CN112316966A - 一种Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂及其制备方法和应用 - Google Patents
一种Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂及其制备方法和应用 Download PDFInfo
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Abstract
本发明提供了一种Au‑Pt/PtO三元助催化剂痕量负载g‑C3N4光催化剂及其制备方法和应用，该光催化剂g‑C3N4‑Au‑Pt/PtO中在痕量的三元助催化剂负载情况下表现出高效的光催化水解产氢性能，模拟太阳光照射下的光催化水解产氢速率达到20mmol/h/g以上，其420nm单色波长照射下的表观量子效率达到16.0％左右。本发明通过发挥Au的局域等离子体共振效应调控了Pt/PtO的形成，Au‑Pt/PtO三元助催化剂的协同作用发挥出优异的光催化产氢性能并极大地节约了贵金属用量，降低成本。
Description
技术领域
本发明涉及光催化产氢技术领域，具体涉及一种Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂及其制备方法和应用。
背景技术
石墨相氮化碳(g-C3N4)是一种稳定的聚合物半导体，包含着地球富有的C、N元素，具有C-N核心结构的富N前驱体被广泛用来制备g-C3N4。g-C3N4具有独特的层状类石墨相结构和有利于载流子迁移的π-共轭体系，目前已广泛用于光催化水分解制氢、CO2重组储能、环境治理等领域。由于g-C3N4具有较高的HOMO能级(-1.3V) 和适当的禁带宽度(～2.8eV)，大量的研究工作将g-C3N4应用于光催化水分解制氢。助催化剂负载g-C3N4极大地提升了光催化水分解产氢性能，其中以贵金属的优势最为明显，然而贵金属价格昂贵，成本高昂，如何在降低贵金属成本的情况下发挥出最优的光催化水解产氢性能成为亟待解决的问题。
发明内容
有鉴于此，本发明旨在提出Au-Pt/PtO三元助催化剂痕量负载 g-C3N4光催化剂及其制备方法和应用，保持了g-C3N4光生电子的还原能力，拓宽了g-C3N4对可见至近红外光谱的吸收，促进了光生电子的迁移，提供更多的表面活性位点促进水分解反应的进行。
为达到上述目的，本发明的技术方案是这样实现的：
一种Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，该方法包括如下步骤：首先通过高温煅烧的方法制得g-C3N4，然后将Au纳米颗粒利用光沉积还原的方法负载在g-C3N4的表面制得 g-C3N4-Au，之后将Pt/PtO纳米颗粒利用光沉积还原的方法负载在g-C3N4-Au的表面制得。
进一步，该方法包括如下步骤：
(1)制备g-C3N4：
取尿素均匀装入坩埚中，在马弗炉中煅烧后自然降至室温，获得明黄色g-C3N4粉末；
(2)制备g-C3N4-Au：
将g-C3N4溶于去离子水和甲醇的混合溶剂中，持续超声30分钟；然后将四氯金酸的乙醇溶液滴入上述溶液中，在密封光反应器中倒入上述混合溶液，在连续搅拌混合溶液的过程中注入5分钟的高纯度 N2去除溶解O2；连续搅拌混合溶液，用氙灯作为模拟太阳光光源照射，整个光沉积过程持续注入N2；随后用大量去离子水抽滤清洗光催化剂，并将其干燥，得到样品g-C3N4-Au；
(3)制备g-C3N4-Au-Pt/PtO：
将g-C3N4-Au溶于去离子水和甲醇的混合溶剂中，持续超声30 分钟；然后将氯铂酸的乙醇溶液滴入上述溶液中，之后进行与上述(2) 同样的步骤，得到样品g-C3N4-Au-Pt/PtO。
进一步，所述步骤(1)中尿素的用量为10g；所述煅烧的温度为500℃，煅烧时间4h,升温速率为10℃/min。
进一步，所述氙灯为300W，照射时间为30min。
