CN113413920A - 单金属In2S3/In-MOF半导体材料在光解水产氢中的应用 - Google Patents
单金属In2S3/In-MOF半导体材料在光解水产氢中的应用 Download PDFInfo
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Abstract
本发明公开了一种单金属In2S3/In‑MOF半导体材料在光解水产氢中的应用。采用单金属半导体复合材料In2S3/In‑MOF为光催化剂,可见光照射下制备氢气。本发明与现有技术相比,优点为:(1) 制备过程只使用水热法和油浴法,操作过程简单,制备方便,对设备要求低;(2) 制备的单金属异质结的In2S3/In‑MOF复合光催化剂较现有公开报道的其它催化材料的催化效果有明显提升;(3) 反应采用去离子水、DMF作为反应介质,过程安全平稳,无明火、烟雾产生,无三废排放,环境友好且容易工业放大。
Description
技术领域
本发明涉及一种单金属In2S3/In-MOF半导体光催化材料,在可见光照射下分解水来制备氢气的应用方法,属于新型半导体材料与新能源领域。
背景技术
目前,受到我国工业高速发展以及化石燃料消耗的影响,新型能源供应的问题急需解决,同时,将太阳能转化为电能是研究人员面临的主要科学挑战之一,半导体材料可以用于这种能量转换,在此基础上,制备一种新型无污染的能源代替化石燃料变成首要目标。可见光可以通过催化化学键的形成而转化为化学能。这种方法的一个研究重点是光催化分解水以从水中生成氢气和氧气;光催化还原二氧化碳为碳基化学品也是研发的重点之一。利用半导体光催化剂进行人工光合作用生产氢气等清洁化学燃料,作为满足全球可再生能源供应需求、减少化石燃料燃烧有害影响的一种有希望的途径,引起了广泛的关注经过不断研究探索,科研工作者在氧化铟基础上制备了一种半导体光催化材料(In2O3/g-C3N4)用于可见光下制取氢气这种新型无污染的能源(Cao S-W, Liu X-F, Yuan Y-P, Zhang Z-Y,Liao Y-S, Fang J, et al. Solar-to-fuels conversion over In2O3/g-C3N4 hybridphotocatalysts. Applied Catalysis B: Environmental. 2014; 147: 940-6.)以及半导体光催化材料(In2O3/In2S3)用于光电化学制取氢气(Li H, Chen C, Huang X, Leng Y,Hou M, Xiao X, et al. Fabrication of In2O3/In2S3 core-shell nanocubes forenhanced photoelectrochemical performance. Journal of Power Sources. 2014;247:915-9.)。可见光能光催化分解水制氢具有可再生、环保等优点,被认为是解决日益严重的能源危机的一种很有前途的策略,符合世界碳达峰、碳中和的战略方向。
各种半导体光催化剂,包括金属氧化物、硫族化合物、氮化物和金属有机骨架,在各种光催化反应中得到了广泛的应用。最后,发现半导体异质结的形成是一种常见而有效的方法。由于其良好的匹配能带和良好的光电性能,可以提高电荷转移和光电转换效率。因此,我们需要进一步探索一种更经济高效的光催化剂。含有两种或三种不同材料或相的半导体复合材料可以有效地促进电荷分离和载流子转移,大大提高光催化和光电化学的效率,但是,双或多金属复合材料制备、分离、后处理、回收等存在一定难度。因此,本发明采用操作简便、油浴-水热法制备了In2S3和In-MOF单金属复合半导体材料,构建了In2S3/In-MOF异质结复合光催化剂,应用于自然光催化产氢。
发明内容
本发明的目的在于提出一种In2S3和In-MOF单金属复合半导体材料在制备氢气中的新的应用方法。采用In2S3/In-MOF单金属复合半导体材料为光催化剂,加入到10 wt%三乙醇胺水溶液中,超声波或搅拌分散30 min,转移至产氢装置中,光照条件下制备氢气。
实现本发明目的的技术解决方案是由制备的In-MOF前驱体、硝酸铟水合物In(NO3)3·4H2O和硫代乙酰胺通过水热法等手段完成,其中,单金属硫化铟半导体材料In2S3/In-MOF的构建具体步骤如下:
