CN112536016A - 一类用于有害离子吸附的新型锑/铋基过渡金属层状硫属化合物材料 - Google Patents
一类用于有害离子吸附的新型锑/铋基过渡金属层状硫属化合物材料 Download PDFInfo
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Abstract
本发明涉及一类用于有害离子吸附的新型锑/铋基过渡金属层状硫属化合物材料,其结构通式为AyMxPn4‑xQ6,其中A=Li、Na、K,M=Mn、Fe、Co、Ni、Cu、Zn、Hg,Pn=Sb、Bi,Q=S、Se,0<x<4,0<y<8。此类材料具有层状结构,由Bi2Se3型[MxPn4‑xQ6]层与层间A离子构成,[MxPn4‑xQ6]层中M与Pn占据同一结晶学位置。层间A离子可发生离子交换反应,因此可以高效吸附有害金属离子。此类材料对于水溶液中多种有害金属离子表现出良好的吸附特性,具有吸附量较高,吸附彻底(去除率高达99.9%)的特点。该材料具有较广的pH适用范围(pH=2.5~11.0),且吸附量不受溶液中高浓度竞争离子的影响,具有良好的选择性。将该吸附材料与高分子材料结合,可制备得到特定大小形状的吸附剂。
Description
技术领域
本发明涉及一种基于离子交换的有害金属离子吸附材料,具体地涉及一类新型锑/铋基过渡金属层状硫属化合物的制备及吸附应用,属于材料领域。
背景技术
洁净的水资源是人类生存的首要条件之一,然而目前仍有多达十亿人不能获取洁净用水。重金属离子如铅(Pb2+)、镉(Cd2+)及放射性离子如铯(137Cs)、锶(90Sr)、铀(235U)等是水中主要的污染物质之一。传统的沉淀法很难将污染离子的浓度降低至国家规定标准之下,且放射性废水中极端的pH条件以及高盐环境使得一般的吸附剂很难发挥作用。离子交换作为一种高效、低成本的吸附方式,被广泛应用于去除各种水污染物。黏土与沸石是常见的离子交换材料,但其对有害金属离子的吸附量不高、吸附选择性差,且不能在高盐浓度或极端pH条件的水体中使用,因此,亟需寻找其他新型高效有害金属吸附材料。
近年来,基于硫属化合物的离子交换材料受到了广泛的关注。由于重金属及放射性离子大部分为Lewis软酸,而S为Lewis软碱,因此对于硫属化合物离子交换材料,无需引入额外的功能性基团即可对这些离子表现出很强的选择性。S与金属离子间强的共价相互所用使得此类吸附材料能够将污染离子浓度降至国标浓度之下。此类材料中具有代表性包括:层状的KMS系列材料如KMS-1(K2xMnxSn3-xS6,x=0.5-1)、KMS-2(K2xMgxSn3-xS6,x=0.5-1)、KMS-5(KIn2SnS6),有机分子插层的FJSM-SnS(Me2NH2)4/3(Me3NH)2/3Sn3S7·1.25H2O等。此类材料对于重金属离子及放射性离子(Rb+、Cs+、Sr2+、Ba2+、Cd2+、Hg2+、Pb2+、UO2 2+、Cu+、Ni2+、Ag+、TcO4 -、Am3+、Eu3+等)表现出较高的吸附量、较强的吸附选择性及较大的pH适应范围。目前基于层状硫属化合物的吸附材料数量仍然十分有限,开发新型的硫属化合物离子交换材料无论在科学研究还是实际应用方面均具有非常重要的意义。
发明内容
本发明的目的在于合成一类具有新型结构组成的锑/铋基过渡金属层状硫属化合物,用以吸附水体系中的有害金属离子。
本发明提供了一类新型锑/铋基过渡金属层状硫属化合物,结构通式为AyMxPn4- xQ6,晶体结构由Bi2Se3型[MxPn4-xQ6]层与层间A离子构成,[MxPn4-xQ6]层中M与Pn占据同一结晶学位置;其中A选自碱金属Li、Na、K等元素中的一种或两种以上的组合,M选自过渡金属Mn、Fe、Co、Ni、Cu、Zn、Hg等元素中的一种或两种以上的组合,Pn选自Sb、Bi中的一种或两种,Q选自S、Se中的一种或两种;且0<x<4,0<y<8。可利用Zr、V、Nb、Ta、Cr、Mo、W、Ru、Rh、Pd等过渡金属元素中的一种或两种以上对AyMxPn4-xQ6进行掺杂。