进一步，所述甲醇的纯度≥99.5％，g-C3N4、去离子水和甲醇的质量比为1:250:40，g-C3N4混合溶剂的浓度为0.036M；g-C3N4-Au、去离子水和甲醇的质量比为1:250:40，g-C3N4-Au混合溶剂的浓度为 0.0115M。
进一步，所述步骤(2)中Au相对于g-C3N4的质量百分比为0.3％-1.0％。
进一步，所述步骤(3)中Pt相对于g-C3N4的质量百分比 0.3％-1.0％。
进一步，所述四氯金酸的乙醇溶液的浓度为0.1M，氯铂酸的乙醇溶液的浓度为0.1M。
本发明还提供了一种根据上述所述的制备方法制备得到的 Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂。
本发明还提供了一种根据上述所述的制备方法制备得到的 Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂在光催化水分解产氢上的应用。
相对于现有技术，本发明所述的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂及其制备方法剂和应用具有以下优势：
本发明所述提供的g-C3N4-Au-Pt/PtO光催化剂实现高效光解水制氢速率达到20mmol/h/g以上，在420nm单色波长下的表观量子效率达到16.0％左右。相对于别的研究中助催化剂含量的60％，其表观量子效率增长了7-8倍。
附图说明
图1为g-C3N4、g-C3N4-Au、和g-C3N4-Au-Pt/PtO的XRD图谱；
图2为g-C3N4-Au、g-C3N4-Au-Pt/PtO的Au 4f、Pt 4f XPS图谱；
图3为g-C3N4、g-C3N4-Au、和g-C3N4-Au-Pt/PtO的DRS图谱；
图4为g-C3N4、g-C3N4-Au、和g-C3N4-Au-Pt/PtO在模拟太阳光下的光催化水解产氢速率图谱；
图5为实施例1-4、对比例1-2和对照例的光催化产氢性能对比图；
图6为本发明所述的光催化剂的原理图。
具体实施方式
需要说明的是，在不冲突的情况下，本发明中的实施例及实施例中的特征可以相互组合。
下面结合实施例来详细说明本发明。
实例1：
一种Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，该方法包括如下步骤：
(1)制备g-C3N4：
取10g尿素均匀装入坩埚中，在马弗炉中500℃煅烧4h，升温速率为10℃/min，之后自然降至室温，获得明黄色g-C3N4粉末；
(2)制备g-C3N4-Au：
将200mg的g-C3N4溶于50mL去离子水和10mL甲醇混合溶剂中，持续超声30分钟；然后将相对于g-C3N4质量为0.3％的30μL 0.1M 的四氯金酸的乙醇溶液滴入上述溶液中，在密封光反应器中倒入上述混合溶液，在连续搅拌混合溶液的过程中注入5分钟的高纯度N2去除溶解O2；连续搅拌混合溶液，用300W氙灯HAYASHILA 410-UV 作为模拟太阳光光源照射30min，整个光沉积过程持续注入N2；随后用大量去离子水抽滤清洗光催化剂，并将其干燥，得到样品g-C3N4-Au；
(3)制备g-C3N4-Au-Pt/PtO：
将200mg g-C3N4-Au溶于50mL去离子水和10mL甲醇混合溶剂中，持续超声30分钟；然后将相对于g-C3N4质量百分比为0.3％的30μL 0.1M的氯铂酸的乙醇溶液滴入上述溶液中，之后进行与上述2)同样的步骤，得到样品g-C3N4-Au-Pt/PtO，简称为g-A(0.3)-P(0.3)，(g代表g-C3N4，A代表Au，P代表Pt)。
实例2：
一种Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，该方法包括如下步骤：
(1)制备g-C3N4：
取10g尿素均匀装入坩埚中，在马弗炉中500℃煅烧4h，升温速率为10℃/min，之后自然降至室温，获得明黄色g-C3N4粉末；
(2)制备g-C3N4-Au：
