CN106268867B - 一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途 - Google Patents
一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途 Download PDFInfo
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Abstract
本发明公开了一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途。以碱金属碳酸盐、过渡金属(Mn)、二元固溶体(Sb2S3)和硫粉(S)为原料，氨水、水合肼和聚乙二醇400为溶剂，在120‑180℃环境中反应5‑8天，得到四元硫化物半导体材料，化学组成式为：AMn2Sb3S7(A＝K,Rb)。本发明具有合成产率高，操作过程简单，原料成本低，反应条件温和，合成温度低等优点。采用本发明得到的四元硫化物产率达40％以上，化学纯度高，可用于防腐、抑菌、电池、催化等领域。
Description
技术领域
本发明属于无机半导体材料领域，具体涉及一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料及制备方法和用途。
背景技术
硫属化合物晶体材料是一类公认的优良半导体材料，且这类化合物由于组成和结构的不同，可以在光、电、磁等多方面具有重要的用途。这类化合物具有特殊的结构，离子键、共价键混合存在，可以构成各种一维链状、二维层状或三维骨架结构。硫属化合物独特的成键特点使其具有丰富的结构，根据结构、组成不同，这种化合物可以是绝缘体、半导体、电子导体甚至是超导体，并已在技术上得到广泛开发和应用，它们的合成研究亦成为目前无机合成化学中一个十分活跃的研究领域。如AgBiS2和Cu3BiS3等三元硫化物显示出良好的热稳定性，是良好的半导体材料，其光学吸收在可见光区域具有潜在的应用价值。同时作为新型催化剂材料，在催化、抑菌、防腐等领域具有潜在的用途。
混凝土结构中钢筋被锈蚀成为影响钢筋混凝土耐久性的一项主要因素，每年都造成重大的经济损失，解决钢筋腐蚀问题是当前土木工程领域科技工作者面临的最紧迫的任务之一。其中，T-硫氧化菌、硫杆菌X、噬硅菌造成的生物硫酸腐蚀是其中一种常见的混凝土腐蚀，其具体过程为：环境水体中的有机和无机悬浮物随着水体的流动而逐渐沉积于混凝土结构的表面成为附着物，附着物中的硫酸根离子被硫还原菌还原，生成硫化氢气体。同时，硫化氢气体通过复杂的生物化学反应，氧化生成酸性较强的硫酸，从而降低周围环境的pH值。硫酸溶解释放的氢离子通过扩散进入混凝土的内部，并与混凝土内部的钢筋结构相接触，从而发生混凝土和钢筋的腐蚀，严重威胁着混凝土建筑结构的安全。半导体材料可以作为表面涂层材料，涂覆在混凝土表面起到很好的抑菌作用。由于半导体在受到光激发后能够进行“光催化反应”，产生化学能，利用产生的化学能来进行氧化还原反应。半导体光催化的基本原理是利用半导体作为光催化材料(或与某种氧化剂结合)，在特定波长的光辐射下，在半导体表面产生氧化性极强的空穴或反应性极高的羟基自由基。这些氧化活性离子与有机污染物、病毒、细菌发生接触和复合而产生强烈的破坏作用，导致有机污染物被降解，病毒与细菌被杀灭，从而达到降解环境污染物，抑菌杀菌和防腐的目的。
目前，TiO2被证明是应用最广泛的光催化剂。但是其瓶颈在于，只有在短波紫外光的照射下Ti02才能表现出光催化特性，其中能被Ti02吸收用于光催化反应的紫外光部分也较低。因此增强可见光吸收能力，充分有效地利用太阳能资源，已成为目前光催化剂一个前沿的发展方向。金属硫化物具有很宽的可见光吸收范围。因此，开发新的材料合成路线，探索合成新的硫化物半导体体系是解决上述问题的重要途径之一。
