CN109647340A - 一种3R-MoS2/碳布复合材料的制备方法及其应用 - Google Patents
一种3R-MoS2/碳布复合材料的制备方法及其应用 Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 90
- 239000004744 fabric Substances 0.000 title claims abstract description 90
- 239000002131 composite material Substances 0.000 title claims abstract description 75
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims abstract description 54
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 52
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003463 adsorbent Substances 0.000 claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 12
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000011733 molybdenum Substances 0.000 claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 claims abstract description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
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- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000002751 molybdenum Chemical class 0.000 claims abstract description 7
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- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000001103 potassium chloride Substances 0.000 claims abstract description 4
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- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 claims description 4
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 claims description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 4
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- YJCZGTAEFYFJRJ-UHFFFAOYSA-N n,n,3,5-tetramethyl-1h-pyrazole-4-sulfonamide Chemical compound CN(C)S(=O)(=O)C=1C(C)=NNC=1C YJCZGTAEFYFJRJ-UHFFFAOYSA-N 0.000 claims 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 18
- 238000011067 equilibration Methods 0.000 abstract description 3
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 5
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- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种3R‑MoS2/碳布复合材料的制备方法及其应用，它是要解决现有的水热合成的MoS2纳米片制备过程复杂，对U(VI)的吸附量低、不容易回收的技术问题，本方法：一、将KCl、NaCl、钼盐和硫盐加热熔融，并加入碳布；二、以金属钼为工作电极，钼丝为辅助电极进行恒电流电解，然后将碳布取出，洗涤、烘干，得到3R‑MoS2/碳布复合材料。该复合材料可作为吸附剂、电解水制氢的催化剂或光催化的催化剂。作为吸附剂去除水中U(VI)时，吸吸咐量为170～190mg/g，吸咐平衡时间仅为1分钟，可应用于电解水制氢、吸附和光催化领域。
