CN113666341A - 一种硫属化合物管状材料的制备方法 - Google Patents
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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
- C01B17/00—Sulfur; Compounds thereof
- C01B17/20—Methods for preparing sulfides or polysulfides, in general
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B19/00—Selenium; Tellurium; Compounds thereof
- C01B19/007—Tellurides or selenides of metals
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G19/00—Compounds of tin
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G21/00—Compounds of lead
- C01G21/21—Sulfides
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- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
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Abstract
本发明涉及一种硫属化合物管状材料的制备方法,属于光电材料制备技术领域。本发明将固体硫族元素原料放置在双温区炉反应器的低温加热区,将金属原料放置在双温区炉反应器的高温硫化反应区,采用惰性气体进行洗气,然后对低温加热区的固体硫族元素原料和高温硫化反应区的金属原料进行加热,低温加热区的固体硫族元素原料释放气态硫族元素与高温硫化反应区的金属原料反应生成气相硫属化合物,气相硫属化合物在基底上冷凝即得硫属化合物管状材料。本发明硫属化合物管状材料的制备工艺简单,可大规模生产,硫属化合物管状材料的比表面积大,能够更好的捕集光子,加速光生载流子的传输速率,适合应用于光电半导体领域。
Description
技术领域
本发明涉及一种硫属化合物管状材料的制备方法,属于光电材料制备技术领域。
背景技术
金属硫属化合物是重要的工业生产原料,被广泛应用于各个领域。其中大多金属硫属化合物具有半导体性质,常被用于光伏及光电催化材料。硫化铜(CuS)薄膜,拥有良好的光电效应,并且具有光敏性和光吸收性是理想的光电化学材料;硒化锑(Sb2Se3)为二元单相化合物,具有合适的禁带宽度(~1.15eV)以及较大的吸收系数(>105cm-1),非常适合制作新型低成本低毒的太阳能电池;二硫化锡(SnS2)为二维结构材料,SnS2是一种具有2.2eV禁带宽度的层状材料,带隙较窄,具有宽的太阳光谱吸收范围,而广泛应用于光催化领域;碲化镉(GdTe)是一种重要的Ⅱ-Ⅵ族化合物半导体材料,晶体结构为闪锌矿型,具有直接跃迁型能带结构,禁带宽度为1.5eV,吸收系数高(>5×105cm-1),因此被广泛应用于光谱分析、红外电光调制器、红外探测器等领域。