发明内容
本发明的目的在于克服现有技术中存在的不足，并提供一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料制备方法。具体技术方案如下：
一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料，其化学组成式为KMn2Sb3S7，属于四方晶系，I-4 2m空间群，晶胞参数 α＝90°，β＝90°，γ＝90°，Z＝1，晶体为暗红色棒状，能隙为1.44eV。
上述用于混凝土抑菌防腐的四元硫化物半导体光催化材料KMn2Sb3S7的制备方法为：以摩尔比为1.0-2.0：1.0-2.0：0.5：2.0-3.0的碳酸钾、金属锰、二元固溶体三硫化二锑和单质硫为原料；以体积比为0.3-0.8：1.0-2.0：2.0-3.0的氨水、水合肼和聚乙二醇400为溶剂；将每0.427-0.652克的原料加入3.3-5.8mL所述的溶剂中，在120-180℃环境中反应4-7天，经去离子水和乙醇洗涤后得到四元硫化物半导体材料KMn2Sb3S7。
另一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料，其化学组成式为RbMn2Sb3S7，属于四方晶系，I-4 2m空间群，晶胞参数 α＝90°，β＝90°，γ＝90°，Z＝1，晶体为暗红色棒状，能隙为1.43eV。
上述用于混凝土抑菌防腐的四元硫化物半导体光催化材料RbMn2Sb3S7的制备方法为：以摩尔比为1.0-2.0：1.0-2.0：0.5：2.0-3.0的碳酸铷、金属锰、二元固溶体三硫化二锑和单质硫为原料；以体积比为0.3-0.8：1.0-2.0：2.0-3.0的氨水、水合肼和聚乙二醇400为溶剂；将总量为0.52-0.838克的原料加入3.3-5.8mL所述的溶剂中，在120-180℃环境中反应4-7天，经去离子水和乙醇洗涤后得到四元硫化物半导体材料RbMn2Sb3S7。
上述四元硫化物半导体材料的用途，可以作为用于混凝土抑菌防腐的光催化材料，或用于制备光电化学半导体器件或太阳能电池过渡层材料。
本发明操作过程简单方便，原料成本低，反应条件温和等，采用本方法制备的四元硫化物半导体材料，产率可达到40％以上，晶粒尺寸达到微米级以上，且化学纯度较高，在半导体光催化杀菌方面具有潜在的应用价值。
附图说明
图1为晶体的形貌图，其中a)为KMn2Sb3S7晶体的形貌图；b)为RbMn2Sb3S7晶体的形貌图；
图2为晶体的EDX图谱，其中a)为KMn2Sb3S7晶体的EDX图谱，表明了K、Mn、Sb和S元素的存在及其含量；b)为RbMn2Sb3S7晶体的EDX图谱，表明了Rb、Mn、Sb和S元素的存在及其含量；
图3为根据晶体得到的XRD图谱与单晶模拟衍射图，其中a)为根据KMn2Sb3S7晶体得到的XRD图谱与单晶模拟衍射图；b)为根据RbMn2Sb3S7晶体得到的XRD图谱与单晶模拟衍射图；
图4为固态紫外可见漫反射光谱；其中a)为KMn2Sb3S7的固态紫外可见漫反射光谱；b)为RbMn2Sb3S7的固态紫外可见漫反射光谱；
图5为AMn2Sb3S7(A＝K,Rb)的晶体结构图；
图6为AMn2Sb3S7(A＝K,Rb)作为混凝土防腐涂层材料时，混凝土中钢筋的腐蚀电位-时间曲线。
具体实施方式
下面结合附图和实施例对本发明做进一步阐述和说明。本发明中各个实施方式的技术特征在没有相互冲突的前提下，均可进行相应组合。
本发明中具体公开了以下一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料AMn2Sb3S7(A＝K,Rb)。
