am.Chem.Soc.,2003,125:3568-3575)。Zhao等将氧化石墨烯和高锰酸钾混合悬液在60℃水浴15h制得高活性的片状水钠锰矿，能有效降解亚甲基蓝(RSC Advances,2013,3:12909-12914)。这些合成方法具有反应时间长、操作复杂、能耗大、原材料昂贵等缺点。作为能耗低、快速和便捷的方法，光化学反应被广泛应用于污染物降解和灭菌消毒等领域，而其在材料制备方面鲜有报道。
光化学反应现多用于有机污染物降解。苯并噻吩作为原油组分，在阳光照射下会被氧化成苯并噻吩-2，3-醌(海洋科学,1996,24:201)。光催化降解有机污染物如除草剂、农药和抗生素等，生成CO2、H2O或其他低毒无害物质。光催化反应一般需要在光催化剂作用下进行，常用的光催化剂为纳米二氧化钛。NO3 -/NO2 -是天然水体中.OH的重要来源之一，也可诱导一系列光氧化反应，引起有机物的氧化。但在NO3 -/NO2 -诱导下光化学氧化制备锰氧化物的研究却少有见到。
发明内容
本发明的目的是提供一种工艺简单，形貌可控，纯度高的薄片状纳米水钠锰矿的制备方法。
为了实现上述的目的，本发明采用以下技术措施：
一种薄片状纳米水钠锰矿的制备方法，包括以下步骤：
第一步：将二价锰盐和硝酸盐或亚硝酸盐加入去离子水中，搅拌溶解，二价锰盐浓度为0.05～2mol/L；硝酸根或亚硝酸根离子浓度为0.05～2mol/L，调节反应液pH，使反应体系的初始pH为3～8；
第二步：将上述溶液分装到石英管中，用紫外光或可见光或太阳光照射，反应6～24h；
第三步：将第二步反应所得悬浊液过滤或离心分离，收集沉淀物，用水或乙醇洗涤，直至洗涤液的电导≤20μS/cm，将沉淀物干燥，即得。
优选地，所述二价锰盐为MnSO4或MnCl2或Mn(CH3COO)2或Mn(NO3)2。
优选地，所述硝酸盐为NaNO3或KNO3或Mg(NO3)2或Ca(NO3)2；所述亚硝酸盐为NaNO2或KNO2或Mg(NO2)2或Ca(NO2)2。
优选地，所述紫外光或可见光的功率为50-1500W。
优选地，第二步中，所述反应时间为12h。
本发明利用NO3 -/NO2 -在紫外、可见或太阳光照下产生自由基，氧化二价锰盐生成薄片状纳米水钠锰矿，产物厚度低、粒径小。本发明具有工艺简便、节约能源，原料丰富、价格低廉、产物纯度高、形貌可控等优点。
附图说明
图1是一种实施例1、2和3中反应产物的XRD谱图：
图2是实施例1-3的产物TEM形貌对比图，图中：A为实施例1产物的TEM照片；B是实施例2产物的TEM照片；C是实施例3产物的TEM照片。
具体实施方式
以下通过实施例对本发明进行详细地说明。
实施例1
一种薄片状纳米水钠锰矿的制备方法，包括以下步骤：
第一步：将MnSO4和NaNO3加入去离子水中，搅拌溶解，MnSO4浓度为2mol/L，NaNO3浓度为2mol/L，调节反应液pH，使反应体系的初始pH为8；
第二步：将上述溶液分装到石英管中，用功率为50W紫外光照射，反应24h；
第三步：将第二步反应所得悬浊液用0.22μm滤膜过滤，收集沉淀物，用水洗涤，直至洗涤液的电导为15μS/cm，将沉淀物干燥，即得。
由图1中XRD谱图结果可知，在此条件下产物为纯相水钠锰矿，形貌为卷曲的薄片状(图2A)。
实施例2
一种薄片状纳米水钠锰矿的制备方法，包括以下步骤：
第一步：将Mn(CH3COO)2和Mg(NO2)2加入去离子水中，搅拌溶解，Mn(CH3COO)2浓度为0.05mol/L，Mg(NO2)2浓度为0.25mol/L，调节反应液pH，使反应体系的初始pH为3；
第二步：将上述溶液分装到石英管中，用功率为1500W可见光照射，反应6h；
第三步：将第二步反应所得悬浊液离心分离并收集沉淀物，用乙醇洗涤，直至洗涤液的电导为20μS/cm，将沉淀物干燥，即得。
由图1中XRD谱图结果可知，在此条件下产物为纯相水钠锰矿，形貌为卷曲的薄片状，薄片厚度较实施例1略有增加，颗粒粒径较实施例1略有减小(图2B)。
实施例3
一种薄片状纳米水钠锰矿的制备方法，包括以下步骤：
第一步：将Mn(NO3)2和KNO3加入去离子水中，搅拌溶解，Mn(NO3)2浓度为0.5mol/L，KNO3浓度为0.2mol/L，调节反应液pH，使反应体系的初始pH为6；
第二步：将上述溶液分装到石英管中，用太阳光照射，反应12h；
第三步：将第二步反应所得悬浊液用0.22μm滤膜过滤，收集沉淀物，用水洗涤，直至洗涤液的电导为15μS/cm，将沉淀物干燥，即得。
由图1中XRD谱图结果可知，在此条件下产物为纯相水钠锰矿，形貌为卷曲的薄片状，薄片厚度和颗粒粒径较实施案例1和2最小(图2C)。

Claims (5)

1.一种薄片状纳米水钠锰矿的制备方法，其特征在于包括以下步骤：
第一步：将二价锰盐和硝酸盐或亚硝酸盐加入去离子水中，搅拌溶解，二价锰盐浓度为0.05～2mol/L；硝酸根或亚硝酸根离子浓度为0.05～2mol/L，调节反应液pH，使反应体系的初始pH为3～8；
第二步：将上述溶液分装到石英管中，用紫外光或可见光或太阳光照射，反应6～24h；
第三步：将第二步反应所得悬浊液过滤或离心分离，收集沉淀物，用水或乙醇洗涤，直至洗涤液的电导≤20μS/cm，将沉淀物干燥，即得。
2.根据权利要求1所述薄片状纳米水钠锰矿的制备方法，其特征在于：所述二价锰盐为MnSO4或MnCl2或Mn(CH3COO)2或Mn(NO3)2。
3.根据权利要求1所述薄片状纳米水钠锰矿的制备方法，其特征在于：所述硝酸盐为NaNO3或KNO3或Mg(NO3)2或Ca(NO3)2；所述亚硝酸盐为NaNO2或KNO2或Mg(NO2)2或Ca(NO2)2。
4.根据权利要求1所述薄片状纳米水钠锰矿的制备方法，其特征在于：所述紫外光或可见光的功率为50-1500W。
5.根据权利要求1所述薄片状纳米水钠锰矿的制备方法，其特征在于：第二步中，所述反应时间为12h。
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