制备不同特性的硫属化合物,常采用不同的制备方法。一般情况下,电化学法可以实现硫属化合物薄膜的制备,普通的加热合成法可以实现硫属化合物的规模化制备,例如:在三乙醇胺为络合剂的水溶液体系下可通过电沉积手段实现实现CuS薄膜的制备;PbS制备方法主要为将铅屑与单斜硫在真空石英管内,加热到1100℃,或PbO与H2S在石英管内加热到500℃,均可制备得到硫化铅粉体;Sb2Se3常用的制备方法为将反应原料Sb、Se和助熔剂CsCl,混合后获得前驱体,对前驱体进行充分研磨,使其混合均匀,将混合后的样品装入石英瓶中,利用真空泵机组抽真空达到10~102Pa(也可以用惰性气体保护),从而排除空气对熔盐反应的影响,用氢氧火焰将石英瓶封口;将密封后装有混合样品的石英瓶放在普通升温炉中从常温加热到700℃保持72h,然后降温到450℃取出石英瓶放入水中快速降温至室温,最后将石英瓶中的样品取出,超声水洗多次除去助熔剂CsCl,之后将样品置于干燥箱80℃干燥2h,得到表面具有晶体光泽的微米尺寸Sb2Se3单晶颗粒;SnS2薄膜常用的制备方法为化学气相沉积法(CVD),在反应温度为710℃的条件下反应5分钟,采用二氧化锡(SnO2)和硫作为Sn和S前体来生长SnS2薄膜;ZnS粉体的制备方法主要为化学气相沉积法(CVD),以Zn蒸汽和H2S气体为原料,在沉积温度为650℃~750℃,沉积室的压力为5~72kPa的参数下制得硫化锌;GaTe的常用制备为烧结法,将Ga粉与Te混合热压烧结,将混合粉体首先加热至400℃,保温2h,压力维持在20Mpa,随后将温度升至800℃,继续保温2h,压力维持在60Mpa,最后自然冷却至室温即可得到GaTe粉体;MoS2粉体的制备方法为化学合成法以钼酸铵为原料,先将其硫化为硫代钼酸铵,再转化为三硫化钼,然后经过热分解制备纯净二硫化钼;WS2的常用制备方法为焙烧分解法,将钨酸与氨水在57~60℃搅拌下反应3h,保温自然沉降16h以上,生成的钨酸铵再与硫化氢气体反应,生成四硫代钨酸铵经高温焙烧,分解为二硫化钨。
然而,现有制备方法得到的硫属化合物多数为薄膜或者无规则颗粒形貌,在光电半导体领域的应用不具备管状材料比表面积大的优点,因此对于光生载流子的传输与分离较差。
发明内容
本发明针对现有技术中硫属化合物制备问题,提供一种硫属化合物管状材料的制备方法,即基于气固反应原理,采用双温区加热,将气态硫族元素与金属原料反应,制备出硫属化合物管状材料,其工艺简单,可大规模制备形貌完整、结晶质量好、结构紧密、单根分散的硫属化合物管状材料,有利于实现光生载流子在径向上的传输与分离,相较于普通球型或无规则硫属化合物材料具有更大的比表面积。
一种硫属化合物管状材料的制备方法,具体步骤如下:
将固体硫族元素原料放置在双温区炉反应器的低温加热区,将金属原料放置在双温区炉反应器的高温硫化反应区,采用惰性气体进行洗气,然后对低温加热区的固体硫族元素原料和高温硫化反应区的金属原料进行加热,低温加热区的固体硫族元素原料释放气态硫族元素与高温硫化反应区的金属原料反应1~3h生成气相硫属化合物,气相硫属化合物在基底上冷凝即得硫属化合物管状材料;
所述硫族元素为氧、硫、硒或碲;硫族元素原料中硫族元素的含量不低于10wt%;
所述金属原料包括但不限于锌、铜、钨、锡、钼、银、锑、镓;
所述金属原料中金属的含量不低于98wt%;
所述低温加热区的加热温度为硫族属元素释放气态硫族元素的温度,高温硫化反应区的加热温度为气态硫分子与金属原料硫化所需的温度;
所述惰性气体纯度不低于98%;
所述基底为硅的氧化物、氮化物或碳化物、卤素化合物、金属酸盐、磷酸盐或硼酸盐;
所述硫属化合物管状材料的直径为10~100μm;
所述双温区炉反应器的加热方式包括但不限于电阻加热、等离子加热、激光加热、微波加热;
所述金属原料包括但不限于粉状、块状、粒状。
硫属化合物管状材料的制备原理:基于气相-固相反应机制,气固反应机理的通式可写成:
A(g)+bB(s)=cC(g)+dD(s)
式中,b,c,d为计量系数,A为硫族元素,B为金属,C为硫属管状化合物前体,D为高温反应区所得产物。
在反应时,气体反应物A由气相主体与无机非金属B通过颗粒外部的边缘层反应,生成的气体生成物C;与此同时气体反应物A由气相主体经无机非金属B颗粒的固体产物层扩散至内部反应界面,生成固相生成物D,气体生成物C则通过固体产物层及边界层又随之扩散至气相主体;
硫族元素反应物A与无机非金属边缘层反应生成气相生成物C,气相生成物C随着气体的扩散冷凝于反应装置的低温端口盛有无机非金属颗粒的基底处。随着反应的不断进行,气相反应产物C不断吸附在无机非金属颗粒表面,颗粒边缘处逐渐率先达到饱和状态,原子之间不断调整构象,实现轨道杂化,形成沿某个晶面择优生长的生长趋势,最后生成管状材料。
