CN108722395A - 一种利用酿酒葡萄残渣制备的铂纳米催化剂及其制氢方法 - Google Patents
一种利用酿酒葡萄残渣制备的铂纳米催化剂及其制氢方法 Download PDFInfo
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Abstract
一种利用酿酒葡萄残渣制备的铂纳米催化剂及其制氢方法,所述的铂纳米催化剂由以下步骤制备而成:1)将酿酒葡萄残渣晾干,研磨成粉末;2)将酿酒葡萄残渣粉末与水混合提取,离心,过滤,得酿酒葡萄残渣水提液,将水提液冷冻干燥,得固体植物质;3)将酿酒葡萄残渣水提液的固体植物质与水混合后,再与氯铂酸溶液混合反应,制得铂纳米溶胶。本发明还包括一种利用酿酒葡萄残渣制备的铂纳米催化剂进行制氢的方法。本发明使用酿酒葡萄残渣作为原料,成本低廉,符合低资源高值化的理念,整个过程工艺简单,无其他化学试剂的加入,绿色环保;产氢效果佳且催化剂稳定性良好,在光催化领域具有良好的应用前景。
Description
技术领域
本发明涉及一种铂纳米颗粒及其应用,具体涉及一种利用酿酒葡萄残渣制备的铂纳米催化剂及其制氢方法。
背景技术
随着化石燃料的日益枯竭,寻找新型可替代能源已成为全球科学家的关注热点。普通化石燃料在燃烧过程中会产生二氧化硫、一氧化碳、一氧化氮、二氧化碳等气体,对环境造成严重损害,而氢能源的燃烧效率高,燃烧产物只有水,不会对环境造成污染,且属于可再生能源,因此是理想的替代能源。
光催化分解水制氢是利用太阳能分解水生成氢气,是最理想、最经济的制备方法,对人类社会的发展具有重要意义。在光催化产氢中,催化剂的选择至关重要,而通常的光催化产氢方法中,催化剂的制备需要高温煅烧、水热处理等过程,制备步骤繁琐且耗能高。因此,探究出一条工艺简单,耗能低的光催化产氢方法具有重要的现实意义。
铂纳米是一种优异的催化材料,在光催化领域应用广泛。例如:将二氧化钛修饰的铂催化剂用于光催化降解苯酚等污染物具有显著效果(Anna Golabiewska etal.Molecular Catalysis 2017,442:154–163),将铂纳米作为助催化剂用于二氧化钛半导体光催化高效产氢(X Jiang et al.Journal of Materials Chemistry A,2015,3(5):2271-2282;2.李书军等,专利号201610808987.9),将铂纳米作为助催化剂用于C3N4光催化产氢体系(郝旭强等.物理化学学报2016,32(10):2581-2592),将铂纳米作为催化剂直接产氢等(Li Wang et al.Optics Communications 2016,370:122–126)。
铂纳米具有优异的催化性能,使其在光催化产氢领域成为明星材料。但在目前已有的光催化产氢研究中,使用的铂纳米是由光照法或化学法制备而成,这些方法通常需要引入PVP(聚乙烯吡咯烷酮)、CTAB(三甲基十六烷基溴化铵)等表面活性剂以及甲醇、乙二醇、硼氢化钠等还原剂,这些物质通常有毒且易污染环境,与光催化绿色环保的理念相违背。因此,绿色制备铂纳米,再将铂纳米用于光催化产氢体系,对光催化的发展具有重要意义。
植物法制备贵金属纳米材料具有绿色、环保、经济的特点,近年来,植物法制备铂纳米及其应用引起了全球科学家的关注(Birgütay Sahin et al.Colloids and SurfacesB:Biointerfaces 2018,163:119–124;2.A.Thirumurugan et al.Materials Letters 170(2016):175–178)。然而至今,将植物法制备的铂纳米用于光催化产氢领域却尚无研究。
发明内容