步骤1)In-MOF的制备:N,N-二甲基甲酰胺中加入对苯二甲酸和硝酸铟水合物In(NO3)3·4H2O,然后将其放入超声波清洗器中超声30 min使其充分混合,搅拌均匀后油浴加热至120 ℃维持1 h。随油浴锅自然冷却至室温并静置分层后,吸除大部分清液,然后在转速3000 rpm下离心,并用DMF洗涤一次和乙醇洗涤二次得到白色沉淀,在60 ℃真空干燥2 h得到目标中间体,其中,对苯二甲酸与硝酸铟水合物In(NO3)3·4H2O的质量比为1:1;
步骤2)In2S3/In-MOF复合光催化剂的制备:将步骤1得到的In-MOF,硝酸铟水合物In(NO3)3·4H2O和硫代乙酰胺溶于去离子水,混合物超声30 min使其充分混合,置入不锈钢水热反应釜中,在180 ℃下加热10 h至12 h后冷却至室温,所得混合溶液在3000 rpm转速下离心并用去离子水、乙醇分别洗涤两次,在60 ℃下真空干燥2 h得到土黄色In2S3/In-MOF。在实验中通过改变硝酸铟水合物InCl3·4H2O和TAA的投料来改变其In、S的摩尔比,从而合成一系列不同比例的In2S3/In-MOF,In : S为1:1、1:1.5、1:2、1:4、1:6分别记为In2S3/In-MOF-1,In2S3/In-MOF-1.5,In2S3/In-MOF-2,In2S3/In-MOF-4,In2S3/In-MOF-6。
本发明的In2S3/In-MOF半导体材料与10 wt%三乙醇胺水溶液质量比为1:2500,产氢装置抽取真空后,光照一定时间,根据气相色谱所得峰面积及时间点计算产氢速率。
实现本发明目的的技术解决方案的关键技术在于:首先油浴加热制备出In-MOF前驱体,后与硝酸铟水合物In(NO3)3·4H2O和硫代乙酰胺通过水热反应釜中得到单金属异质结的In2S3/In-MOF复合光催化剂(见附图1~4),半导体In经光照激发的电子经异质结MOF结构中的碳骨架迅速传导出来,进行光催化反应,有效阻止了电子、空穴的再次复合而失去催化活性,这极大地提高了其光催化制取氢气的性能。
本发明与现有技术相比,优点为:(1) 制备过程只使用水热法和油浴法的普通加热方式,无需马沸炉、管式炉中高温煅烧、惰性气体保护等繁琐工艺,操作过程简单,制备方便,对设备要求低;(2) 制备的单金属异质结的In2S3/In-MOF复合光催化剂较现有公开报道的其它单金属催化材料的催化效果有显著提升,结构稳定性、催化活性较好,可接近、甚至优于双金属、多金属等复合催化剂;(3) 反应采用去离子水、DMF作为反应介质,整个反应、后处理过程安全平稳,溶剂均可回收,环境友好且容易工业放大。
附图说明
本发明有如下11幅附图:
图1是单金属In2S3/In-MOF、In2S3、In-MOF、In2S3标准图谱的XRD衍射图,
图2是In2S3 (a) In-MOF, (b), In2S3/In-MOF (c) 的SEM 图之一,
图3是In2S3 (a) In-MOF, (b), In2S3/In-MOF (c) 的SEM 图之二,
图4是In2S3 (a) In-MOF, (b), In2S3/In-MOF (c) 的SEM 图之三,
图5是In2S3/In-MOF 的TEM 图之一,
图6是In2S3/In-MOF 的TEM 图之二,
图7是In2S3/In-MOF 的TEM 图之三,
图8是In2S3/In-MOF 的TEM 图之四,
图9是In2S3/In-MOF 的XPS全扫描图,
图10是光催化产氢的速率图之一,
图11是光催化产氢的速率图之二。
具体实施方式
下面的实施例对本发明做进一步说明,其目的是能够更好理解本发明的内容。但是实施例不以任何方式限制本发明的范围。本专业领域的技术人员在本发明权利要求范围内做出的改进和调整也应属于本发明的权利和保护范围。
实施例1
In-MOF的制备:在150 ml N,N-二甲基甲酰胺中加入1.2 g对苯二甲酸和1.2 g硝酸铟水合物In(NO3)3·xH2O,然后将其放入超声波清洗器中超声30 min使其充分混合,搅拌均匀后油浴加热至120 ℃维持1 h。随油浴锅自然冷却至室温并静置分层后,倒出上层大部分清液,然后离心(3000 rpm)并用DMF洗涤一次和乙醇洗涤二次得到白色沉淀。最后,在60℃真空干燥2 h获得白色粉末,产量约0.8 g。