本发明还提供了制备上述新型锑/铋基过渡金属层状硫属化合物的方法,可采用高温固相合成、高温助溶剂合成、水热(溶剂热)合成、微波合成、球磨法合成等。
通过以上方法制备的新型锑/铋基过渡金属层状硫属化合物能够吸附水溶液中的重金属离子及放射性离子,其中包括离子Rb+、Cs+、Sr2+、Ba2+、Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Ag+、Zn2+、Cd2+、Pb2+、Hg2+、241Am、152Eu、UO2 2+等中的一种或多种。
典型的吸附过程以此为例:
(1)室温配制金属离子溶液,其中金属离子为(Rb+、Cs+、Sr2+、Ba2+、Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Ag+、Zn2+、Cd2+、Pb2+、Hg2+、241Am、152Eu、UO2 2+)中的一种或多种;
(2)室温下量取10ml步骤(1)中含有金属离子的水溶液,向水溶液中加入10mg本发明制备的新型层状硫属化合物AyMxPn4-xQ,室温下1000r/min搅拌10~36h;
(3)将步骤(2)中的溶液过滤,通过原子吸收光谱或质谱测定其中金属离子的剩余浓度;
(4)通过以上方法测定吸附离子的等温吸附线、动力学曲线、不同pH下吸附情况以及在竞争离子存在下的吸附行为等。
附图说明
图1示出本发明制备的新型层状硫属化合物AyMxPn4-xQ6的晶体结构。
图2示出本发明制备的新型层状硫属化合物AyMxPn4-xQ6吸附各种重金属离子后的扫描电子显微镜照片以及元素分布图。
图3示出本发明制备的新型层状硫属化合物AyMxPn4-xQ6吸附水溶液中重金属离子Cd2+的吸附等温线。
图4示出本发明制备的新型层状硫属化合物AyMxPn4-xQ6吸附水溶液中重金属离子Pb2+的吸附等温线。
图5示出本发明制备的新型层状硫属化合物AyMxPn4-xQ6在不同pH水溶液吸附Cd2+或Pb2+的分配系数Kd。
图6示出本发明制备的新型层状硫属化合物AyMxPn4-xQ6在高浓度竞争离子Na+、Ca2+存在条件下对Cd2+、Pb2+的去除率。
具体实施方式
下面结合实施例对本发明作进一步详细说明。需要注意的是,本发明的内容并不限于这些具体的实施方式。在不背离本发明背景和精神的前提下,本领域技术人员在阅读本发明的内容的基础上可以进行等价替换和修改,其内容也包括在本发明要求保护的范围内。另外,下述工艺参数中的具体配比、时间、温度等也仅是示例性,本领域技术人员可以再上述限定范围内选择合适的值。
实施实例1
称取0.51g K、0.71g Mn、2.77g Bi和1.92g S,在手套箱中混合均匀后,转移至内径1cm的石英管中真空封装。将密封的石英管放入马弗炉中,设置保温程序如下:10小时升温至700℃,在700℃保温24小时,之后自然冷却至室温。将产物从石英管内取出,可得新型层状化合物K1.3Mn1.3Bi2.7S6。
实施实例2
称取0.78g Na2S、0.64g Cu、2.77g Bi和1.60g S,在手套箱中混合均匀后转移至球磨罐中。将球磨罐放置于高能球磨机中,球磨3小时。将产物从球磨罐内取出,可得新型层状化合物Na2CuBi3S6。
实施实例3
称取0.39g Na2S、0.65g Zn、2.77g Bi和1.75g S,混合均匀后分散在18ml乙腈中。将混合体系转移至聚四氟乙烯反应釜中,200℃反应三天,之后取出冷却至室温。将所得固体产物用去离子水清洗三次、乙醇清洗两次后烘干,可得最终产物新型层状化合物NaZnBi3S6。