其中：KMn2Sb3S7，属于四方晶系，I-4 2m空间群，晶胞参数 α＝90°，β＝90°，γ＝90°，Z＝1，晶体为暗红色棒状，能隙为1.44eV。制备方法为：以摩尔比为1.0-2.0：1.0-2.0：0.5：2.0-3.0的碳酸钾、金属锰、二元固溶体三硫化二锑和单质硫为原料；以体积比为0.3-0.8：1.0-2.0：2.0-3.0的氨水、水合肼和聚乙二醇400为溶剂；将总量为0.427-0.652克的原料加入3.3-5.8mL所述的溶剂中，在120-180℃烘箱中反应4-7天，经去离子水和乙醇洗涤后得到四元硫化物半导体材料KMn2Sb3S7。
而RbMn2Sb3S7属于四方晶系，I-4 2m空间群，晶胞参数 α＝90°，β＝90°，γ＝90°，Z＝1，暗红色棒状，能隙为1.43eV。制备方法为：以摩尔比为1.0-2.0：1.0-2.0：0.5：2.0-3.0的碳酸铷、金属锰、二元固溶体三硫化二锑和单质硫为原料；以体积比为0.3-0.8：1.0-2.0：2.0-3.0的氨水、水合肼和聚乙二醇400为溶剂；将总量为0.52-0.838克的原料加入3.3-5.8mL所述的溶剂中，在120-180℃烘箱中反应4-7天，经去离子水和乙醇洗涤后得到四元硫化物半导体材料RbMn2Sb3S7。
下述实施例中二元固溶体硫化锑的制备方法为：将摩尔比为2:3的Sb和S装入石英管进行封管，再把密封的石英管放入马弗炉中，缓慢升温至560℃，并保温8小时，再自然冷却至室温，打开石英管将块状原料研磨成粉末备用。制备过程中的参数可以根据需要进行调整。当然二元固溶体硫化锑也可采用市售的现有材料。
实施例1
KMn2Sb3S7晶体。称取初始原料K2CO3 1.0mmol(0.138g)、Mn 2.0mmol(0.11g)、Sb2S30.5mmol(0.170g)和S 2.0mmol(0.064g)放入水热釜中，再加入氨水0.3ml，85wt％水合肼1.5mL和聚乙二醇400 2.0ml，将水热釜置于140℃下反应7天。反应结束后，打开水热釜，取出产物，分别用蒸馏水和无水乙醇洗涤2次，得到暗红色棒状晶体，产率为40％，晶粒尺寸100-360μm(见图1a)。经单晶X射线衍射分析，该晶体组成式为KMn2Sb3S7，属于四方晶系，I-42m空间群，晶胞参数α＝90°，β＝90°，γ＝90°，Z＝1，晶体结构图如图5所示。EDX元素分析表明晶体含K、Mn、Sb、S四种元素，且各元素含量比与单晶衍射分析结果一致(见图2a)。XRD粉末衍射峰与单晶衍射分析模拟图谱相吻合(见图3a)。UV-vis图谱测得半导体材料能隙为1.44eV(见图4a)。
制备过程中，各参数可以略作调整，其产品的基本性能参数基本相同。进一步提供下述两个实施例。
实施例2
RbMn2Sb3S7晶体。称取初始原料Rb2CO3 1.0mmol(0.231g)、Mn 2.0mmol(0.11g)、Sb2S3 0.5mmol(0.170g)和S 2.0mmol(0.064g)放入水热釜中，再加入氨水0.3ml，85wt％水合肼1.5mL和聚乙二醇400 2.0ml，将水热釜置于140℃下反应7天。反应结束后，打开水热釜，取出产物，分别用蒸馏水和无水乙醇洗涤2次，得到暗红色棒状晶体，产率为45％，晶粒尺寸60-150μm(见图1b)。经单晶X射线衍射分析，该晶体组成式为RbMn2Sb3S7，属于四方晶系，I-4 2m空间群，晶胞参数α＝90°，β＝90°，γ＝90°，Z＝1，晶体结构图如图5所示。EDX元素分析表明晶体含Rb、Mn、Sb、S四种元素，且各元素含量比与单晶衍射分析结果一致(见图2b)。XRD粉末衍射峰与单晶衍射分析模拟图谱相吻合(见图3b)。UV-vis图谱测得半导体材料能隙为1.43eV(见图4b)。
实施例3
以实施例1～2中所得的四元硫化物半导体材料AMn2Sb3S7(A＝K,Rb)，制备光催化材料，作为混凝土防腐蚀涂层，具体如下：