本发明所要解决的技术问题是,针对现有技术的不足,提供一种绿色环保,不会对环境造成污染的利用酿酒葡萄残渣制备的铂纳米催化剂。
本发明进一步要解决的技术问题是,提供一种工艺简单,能耗低,绿色环保的利用酿酒葡萄残渣制备的铂纳米催化剂制氢方法。
本发明解决其技术问题所采用的技术方案是:一种利用酿酒葡萄残渣制备的铂纳米催化剂,由以下步骤制备而成:
1)将酿酒葡萄残渣晾干,研磨成粉末;
2)将酿酒葡萄残渣粉末与水混合提取,离心,过滤,得酿酒葡萄残渣水提液,将水提液冷冻干燥,得固体植物质;
3)将酿酒葡萄残渣水提液的固体植物质与水混合后,再与氯铂酸溶液混合反应,制得铂纳米溶胶。
进一步,步骤1)中,将酿酒葡萄残渣研磨后,可使用筛子筛得较细粉末,优选30-100目的筛子。
进一步,步骤2)中,酿酒葡萄残渣粉末与水的比例可为10-150g/L(优选30-100g/L,更优选40-60g/L),其中,酿酒葡萄残渣粉末按质量计算,水按体积计算。
进一步,步骤2)中,混合提取过程的温度可为20-90℃(优选25-70℃,更优选30-50℃),时间可为0.5-35h(优选2-24h,更优选4-12h)。
进一步,步骤3)中,酿酒葡萄残渣水提液的固体植物质与水的比例可为0.1-20g/L(优选3-15g/L,更优选5-9g/L),其中,酿酒葡萄残渣水提液的固体植物质按质量计算,水按体积计算;控制溶液中氯铂酸的浓度为0.5×10-4-3.0×10-4mol/L(优选1.0×10-4-2.0×10-4mol/L)。
进一步,步骤3)中,反应温度可为20-90℃(优选25-70℃,更优选30-50℃),时间可为1-35h(优选3-12h)。
本发明进一步解决其技术问题所采用的技术方案是:一种利用酿酒葡萄残渣制备的铂纳米催化剂进行制氢的方法,包括以下步骤:
将上述方法制得的铂纳米溶胶转移至石英光催化反应瓶,加入光敏剂曙红和牺牲剂三乙醇胺溶液,通入氮气置换后,放入光催化反应器中反应,即可。每隔一小时用气相色谱仪检测氢气含量。
进一步,对于10mL浓度为0.5×10-4-3.0×10-4mol/L的铂纳米溶胶,光敏剂曙红添加量可为5-80mg(优选10-60mg,更优选20-40mg),牺牲剂三乙醇胺溶液添加量可为30mL,pH可为6-12(优选pH为9)。
进一步,牺牲剂三乙醇胺溶液为15wt%的水溶液。
进一步,氮气置换≥30分钟。
本发明之利用酿酒葡萄残渣制备的铂纳米催化剂,使用废料酿酒葡萄残渣作为制备纳米铂的还原剂和稳定剂,成本低廉,符合低资源高值化的理念,整个过程无其他化学试剂的加入,绿色环保,不会对环境造成伤害。
本发明之利用酿酒葡萄残渣制备的铂纳米催化剂制氢方法,与已有的化学法制备纳米铂产氢以及以纳米铂作为助催化剂产氢的结果对比(Li Wang et al.OpticsCommunications 2016,370:122–126;2.李书军等,专利号201610808987.9),本发明在铂添加量低(浓度为1.25×10-4mol/L)的情况下能实现更高效的产氢,且催化剂稳定性良好(产氢量最高可达700μmol以上,且实验循环6次产氢效果仍未见明显降低),因此在光催化领域具有良好的应用前景。
附图说明
图1为本发明实施例1中不同浓度的酿酒葡萄残渣植物质制备的铂纳米产氢效果图;
图2为本发明实施例2中9g/L的酿酒葡萄残渣植物质反应不同时间制备的铂纳米产氢效果图;
图3为本发明实施例3中使用不同pH的三乙醇胺溶液的产氢效果图;
图4为本发明实施例4中使用不同曙红添加量的产氢效果图;
图5为本发明实施例5中铂纳米催化剂的稳定性循环实验产氢效果图。
具体实施方式
以下结合附图及实施例对本发明作进一步说明,但本发明的实施并不局限于此。
实施例1
一种利用酿酒葡萄残渣制备的铂纳米催化剂,由以下步骤制备而成:
1)将酿酒葡萄残渣自然晾干,使用研磨机研磨成粉末;
2)将酿酒葡萄残渣粉末与水混合提取,离心,过滤,得酿酒葡萄残渣水提液,将水提液冷冻干燥,得固体植物质;
酿酒葡萄残渣粉末与水的比例为60g/L,其中,酿酒葡萄残渣粉末按质量计算,水按体积计算;混合提取过程的温度为30℃,时间为6h;
3)将酿酒葡萄残渣水提液的固体植物质分别配成浓度为5g/L、9g/L、15g/L的溶液,加入氯铂酸溶液,控制溶液中氯铂酸的浓度为1.25×10-4mol/L,分别反应12h,制得铂纳米催化剂。
制氢方法,包括以下步骤:
取10mL上述步骤3)所得的反应液,加入曙红20mg,pH为9的15wt%三乙醇胺溶液30mL,氮气置换后放入光催化反应器中反应。每隔一小时用气相色谱仪检测氢气含量。以五小时的产氢量作为对比,9g/L为最佳浓度,产氢量为484.3μmol。各浓度产氢结果见图1。
实施例2
一种利用酿酒葡萄残渣制备的铂纳米催化剂,由以下步骤制备而成:
1)将酿酒葡萄残渣自然晾干,使用研磨机研磨成粉末;
2)将酿酒葡萄残渣粉末与水混合提取,离心,过滤,得酿酒葡萄残渣水提液,将水提液冷冻干燥,得固体植物质;
酿酒葡萄残渣粉末与水的比例为60g/L,其中,酿酒葡萄残渣粉末按质量计算,水按体积计算;混合提取过程的温度为30℃,时间为6h;
3)将酿酒葡萄残渣水提液的固体植物质分别配成三份9g/L的溶液,加入氯铂酸溶液,控制溶液中氯铂酸的浓度为1.25×10-4mol/L,分别反应3h、6h、12h,制得铂纳米催化剂。
制氢方法,包括以下步骤:
取10mL上述步骤3)所得的反应液,加入曙红20mg,pH为9的15wt%三乙醇胺溶液30mL,氮气置换后放入光催化反应器中反应。每隔一小时用气相色谱仪检测氢气含量。以五小时的产氢量作为对比,反应6h为最佳反应时间,产氢量为537.03μmol。不同反应时间制备铂纳米的产氢结果见图2。
实施例3
一种利用酿酒葡萄残渣制备的铂纳米催化剂,由以下步骤制备而成:
1)将酿酒葡萄残渣自然晾干,使用研磨机研磨成粉末;
2)将酿酒葡萄残渣粉末与水混合提取,离心,过滤,得酿酒葡萄残渣水提液,将水提液冷冻干燥,得固体植物质;
酿酒葡萄残渣粉末与水的比例为60g/L,其中,酿酒葡萄残渣粉末按质量计算,水按体积计算;混合提取过程的温度为30℃,时间为6h;
3)将酿酒葡萄残渣水提液的固体植物质分别配成三份9g/L的溶液,加入氯铂酸溶液,控制溶液中氯铂酸的浓度为1.25×10-4mol/L,分别反应6h,制得铂纳米催化剂。
制氢方法,包括以下步骤:
取10mL上述步骤3)所得的反应液,加入曙红20mg,分别加入pH=7、pH=9、pH=11的15wt%三乙醇胺溶液30mL,氮气置换后放入光催化反应器中反应。每隔一小时用气相色谱仪检测氢气含量。以五小时的产氢量作为对比,pH=9的三乙醇胺溶液为最佳pH,产氢量为537.03μmol。不同pH的三乙醇胺溶液产氢结果见图3。
实施例4
一种利用酿酒葡萄残渣制备的铂纳米催化剂,由以下步骤制备而成:
1)将酿酒葡萄残渣自然晾干,使用研磨机研磨成粉末;
2)将酿酒葡萄残渣粉末与水混合提取,离心,过滤,得酿酒葡萄残渣水提液,将水提液冷冻干燥,得固体植物质;
酿酒葡萄残渣粉末与水的比例为60g/L,其中,酿酒葡萄残渣粉末按质量计算,水按体积计算;混合提取过程的温度为30℃,时间为6h;
3)将酿酒葡萄残渣水提液的固体植物质分别配成三份9g/L的溶液,加入氯铂酸溶液,控制溶液中氯铂酸的浓度为1.25×10-4mol/L,分别反应6h,制得铂纳米催化剂。
制氢方法,包括以下步骤:
取10mL上述步骤3)所得的反应液,分别加入曙红20mg、40mg、60mg,pH为9的15wt%三乙醇胺溶液30mL,氮气置换后放入光催化反应器中反应。每隔一小时用气相色谱仪检测氢气含量。以五小时的产氢量作为对比,40mg的曙红为最佳添加量,产氢量724.03μmol。不同曙红添加量的产氢结果见图4。