实施实例4
称取0.29g Na2S、0.71g Mn、1.62g Sb和1.75g S,在手套箱中混合均匀后,转移至内径1cm的石英管中真空封装。将密封的石英管放入马弗炉中,设置保温程序如下:10小时升温至700℃,在700℃保温24小时,之后自然冷却至室温。将产物从石英管内取出,可得新型层状化合物NaMnSb3S6。
实施实例5
称量10mg K1.3Mn1.3Bi2.7S6,分别放入盛有10ml 6~500ppm的Cd2+溶液中,室温下以1000r/min转速搅拌24h,吸附结束后过滤。利用原子吸收光谱测试溶液中剩余Cd2+浓度,绘制等温吸附线。利用Langmuir等温吸附模型对曲线进行拟合,如图3所示,得到对Cd2+的吸附量为221.2mg/g。
实施实例6
称量10mg K1.3Mn1.3Bi2.7S6,分别放入盛有10ml 6~700ppm的Pb2+溶液中,室温下以1000r/min转速搅拌24h,吸附结束后过滤。利用原子吸收光谱测试溶液中剩余Pb2+浓度,绘制等温吸附线。利用Langmuir等温吸附模型对曲线进行拟合,如图4所示,得到对Pb2+的吸附量为342.4mg/g。
实施实例7:
称量10mg Na2CuBi3S6,分别放入10瓶盛有300ppm的Pb2+溶液中,室温下以1000r/min转速搅拌,在搅拌5、10、20、60、100、150、300、480、600、1440min后过滤溶液。利用原子吸收光谱测试溶液中剩余Pb2+浓度。结果表明,材料可以在600min之内吸附溶液中99%的以上的Pb2+。
实施实例8:
称量10mg NaZnBi3S6,分别放入10瓶盛有200ppm的Cd2+溶液中,室温下以1000r/min转速搅拌,在搅拌5、10、20、60、100、150、300、480、600、1440min后过滤溶液。利用原子吸收光谱测试溶液中剩余Cd2+浓度。结果表明,材料可以在600min之内吸附溶液中97%的以上的Cd2+。
实施实例9
称量10mg K1.3Mn1.3Bi2.7S6分别放入6瓶pH在2.5~6.0之间的20ppm Pb2+溶液中,室温下以1000r/min转速搅拌24h,吸附结束后过滤,利用原子吸收光谱测试溶液中剩余Pb2+浓度,计算吸附的分配系数Kd,结果如图5所示。在pH=2.5~6.0范围内,K1.3Mn1.3Bi2.7S6对Pb2+的吸附能力无明显下降。
实施实例10
称量10mg K1.3Mn1.3Bi2.7S6分别放入7瓶pH在2.5~7.0之间的20ppm Cd2+溶液中,室温下以1000r/min转速搅拌24h,吸附结束后过滤,利用原子吸收光谱测试溶液中剩余Cd2+浓度,计算吸附的分配系数Kd,结果如图5所示。在pH=2.5~7.0范围内,K1.3Mn1.3Bi2.7S6对Cd2+的吸附能力无明显下降。
实施实例11
称量10mg K1.3Mn1.3Bi2.7S6分别放入3瓶10ml的200ppb Cd2+或者Pb2+溶液中,其中分别含有Na+1、5、10ppm,室温下以1000r/min转速搅拌24h,吸附结束后过滤,利用质谱测试溶液中剩余Cd2+或Pb2+浓度,结果如图6所示,结果表明各溶液中99.9%以上的Cd2+或Pb2+已被除去,吸附性质不受相对浓度较高的Na+影响。
实施实例12
称量10mg K1.3Mn1.3Bi2.7S6分别放入3瓶10ml的200ppb Cd2+或者Pb2+溶液中,其中分别含有Ca2+1、5、10ppm,室温下以1000r/min转速搅拌24h,吸附结束后过滤,利用质谱测试溶液中剩余Cd2+浓度,结果如图6所示,结果表明各溶液中99.9%以上的Cd2+或Pb2+已被除去,吸附性质不受相对浓度较高的Ca2+影响。