实施例2
In2S3/In-MOF的制备:将0.1190 g In-MOF,一定量的硝酸铟水合物InCl3·4H2O和0.02910 g TAA溶于20 ml去离子水。混合物超声30 min使其充分混合,磁力搅拌均匀后,置入50 ml的不锈钢反应釜中,在180 ℃下加热10 h至12 h后冷却至室温。将以上溶液离心(3000 rpm)并用去离子水洗涤和乙醇洗涤各两次。最后在60 ℃真空干燥2 h获得土黄色In2S3/In-MOF约0.12 g。通过同样制备方法,不加入In-MOF来制备纯的In2S3用于前驱体的空白对比。
通过改变硝酸铟水合物InCl3·4H2O和TAA的投料来改变其In、S的原子摩尔比,从而合成一系列不同比例的In2S3/In-MOF,选取优化后的In : S原子摩尔比为1:1、1:1.5、1:2、1:4、1:6的几种比例,分别记为In2S3/In-MOF-1,In2S3/In-MOF-1.5,In2S3/In-MOF-2,In2S3/In-MOF-4,In2S3/In-MOF-6,不同比例的In2S3/In-MOF产品均为土黄色粉末。
取40 mg实施例2制备的In2S3/In-MOF,加入到50 mL10 wt%三乙醇胺水溶液中,超声波分散30 min,再加入50 mL 10 wt%三乙醇胺水溶液,混合均匀,转移至产氢反应发生装置中,保持装置密闭,待抽取真空后,开启光源,每30 min自动取样记录峰面积,持续光照3h,根据气相色谱所得峰面积及时间点计算产氢速率,数据如附图10所示,为了比较复合前后的效果,复合材料In2S3/In-MOF 与In2S3、In-MOF 的比较结果如附图11所示。
Claims (2)
1.单金属In2S3/In-MOF材料在光解水产氢中的应用,其特征在于:采用单金属半导体复合材料In2S3/In-MOF为光催化剂,加入到10wt%三乙醇胺水溶液中,超声波或搅拌分散30min,转移到产氢装置中,模拟自然光照条件下制备氢气,其中,单金属硫化铟半导体材料In2S3/In-MOF的构建具体步骤如下:
步骤1)In-MOF的制备:N,N-二甲基甲酰胺中加入对苯二甲酸和硝酸铟水合物In(NO3)3·4H2O,然后将其放入超声波清洗器中超声30 min使其充分混合,搅拌均匀后油浴加热至120 ℃维持1 h,随油浴锅自然冷却至室温并静置分层后,吸除大部分清液,然后在转速3000 rpm下离心,并用DMF洗涤一次和乙醇洗涤二次得到白色沉淀,在60 ℃真空干燥2 h得到目标中间体,其中,对苯二甲酸与硝酸铟水合物In(NO3)3·4H2O的质量比为1:1;
步骤2) In2S3/In-MOF复合光催化剂的制备:将步骤1得到的In-MOF,硝酸铟水合物In(NO3)3·4H2O和硫代乙酰胺溶于去离子水,混合物超声30 min使其充分混合,置入不锈钢水热反应釜中,在180 ℃下加热10 h至12 h后冷却至室温,所得混合溶液在3000 rpm转速下离心并用去离子水、乙醇分别洗涤两次,在60 ℃下真空干燥2 h得到In2S3/In-MOF,实验中通过改变硝酸铟水合物In(NO3)3·xH2O与硫代乙酰胺的物料比来调控In2S3/In-MOF材料表面In2S3的铟、硫比,从而可以得到一系列不同比例的In2S3/In-MOF。
2.根据权利要求1所述的单金属In2S3/In-MOF材料在光解水产氢中的应用,其特征在于:单金属In2S3/In-MOF与10wt%的三乙醇胺水溶液质量比为1:2500,产氢装置抽取真空后,光照一定时间,根据气相色谱所得峰面积及时间点计算产氢速率。
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CN116393145A (zh) * | 2023-02-27 | 2023-07-07 | 广东石油化工学院 | 一种Ga掺杂In2S3催化剂的制备方法及其应用 |
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CN116393145A (zh) * | 2023-02-27 | 2023-07-07 | 广东石油化工学院 | 一种Ga掺杂In2S3催化剂的制备方法及其应用 |
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