将200mg的g-C3N4溶于50mL去离子水和10mL甲醇混合溶剂中，持续超声30分钟；然后将相对于g-C3N4质量为0.3％的30μL 0.1M 的四氯金酸的乙醇溶液滴入上述溶液中，在密封光反应器中倒入上述混合溶液，在连续搅拌混合溶液的过程中注入5分钟的高纯度N2去除溶解O2；连续搅拌混合溶液，用300W氙灯HAYASHILA 410-UV 作为模拟太阳光光源照射30min，整个光沉积过程持续注入N2；随后用大量去离子水抽滤清洗光催化剂，并将其干燥，得到样品g-C3N4-Au；
(3)制备g-C3N4-Au-Pt/PtO：
将200mg g-C3N4-Au溶于50mL去离子水和10mL甲醇混合溶剂中，持续超声30分钟；然后将相对于g-C3N4质量为0.5％的50μL 0.1M的氯铂酸的乙醇溶液滴入上述溶液中，之后进行与上述2)同样的步骤，得到样品g-C3N4-Au-Pt/PtO，简称为g-A(0.3)-P(0.5)，(g代表g-C3N4，A代表Au，P代表Pt)。
实例3：
一种Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，该方法包括如下步骤：
(1)制备g-C3N4：
取10g尿素均匀装入坩埚中，在马弗炉中500℃煅烧4h，升温速率为10℃/min，之后自然降至室温，获得明黄色g-C3N4粉末；
(2)制备g-C3N4-Au：
将200mg的g-C3N4溶于50mL去离子水和10mL甲醇混合溶剂中，持续超声30分钟；然后将相对于g-C3N4质量为0.5％的50μL 0.1M 的四氯金酸的乙醇溶液滴入上述溶液中，在密封光反应器中倒入上述混合溶液，在连续搅拌混合溶液的过程中注入5分钟的高纯度N2去除溶解O2；连续搅拌混合溶液，用300W氙灯HAYASHILA 410-UV 作为模拟太阳光光源照射30min，整个光沉积过程持续注入N2；随后用大量去离子水抽滤清洗光催化剂，并将其干燥，得到样品g-C3N4-Au；
(3)制备g-C3N4-Au-Pt/PtO：
将200mg g-C3N4-Au溶于50mL去离子水和10mL甲醇混合溶剂中，持续超声30分钟；然后将相对于g-C3N4质量为0.5％的50μL 0.1M的氯铂酸的乙醇溶液滴入上述溶液中，之后进行与上述(2)同样的步骤，得到样品g-C3N4-Au-Pt/PtO，简称为g-A(0.5)-P(0.5)，(g 代表g-C3N4，A代表Au，P代表Pt)。
实例4：
一种Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，该方法包括如下步骤：
(1)制备g-C3N4：
取10g尿素均匀装入坩埚中，在马弗炉中500℃煅烧4h，升温速率为10℃/min，之后自然降至室温，获得明黄色g-C3N4粉末；
(2)制备g-C3N4-Au：
将200mg的g-C3N4溶于50mL去离子水和10mL甲醇混合溶剂中，持续超声30分钟；然后将相对于g-C3N4质量为1.0％的100μL 0.1M的四氯金酸的乙醇溶液滴入上述溶液中，在密封光反应器中倒入上述混合溶液，在连续搅拌混合溶液的过程中注入5分钟的高纯度 N2去除溶解O2；连续搅拌混合溶液，用300W氙灯HAYASHILA 410-UV，整个光沉积过程持续注入N2；随后用大量去离子水抽滤清洗光催化剂，并将其干燥，得到样品g-C3N4-Au；
(3)制备g-C3N4-Au-Pt/PtO：
将200mg g-C3N4-Au溶于50mL去离子水和10mL甲醇混合溶剂中，持续超声30分钟；然后将相对于g-C3N4质量为1.0％的100μL 0.1M的氯铂酸的乙醇溶液滴入上述溶液中，之后进行与上述2)同样的步骤，得到样品g-C3N4-Au-Pt/PtO，简称为g-A(1)-P(1)，(g代表 g-C3N4，A代表Au，P代表Pt)。
对比例1
在实施例1的基础上，仅制备g-C3N4。
对比例2
在实施例1的基础上，仅制备g-C3N4-Au。
光催化水解产氢试验：
采用等量的实施例1-4制备的g-C3N4-Au-Pt/PtO、对比例1制备的g-C3N4、对比例2制备的g-C3N4-Au分别在同样的真空系统环境下的光催化水解产氢。首先将催化剂溶解超声注入到光催化反应瓶内；然后连接光催化反应瓶与光催化反应系统，将系统内环境抽至真空状态；最后300W的氙灯光源照射光催化剂溶液，1h之后停止光照，气相色谱仪检测H2的浓度。另外，采用常用的催化剂TiO2进行催化产氢作为对照组。