Description
技术领域
本发明涉及3R-MoS2/碳布复合材料的制备方法及其应用。
背景技术
采矿作业和核燃料循环产生的含U(VI)放射性废水的处理，对核电的可持续发展具有重要意义。为了应对上述问题，寻求一种对放射性核素具有快速有效吸附能力的材料是吸附法去除水溶液中U(VI)的关键。过渡金属硫化物MoS2具有良好的物理化学性能，比表面大、反应活性高和催化性能优异等特性。但国内外对其研究主要集中在电催化和电极材料等方面，而在吸附方面的研究则相对较少。作为一种特殊的层状化合物，MoS2各向异性的性质使得MoS2易于形成离子吸附和运输的二维渗透通道，此外，表面和边缘含有丰富的硫基团，优良的化学和热稳定性，高的分散性以及良好的亲水性等，这些都有利于MoS2对U(VI)的吸附。《美国化学学会杂志》(Journal of the American Chemical Society)2013年的第136卷4期的文章《可控合成多氧MoS2纳米薄片对水溶液中铀吸附性能的研究》(Controllable disorder engineering in oxygen-incorporated mos 2ultrathinnanosheets for efficient hydrogen evolution)公开了一种采用水溶液法制备MoS2纳米片的方法，并利用该MoS2纳米片作为吸附剂去除水中U(VI)，在pH为5.5条件下2h内达到吸附平衡，二硫化钼对U(VI)的最大吸附量为492.72mg/g。《环境技术与创新》(Environmental Technology&Innovation)2018年的第11卷的文章《pH值、离子强度、接触时间、腐殖酸和温度对二维MoS2纳米片吸咐U(VI)和Th(IV)性能的影响》(Sorptionproperties of U(VI)and Th(IV)on two-dimensional Molybdenum Disulfide(MoS2)nanosheets:Effects of pH,ionic strength,contact time,humic acids andtemperature)一文中也公开了一种MoS2纳米片，但是这种MoS2纳米片的制备过程复杂并且含有杂质，此外，这种粉体材料不容易回收。
发明内容
本发明是要解决现有的水热合成的MoS2纳米片制备过程复杂、不容易回收的技术问题，而提供一种3R-MoS2/碳布复合材料的制备方法及其应用。
本发明的3R-MoS2/碳布复合材料的制备方法，按以下步骤进行：
一、按KCl、NaCl、钼盐和硫盐的质量比为37：30：(4～5)：(6～7)加入电解炉的电解槽中，加热熔融，然后再将碳布加入到电解槽中；
二、以金属钼为工作电极，钼丝为辅助电极，在电解温度为657～700℃、电流为0.5～1.0Acm-2的条件下电解0.5～1.0小时，将电解槽内的碳布取出，洗涤、烘干，得到3R-MoS2/碳布复合材料。
本发明的3R-MoS2/碳布复合材料的应用，是将3R-MoS2/碳布复合材料作为吸附剂、电解水制氢的催化剂或光催化的催化剂。
其中用3R-MoS2/碳布复合材料作为吸附剂去除水中U6+的方法，按以下步骤进行：
将3R-MoS2/碳布复合材料放入pH值为4.5～5.0的含U6+的废水中，搅拌10～15min，然后将3R-MoS2/碳布复合材料过滤出来，完成含U6+的废水的处理。
本发明采用来源广泛的钼盐和硫盐为原料，在熔盐电解条件下反应制备的3R-MoS2/碳布复合材料，该复合材料是片状结构斜方六面体对称的3R相MoS2均匀原位生长在碳布上形成的。3R相MoS2颗粒尺寸可控并结晶性好，具有比表面积大、产量大、无杂质的特点，简化了生产工艺和流程。本发明的电解温度是在657～700℃、电流为0.5～1.0Acm-2的条件下电解0.5～1.0小时，对设备要求低，节省能源，降低生产成本。利用一步法制备出的3R-MoS2/碳布复合材料，可应用于电解水制氢、吸附和光催化领域。该材料作为吸附剂去除水中U(VI)时，吸吸咐量为170～190mg/g，吸咐平衡时间仅为1分钟，处理速度快，易于回收。
附图说明
图1是试验1制备的3R-MoS2/碳布复合材料的外貌照片；
图2是试验1制备的3R-MoS2/碳布复合材料的XRD谱图；
图3是试验1制备的3R-MoS2/碳布复合材料的SEM图；
图4是试验1制备的3R-MoS2/碳布复合材料的SEM照片；
图5试验1中图4的EDS框选区域的元素分析结果图；