预处理：砂过80目筛网，混凝土试块洒水湿润。
干混：将称量的5份AMn2Sb3S7(A＝K,Rb)，20份铝酸三钙，45份硅酸三钙倒入容器，置于混料机中充分搅拌均匀。
湿混：在上述搅拌均匀的干拌料中加入水5份，置于混料机中充分混合均匀；机械搅拌10分钟后，一边搅拌，一边再把称量好的砂15份和10份水一起倒入搅拌机中，继续搅拌10分钟，最后形成分散均匀的涂料。
涂抹：用滚筒刷沾取上述制备的涂料，均匀涂抹于混凝土试块(40*40*40mm)表面。
养护：试块静置于常温空气中5天后凝固成型。
腐蚀测试：将未涂抹防腐材料(编号UC‐01),涂抹KMn2Sb3S7(编号C‐01)及涂抹RbMn2Sb3S7(编号C‐02)试块同时放入密封杯中，并注入400ml带有细菌(T‐硫氧化菌、硫杆菌X、噬硅菌)的污水，日光灯照射10天后，然后取出试块，用电化学工作站进行测试，进行腐蚀性能评价。测试结果如图6,未涂抹AMn2Sb3S7(A＝K,Rb)(编号UC‐01)的混凝土中钢筋的腐蚀电位低于涂抹AMn2Sb3S7(A＝K,Rb)(编号C‐01和编号C‐02)的混凝土中钢筋的腐蚀电位，说明AMn2Sb3S7(A＝K,Rb)作为防腐涂层材料可以明显降低混凝土中钢筋腐蚀的速度。
以上所述的实施例只是本发明的一种较佳的方案，然其并非用以限制本发明，凡采取等同替换或等效变换的方式所获得的技术方案，均落在本发明的保护范围内。
Claims (5)
1.一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料，其特征在于，其化学组成式为KMn2Sb3S7，属于四方晶系，I-4 2m空间群，晶胞参数a=17.070(2)Å，b=17.070(2)Å，c=11.520(2)Å，α=90°，β=90°，γ=90°，V= 3356.8(8)Å3 ，Z=1，能隙为 1.44 eV。
2.一种如权利要求1所述的用于混凝土抑菌防腐的四元硫化物半导体光催化材料的制备方法，其特征在于以摩尔比为1.0-2.0：1.0-2.0：0.5：2.0-3.0的碳酸钾、金属锰、二元固溶体三硫化二锑和单质硫为原料；以体积比为0.3-0.8：1.0-2.0： 2.0-3.0的氨水、水合肼和聚乙二醇400为溶剂；将每0.427-0.652克原料加入3.3-5.8 mL 所述的溶剂中，在120 -180℃环境中反应4-7天，经去离子水和乙醇洗涤后得到四元硫化物半导体材料KMn2Sb3S7。
3.一种用于混凝土抑菌防腐的四元硫化物半导体光催化材料，其特征在于，其化学组成式为RbMn2Sb3S7，属于四方晶系，I-4 2m空间群，晶胞参数a=17.070(2)Å，b=17.070(2)Å，c=11.520(2)Å，α=90°，β=90°，γ=90°，V= 3356.8(8)Å3 ，Z=1，暗红色棒状，能隙为 1.43 eV。
4.一种如权利要求3所述的用于混凝土抑菌防腐的四元硫化物半导体光催化材料的制备方法，其特征在于以摩尔比为1.0-2.0：1.0-2.0：0.5：2.0-3.0的碳酸铷、金属锰、二元固溶体三硫化二锑和单质硫为原料；以体积比为0.3-0.8：1.0-2.0： 2.0-3.0的氨水、水合肼和聚乙二醇400为溶剂；将每0.52-0.838克原料加入3.3-5.8 mL 所述的溶剂中，在120 -180℃环境中反应4-7天，经去离子水和乙醇洗涤后得到四元硫化物半导体材料RbMn2Sb3S7。
5.一种如权利要求1或3所述的用于混凝土抑菌防腐的四元硫化物半导体光催化材料的用途，其特征在于，作为混凝土防腐光催化材料。
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