本发明的有益效果是:
(1)本发明基于气固反应原理,采用双温区分别加热的火法工艺,将硫族元素蒸气与金属反应生成形貌完整、结晶质量好、结构紧密、单根分散的硫属化合物管状材料,相较于传统湿法工艺繁琐的反应过程与冗长的反应时间,其工艺简单;
(2)本发明采用火法,无需使用强酸和强碱,不产生硫化氢与二甲胺等有毒害的气体,不需使用有毒有机溶剂,不产生有毒有害废液,反应结束后不需进行废液处理,工艺环保;
(3)本发明相较于无机金属与硫源混合加热法更易于控制硫属化合物产物的形态,有利于生成管状的硫属化合物;
(4)本发明硫属化合物管状材料具有高的比表面积,能够更好地捕集光子,并且显著加速光生载流子的传输速率,可很好地应用于光电领域。
附图说明
图1为实施例1中ZnS管状材料的SEM图;
图2为实施例1中ZnS管状材料的Raman图谱;
图3为实施例2中SnS2管状材料的SEM图;
图4为实施例2中SnS2管状材料的Raman图谱;
图5为实施例3中Sb2Se3管状材料的SEM图;
图6为实施例3中Sb2Se3管状材料的Raman图谱;
图7为实施例4中PbS管状材料的SEM图;
图8为实施例4中PbS管状材料的XRD图谱。
具体实施方式
下面结合具体实施方式对本发明作进一步详细说明,但本发明的保护范围并不限于所述内容。
实施例1:本实施例采用双温区管式炉制备ZnS管状材料;
一种ZnS管状材料的制备方法,具体步骤如下:
(1)将0.4mol升华硫(纯度为99.9%)放置在双温区管式炉的低温加热区,将0.2mol金属锌粉放置在双温区管式炉的高温硫化加热区;其中金属锌粉的纯度≥98%;
(2)开启真空泵,将反应体系内的压强抽至10Pa及以下,随后关闭抽气阀,打开进气阀,充入高纯氩气(纯度为99.99%)至压力表时数为100KPa时关闭进气阀,打开进气阀将反应体系内压强重新抽至10Pa及以下,重复洗气三次以排尽体系内的杂质气体,避免生成氧化物杂质;
(3)充入氩气使得体系压强达到100Kpa;
(4)开启加热程序使低温加热区的温度为120℃,高温硫化反应区温度为500℃,低温加热区的固体硫源释放气态硫与高温硫化反应区的金属锌粉反应1h生成气相硫化锌,气相硫化锌在温度为200℃的铝钠尖晶石基底上冷凝即得硫化锌管状材料;
本实施例产物硫化锌颜色为白色,形貌为管状,硫化锌管状材料的SEM形貌图见图1,从图1可知,产物硫化锌的形貌为管状,硫化锌管状材料的Raman图谱见图2,拉曼位移为346cm-1,与硫化锌拉曼特征峰很好地吻合。
实施例2:本实施例采用双温区竖式炉制备硫化锡管状材料;
一种硫化锡管状材料的制备方法,具体步骤如下:
(1)将1.0mol升华硫(纯度为99.9%)放置在双温区竖式炉的低温加热区,将0.4mol锡粉放置在双温区竖式炉的高温硫化加热区;其中锡粉的纯度≥98%;
(2)开启真空泵,将反应体系内的压强抽至10Pa及以下,随后关闭抽气阀,打开进气阀,充入高纯氩气(纯度为99.99%)至压力表时数为100KPa时关闭进气阀,打开进气阀将反应体系内压强重新抽至10Pa及以下,重复洗气三次以排尽体系内的杂质气体,避免生成氧化物杂质;
(3)充入氩气使得体系压强达到50Kpa;
(4)开启加热程序使低温加热区的温度为200℃,高温硫化反应区温度为800℃,低温加热区的固体硫源释放气态硫与高温硫化反应区的锡粉反应1h生成硫化锡,硫化锡在温度为400℃的铝钠尖晶石基底处冷凝即得硫化锡微纳米管;
本实施例产物硫化锡颜色为棕黄色,形貌为管状材料状,硫化锡管状材料的SEM形貌图见图3,从图3可知,产物硫化锡的形貌为管状材料状,硫化锡管状材料的Raman图谱见图4,拉曼位移为2697.4cm-1,与硫化锡拉曼特征峰很好地吻合。
实施例3:本实施例采用双温区管式炉制备硒化锑管状材料;
一种硒化锑管状材料的制备方法,具体步骤如下:
(1)将0.8mol硒粉(纯度大于99.9%)放置在双温区管式炉的低温加热区,将0.3mol金属锑粉放置在双温区管式炉的高温硫化加热区;其中金属锑粉的纯度≥98%;