实施例5
一种利用酿酒葡萄残渣制备的铂纳米催化剂,由以下步骤制备而成:
1)将酿酒葡萄残渣自然晾干,使用研磨机研磨成粉末;
2)将酿酒葡萄残渣粉末与水混合提取,离心,过滤,得酿酒葡萄残渣水提液,将水提液冷冻干燥,得固体植物质;
酿酒葡萄残渣粉末与水的比例为60g/L,其中,酿酒葡萄残渣粉末按质量计算,水按体积计算;混合提取过程的温度为30℃,时间为6h;
3)将酿酒葡萄残渣水提液的固体植物质分别配成9g/L的溶液,加入氯铂酸溶液,控制溶液中氯铂酸的浓度为1.25×10-4mol/L,分别反应12h,制得铂纳米催化剂。
制氢方法,包括以下步骤:
取10mL上述步骤3)所得的反应液,加入曙红20mg,pH为9的15wt%三乙醇胺溶液30mL,氮气置换后放入光催化反应器中反应5小时后,氮气置换放入光催化反应器中继续反应5小时。此时产氢量有所降低,是由于曙红的消耗,加入20mg曙红后氮气置换反应5小时,继续氮气置换反应5小时,再继续加曙红进行第5次和第6次循环操作。每隔一小时用气相色谱仪检测氢气含量,可见循环6次的产氢量仍无明显降低,说明植物法制备的铂纳米在光催化产氢中稳定性良好。各时间段的产氢结果见图5。
以上所述本发明的具体实施方式,仅为本发明的较佳实施例,并不限定本发明的保护范围。任何以本发明的技术构思所做的其他相应的变动和修饰的方案,均属于本发明的保护范围。
Claims (10)
1.一种利用酿酒葡萄残渣制备的铂纳米催化剂,其特征在于,由以下步骤制备而成:
1)将酿酒葡萄残渣晾干,研磨成粉末;
2)将酿酒葡萄残渣粉末与水混合提取,离心,过滤,得酿酒葡萄残渣水提液,将水提液冷冻干燥,得固体植物质;
3)将酿酒葡萄残渣水提液的固体植物质与水混合后,再与氯铂酸溶液混合反应,制得铂纳米溶胶。
2.根据权利要求1所述的利用酿酒葡萄残渣制备的铂纳米催化剂,其特征在于:步骤1)中,将酿酒葡萄残渣研磨后,使用筛子筛得较细粉末。
3.根据权利要求1或2所述的利用酿酒葡萄残渣制备的铂纳米催化剂,其特征在于:步骤2)中,酿酒葡萄残渣粉末与水的比例为10-150g/L,其中,酿酒葡萄残渣粉末按质量计算,水按体积计算。
4.根据权利要求3所述的利用酿酒葡萄残渣制备的铂纳米催化剂,其特征在于:步骤2)中,混合提取过程的温度为20-90℃,时间为0.5-35h。
5.根据权利要求1或2所述的利用酿酒葡萄残渣制备的铂纳米催化剂,其特征在于:步骤3)中,酿酒葡萄残渣水提液的固体植物质与水的比例为0.1-20g/L,其中,酿酒葡萄残渣水提液的固体植物质按质量计算,水按体积计算;控制溶液中氯铂酸的浓度为0.5×10-4-3.0×10-4mol/L。
6.根据权利要求5所述的利用酿酒葡萄残渣制备的铂纳米催化剂,其特征在于:步骤3)中,反应温度为20-90℃,时间为1-35h。
7.一种利用权利要求1所述的铂纳米催化剂进行制氢的方法,其特征在于,包括以下步骤:
将制得的铂纳米溶胶转移至石英光催化反应瓶,加入光敏剂曙红和牺牲剂三乙醇胺溶液,通入氮气置换后,放入光催化反应器中反应,即可。
8.根据权利要求7所述的制氢的方法,其特征在于:对于10mL浓度为0.5×10-4-3.0×10-4mol/L的铂纳米溶胶,光敏剂曙红添加量为5-80mg,牺牲剂三乙醇胺溶液添加量为30mL,pH为6-12。
9.根据权利要求8所述的制氢的方法,其特征在于,牺牲剂三乙醇胺溶液为15wt%的水溶液。
10.根据权利要求7-9任一权利要求所述的制氢的方法,其特征在于,氮气置换≥30分钟。
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