图6是试验1制备的3R-MoS2/碳布复合材料的拉曼光谱；
图7是试验1制备的3R-MoS2/碳布复合材料的N2吸附脱附曲线；
图8是试验1溶液初始pH值对3R-MoS2/碳布复合材料吸附U6+的影响；
图9是试验1时间对3R-MoS2/碳布复合材料吸附U6+的影响；
图10是试验1中3R-MoS2/碳布复合材料吸附U6+的准二级模拟曲线；
图11是实验2中制备的3R-MoS2/碳布复合材料的SEM图；
图12是实验2中制备的3R-MoS2/碳布复合材料的XRD；
图13是试验2制备的3R-MoS2/碳布复合材料的N2吸附脱附曲线。
具体实施方式
具体实施方式一：本实施方式的3R-MoS2/碳布复合材料的制备方法，按以下步骤进行：
一、按KCl、NaCl、钼盐和硫盐的质量比为37：30：(4～5)：(6～7)加入电解炉的电解槽中，加热熔融，然后再将碳布加入到电解槽中；
二、以金属钼为工作电极，钼丝为辅助电极，在电解温度为657～700℃、电流为0.5～1.0Acm-2的条件下电解0.5～1.0小时，将电解槽内的碳布取出，洗涤、烘干，得到3R-MoS2/碳布复合材料。
具体实施方式二：本实施方式与具体实施方式一不同的是所述的钼盐为(NH4)6Mo7O24、MoO3或MoO2；其它与具体实施方式一相同。
具体实施方式三：本实施方式与具体实施方式一或二不同的是所述的硫盐为KSCN、K2S或Na2S；其它与具体实施方式一或二相同。
具体实施方式四：本实施方式与具体实施方式一至三之一不同的是步骤二中电解温度为670～680℃；其它与具体实施方式一至三之一相同。
具体实施方式五：本实施方式与具体实施方式一至四之一不同的是步骤二中电流为0.7Acm-2；其它与具体实施方式一至四之一相同。
具体实施方式六：具体实施方式一制备的3R-MoS2/碳布复合材料的应用，是将3R-MoS2/碳布复合材料作为吸附剂、电解水制氢的催化剂或光催化的催化剂。
具体实施方式七：本实施方式与具体实施方式六不同的是，3R-MoS2/碳布复合材料的应用，是用3R-MoS2/碳布复合材料作为吸附剂去除水中U6+。
具体实施方式八：本实施方式与具体实施方式七不同的是，用3R-MoS2/碳布复合材料作为吸附剂去除水中U6+，具体的方法为：将3R-MoS2/碳布复合材料放入pH值为4.5～5.0的含U6+的废水中，搅拌1～30min，然后将3R-MoS2/碳布复合材料过滤出来，完成含U6+的废水的处理。
用以下的试验验证本发明的有益效果：
试验1：本试验的一种3R-MoS2/碳布复合材料的制备方法，按以下步骤进行：
一、把37克KCl、30克NaCl、6克KSCN、4克(NH4)6Mo7O24加入电解炉的电解槽中，加热至657℃熔融，得到NaCl-KCl-KSCN-(NH4)6Mo7O24电解质体系，然后再将碳布加入到电解槽中；
二、以金属钼为工作电极，钼丝为辅助电极，在电解温度为657℃、电流为0.5Acm-2的条件下电解0.5小时，将电解槽内的碳布取出，用水、乙醇洗涤，25℃干燥1小时，得到3R-MoS2/碳布复合材料。
本试验制备的3R-MoS2/碳布复合材料的外貌如图1所示，图1a为未生长3R-MoS2的外貌图，图1b为生长3R-MoS2的外貌图。对比结果可看，图1b的碳布上有MoS2所产生的金属光泽。
本试验制备的3R-MoS2/碳布复合材料的XRD谱图如图2所示，从图2可以看出，3R-MoS2的XRD衍射峰强度高，衍射峰尖锐并且半高宽小，表明了3R-MoS2结晶好。
本试验制备的3R-MoS2/碳布复合材料的高倍率扫描电镜照片如图3所示，从图3看出3R-MoS2为片状结构并均匀生长在碳布上。
本试验制备的3R-MoS2/碳布复合材料的EDS照片如图4所示，从图4的EDS框选区域的元素分析结果如图5所示，从图5可以看出Mo和S元素完全符合MoS2化合物比例。
本试验制备的3R-MoS2/碳布复合材料的拉曼光谱如图6所示，拉曼光谱在这里用于进一步分析样品的晶体结构。3R-MoS2的单位晶胞由三层根据斜方六面体对称的，根据对称性，3R-MoS2具有4个拉曼活性的震动模式：E2g 2(32cm-1)，E1g(286cm-1)，E2g 1(383cm-1)和A1g(408cm-1)，如图6所示，其中E2g 2是属于层间振动模式，在背散射实验中，在垂直于c轴的表面，E1g模式是禁忌的。E2g 1模式是Mo-S键沿层方向的相对振动模式，而A1g模式是Mo-S键沿垂直于层间方向的相对振动Sm2O2S的荧光激发光谱波长437nm，荧光发射光谱波长649nm。
图7为本试验制备的3R-MoS2/碳布复合材料的N2吸附脱附曲线，从图7可以看出，3R-MoS2/碳布复合材料的N2吸附脱附曲线为Ⅲ型等温线，测得其比表面积为21.9718m2/g。
本试验制备的3R-MoS2/碳布复合材料中3R-MoS2的纯度较高，干扰杂质很低，适用于工业分析及化学实验。在熔盐电解条件下反应制备3R-MoS2/碳布复合材料，成本低，生产工艺简单，易于回收。