(2)开启真空泵,将反应体系内的压强抽至10Pa及以下,随后关闭抽气阀,打开进气阀,充入高纯氩气(纯度为99.99%)至压力表时数为100KPa时关闭进气阀,打开进气阀将反应体系内压强重新抽至10Pa及以下,重复洗气三次以排尽体系内的杂质气体,避免生成氧化物杂质;
(3)充入氩气使得体系压强达到20Kpa;
(4)开启加热程序使低温加热区的温度为250℃,高温硫化反应区温度为700℃,低温加热区的硒粉释放气态硒与高温硫化反应区的金属锑粉反应1.5h生成气相硒化锑,气相硒化锑在温度为300℃的铝钠尖晶石基底上冷凝即得硒化锑管状材料;
本实施例产物硒化锑颜色为银白色,形貌为管状材料状,硒化锑管状材料的SEM形貌图见图4,从图4可知,产物硒化锑的形貌为管状材料状,硒化锑管状材料的Raman图谱见图5,拉曼位移为190.5cm-1、254.1cm-1,与硒化锑拉曼特征峰很好地吻合。
实施例4:本实施例采用双温区箱式炉制备硫化铅管状材料;
一种硫化铅管状材料的制备方法,具体步骤如下:
(1)将1.5mol升华硫(纯度为99.9%)放置在双温区管式炉的低温加热区,将1.0mol金属铅粉放置在双温区管式炉的高温硫化加热区;其中金属铅粉的纯度≥98%;
(2)开启真空泵,将反应体系内的压强抽至10Pa及以下,随后关闭抽气阀,打开进气阀,充入高纯氦气(纯度为99.99%)至压力表时数为100KPa时关闭进气阀,打开进气阀将反应体系内压强重新抽至10Pa及以下,重复洗气三次以排尽体系内的杂质气体,避免生成氧化物杂质;
(3)充入氦气使得体系压强达到10Kpa;
(4)开启加热程序使低温加热区的温度为300℃,高温硫化反应区温度为1000℃,低温加热区的固体硫源释放气态硫与高温硫化反应区的金属铅粉反应1h生成气相硫化铅,气相硫化铅在温度为500℃的铝钠尖晶石基底上冷凝即得硫化铅管状材料;
本实施例产物硫化铅颜色为黑色,形貌为管状材料状,硫化铅管状材料的SEM形貌图见图5,从图5可知,产物硫化铅的形貌为管状材料状,硫化铅管状材料的XRD图谱见图6,与标准卡片JCPD No.05-0592中的25.96°、30.07°、43.06°、50.98°53.41°、62.54°等PbS的特征峰很好地吻合。
以上结合附图对本发明的具体实施方式作了详细说明,但是本发明并不限于上述实施方式,在本领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下作出各种变化。
Claims (7)
1.一种硫属化合物管状材料的制备方法,其特征在于,具体步骤如下:
将固体硫族元素原料放置在双温区炉反应器的低温加热区,将金属原料放置在双温区炉反应器的高温硫化反应区,采用惰性气体进行洗气,然后对低温加热区的固体硫族元素原料和高温硫化反应区的金属原料进行加热,低温加热区的固体硫族元素原料释放气态硫族元素与高温硫化反应区的金属原料反应生成气相硫属化合物,气相硫属化合物在基底上冷凝即得硫属化合物管状材料。
2.根据权利要求1所述硫属化合物管状材料的制备方法,其特征在于:硫族元素为氧、硫、硒或碲。
3.根据权利要求1所述硫属化合物管状材料的制备方法,其特征在于:金属原料包括但不限于锌、铜、钨、锡、钼、银、锑、镓。
4.根据权利要求1所述硫属化合物管状材料的制备方法,其特征在于:低温加热区的加热温度为硫族属元素释放气态硫族元素的温度,高温硫化反应区的加热温度为气态硫分子与金属原料硫化所需的温度。
5.根据权利要求1所述硫属化合物管状材料的制备方法,其特征在于:惰性气体纯度不低于98%。
6.根据权利要求1所述硫属化合物管状材料的制备方法,其特征在于:基底为硅的氧化物、氮化物或碳化物、卤素化合物、金属酸盐、磷酸盐或硼酸盐。
7.根据权利要求1所述硫属化合物管状材料的制备方法,其特征在于:硫属化合物管状材料的直径为10~100μm。
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