实施实例13
模拟水环境配制含有100ppb Cr3+、Ag+、Zn2+、Cd2+、Pb2+、Hg2+的水溶液,加入一定量的Na2CuBi3S6,搅拌24h后过滤,利用质谱测试溶液中剩余离子的浓度,结果表明溶液中99.9%以上的金属离子均已被除去,剩余离子浓度均在1ppb以下。
实施实例14
NaZnBi3S6材料在水溶液中吸附Cs+后,将固体滤出后放入2mol/L NaCl溶液中,搅拌一段时间后,滤出,测试产物的XRD、SEM,结果表明物相与吸附前一致,且用该恢复后的材料进行二次吸附,吸附性能并无明显变化。
实施实例15
将K1.3Mn1.3Bi2.7S6材料研磨后加入海藻酸钠溶液中,超声分散后向溶液中加入CaCl2溶液,静置一段时间后得到了包裹有海藻酸钙的片状吸附剂沉淀。将该片状吸附剂应用于吸附Cd2+、Pb2+等重金属离子,吸附性能与粉末K1.3Mn1.3Bi2.7S6材料并无明显差别。
Claims (9)
1.一类用于有害离子吸附的新型锑/铋基过渡金属层状硫属化合物,其特征在于:
1)结构通式为AyMxPn4-xQ6,其中A选自碱金属Li、Na、K等元素中的一种或两种以上的组合,M选自过渡金属Mn、Fe、Co、Ni、Cu、Zn、Hg等元素中的一种或两种以上的组合,Pn选自Sb、Bi中的一种或两种,Q选自S、Se中的一种或两种;且0<x<4,0<y<8。
2)具有层状结构,由Bi2Se3型[MxPn4-xQ6]层与层间A离子构成。
3)可进行掺杂。
4)可发生离子交换反应。
5)具有优秀的有害离子吸附能力。
6)具有一定的可再生能力。
2.根据权利要求1所述层状结构,其特征在于:[MxPn4-xQ6]层中M与Pn占据同一结晶学位置,M/Pn与Q形成八面体配位形式,八面体通过共棱相互连接。
3.根据权利要求1所述掺杂,其特征在于:在保留原有晶体结构的前提下,可利用Zr、V、Nb、Ta、Cr、Mo、W、Ru、Rh、Pd、As等元素中的一种或两种以上对AyMxPn4-xQ6进行掺杂。
4.根据权利要求1所述离子交换反应,其特征在于:层间A离子可通过离子交换反应被其他金属离子取代,部分M离子也可通过离子交换反应被其他金属离子取代。
5.根据权利要求1所述有害离子吸附能力,其特征在于:在水溶液中吸附Rb+、Cs+、Sr2+、Ba2+、Cr3+、Mn2+、Fe3+、Co2+、Ni2+、Cu2+、Ag+、Zn2+、Cd2+、Pb2+、Hg2+、241Am、152Eu、UO2 2+等离子中的一种或多种,具有吸附容量大、吸附彻底、吸附选择性高等特性。
6.根据权利要求1所述可再生能力,其特征在于:将吸附Rb+、Cs+、Sr2+、Ba2+等离子后的材料浸泡于含有高浓度A离子的水溶液中,该材料能够恢复A离子插层并进行二次利用。
7.制备权利要求1-3所述的新型过渡金属锑/铋基层状硫属化合物的方法,其特征在于:可采用高温固相合成、高温助熔剂合成、水热(溶剂热)合成、微波合成、球磨法合成等。
8.将权利要求1-3所述的新型过渡金属锑/铋基层状硫属化合物进行后加工的方法,其特征在于:利用有机大分子或高分子等将材料封装加工为特定形状与大小的颗粒、板、柱等。
9.权利要求1-8任一项所述的新型过渡金属锑/铋基层状硫属化合物作为吸附剂吸附水溶液中有害金属离子的用途。
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CN116371367A (zh) * | 2022-11-22 | 2023-07-04 | 东华理工大学 | 一种基于含铀废水处理的无机有机杂化材料及其制备方法和应用 |
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