将本试验制备的3R-MoS2/碳布复合材料应用于U6+吸附，具体按以下步骤进行：
准确称取0.01g的3R-MoS2/碳布复合材料置于150mL的锥形瓶中，然后加入50mLpH值为3.0的U6+浓度为50mg L-1的U6+溶液，并将其放入恒温震荡箱中，200rpm下震荡5分钟，取上层清液，并用偶氮砷III的方法测上层清液中U6+的浓度，计算吸附量。然后仅改变pH值重复进行上述的试验，得到吸咐量随pH值的变化关系曲线如图8所示，从图8可以看出，随着pH的增加，吸附剂对U6+的吸附容量都逐渐增大，并且在所研究的pH范围内，当pH＝5.0时，吸附剂对U6+的吸附量达到最大，为187.14mg/g。
将本试验制备的3R-MoS2/碳布复合材料应用于U6+吸附，具体按以下步骤进行：
准确称取0.01g的3R-MoS2/碳布复合材料置于150mL的锥形瓶中，然后加入50mLpH值为5.0的U6+浓度为50mg L-1的U6+溶液，并将其放入恒温震荡箱中，200rpm下震荡1分钟，取上层清液，并用偶氮砷III的方法测上层清液中U(VI)的浓度，计算吸附量。然后仅改变震荡时间重复进行上述的试验，得到吸咐量随震荡时间的变化关系曲线如图9所示，从图9可以看出，3R-MoS2/碳布复合材料吸附剂对U6+的吸附速率都很快，当接触时间为1min时，对U6+的吸附容量就可达到平衡。
为了进一步明确吸附过程中的机理，拟一阶和拟二阶动力学方程，结果表明3R-MoS2/碳布复合材料对U6+的吸附过程更符合拟二阶动力学模型，如图10所示。
试验2：本试验的一种3R-MoS2/碳布复合材料的制备方法，按以下步骤进行：
一、把37克KCl、30克NaCl、6克Na2S、4克MoO3加入电解炉的电解槽中，加热至670℃熔融，得到NaCl-KCl-Na2S-MoO3电解质体系，然后再将碳布加入到电解槽中；
二、以金属钼为工作电极，钼丝为辅助电极，在电解温度为670℃、电流为0.7Acm-2的条件下电解1小时，将电解槽内的碳布取出，用水、乙醇洗涤，25℃干燥1小时，得到3R-MoS2/碳布复合材料。
本试验得到的得到3R-MoS2/碳布复合材料的扫描电镜如图11所示，从图11可以看出，本试验制备的3R-MoS2为片状结构，并均匀生长在碳布上。
本试验得到的得到3R-MoS2/碳布复合材料的XRD照片，如图11所示，从图11可以看出，3R-MoS2的结晶良好。
本试验得到的3R-MoS2/碳布复合材料的N2吸附脱附曲线比表面积如图12，从图12可以看出，3R-MoS2/碳布复合材料的N2吸附脱附曲线为Ⅲ型等温线，测得比表面积20.54774m2/g。
用与试验一相同的方法进行U6+吸附试验，测得3R-MoS2/碳布复合材料的吸咐量为179.79mg/g。吸咐平衡时间是1min。
Claims (8)
1.一种3R-MoS2/碳布复合材料的制备方法，其特征在于该方法按以下步骤进行：
一、按KCl、NaCl、钼盐和硫盐的质量比为37：30：(4～5)：(6～7)加入电解炉的电解槽中，加热熔融，然后再将碳布加入到电解槽中；
二、以金属钼为工作电极，钼丝为辅助电极，在电解温度为657～700℃、电流为0.5～1.0Acm-2的条件下电解0.5～1.0小时，将电解槽内的碳布取出，洗涤、烘干，得到3R-MoS2/碳布复合材料。
2.根据权利要求1所述的一种3R-MoS2/碳布复合材料的制备方法，其特征在于所述的钼盐为(NH4)6Mo7O24、MoO3或MoO2。
3.根据权利要求1或2所述的一种3R-MoS2/碳布复合材料的制备方法，其特征在于所述的硫盐为KSCN、K2S或Na2S。
4.根据权利要求1或2所述的一种3R-MoS2/碳布复合材料的制备方法，其特征在于步骤二中电解温度为670～680℃。
5.根据权利要求1或2所述的一种3R-MoS2/碳布复合材料的制备方法，其特征在于步骤二中电流为0.7Acm-2。
6.权利要求1所述的一种3R-MoS2/碳布复合材料的应用，其特征在于该应用是将3R-MoS2/碳布复合材料用作吸附剂、电解水制氢的催化剂或光催化的催化剂。
7.根据权利要求7所述的一种3R-MoS2/碳布复合材料的应用，其特征在于该应用是将3R-MoS2/碳布复合材料作为吸附剂去除水中U6+。
8.根据权利要求7所述的一种3R-MoS2/碳布复合材料的应用，其特征在于将3R-MoS2/碳布复合材料作为吸附剂去除水中U6+的方法为：将3R-MoS2/碳布复合材料放入pH值为4.5～5.0的含U6+的废水中，搅拌1～30min，然后将3R-MoS2/碳布复合材料过滤出来，完成含U(VI)的废水的处理。
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