如图5所示，实施例1-4、对比例1-2和对照组在同样的真空系统环境下的光催化水解产氢速率分别为21.3mmol/h/g、22.8mmol/h/g、 27.5mmol/h/g、20.4mmol/h/g、0mmol/h/g、9.3mmol/h/g、1.7mmol/h/g。说明了Au/Pt掺杂g-C3N4更有利于提高光催化水解产氢速率，相对于单一负载Au纳米粒子的g-C3N4和TiO2的光催化水解产氢性能明显提升。其中，实例1-4在420nm单色波长下的表观量子效率达到16％左右。
图5还说明了随着Au和Pt含量的增多，随着Au的局部等离子体共振效应的增强和更多Pt/PtO生成，g-A(0.5)-P(0.5)(g代表g-C3N4， A代表Au，P代表Pt)达到最优的光催化水解产氢速率27.5mmol/h/g，而g-A(1.0)-P(1.0)的光催化水解产氢速率最低是归因于过多的Au和 Pt含量影响了g-C3N4对可见光谱的吸收。
如图4所示为对比例1的g-C3N4、对比例2的g-C3N4-Au、实施例1的g-C3N4-Au-Pt/PtO的光催化水解产氢图谱。g-C3N4-Au相对于 g-C3N4具有较高的光催化水解产氢活性，这是由于Au的等离子体共振效应，拓展了g-C3N4对可见至近红外光谱的吸收，增强的局域电场有效避免了光生载流子的复合，Au的热电子注入到g-C3N4的导带增大了电子浓度。g-C3N4-Au-Pt/PtO除了上述中Au的LSPR效应， Pt/PtO纳米颗粒与g-C3N4的有效解除促进了光生电子的迁移，PtO 抑制了H2的逆反应，具有优异电子传导能力的金属Pt加速了H+被还原成H2，从而表现出高效率的光催化产氢性能。
如图1所示为g-C3N4、g-C3N4-Au、和g-C3N4-Au-Pt/PtO的XRD 图谱，所有样品在13.1°和27.4°出现了g-C3N4的衍射峰，分别对应于g-C3N4的(100)晶面和(002)晶面。g-C3N4-Au和g-C3N4-Au-Pt/PtO 位于38.44°出现了Au纳米颗粒的(111)晶面的衍射峰，这说明Au 纳米颗粒结晶性良好。然而没有出现关于Pt/PtO的衍射峰，这是由于PtO的非晶态和较少的金属Pt。
如图2(a)所示为g-C3N4-Au和g-C3N4-Au-Pt/PtO的Au 4f电子的XPS图谱，g-C3N4-Au和g-C3N4-Au-Pt/PtO的Au 4f7/2/Au 4f5/2结合能峰位如图所示，这是归因于Au的存在，与XRD结果一致。图2 (b)所示为Pt 4f电子的XPS图谱，结合能峰位如图所示，证明了 Pt以Pt0和Pt2+的形式存在。
如图3所示为g-C3N4、g-C3N4-Au、g-C3N4-Au-Pt/PtO的DRS 图谱。由于Au的等离子体共振效应，g-C3N4-Au与g-C3N4-Au-Pt/PtO 在500-800nm光谱范围内有稳定的吸收，而g-C3N4-Au-Pt/PtO对可见光谱至近红外有进一步的吸收增强，这是归因于金属Pt对光子的多重散射作用。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。
Claims (10)
1.一种Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，其特征在于：该方法包括如下步骤：首先通过高温煅烧的方法制得g-C3N4，然后将Au纳米颗粒利用光沉积还原的方法负载在g-C3N4的表面制得g-C3N4-Au，之后将Pt/PtO纳米颗粒利用光沉积还原的方法负载在g-C3N4-Au的表面制得。
2.根据权利要求1所述的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，其特征在于：该方法包括如下步骤：
(1)制备g-C3N4：
取尿素均匀装入坩埚中，在马弗炉中煅烧后自然降至室温，获得明黄色g-C3N4粉末；
(2)制备g-C3N4-Au：
将g-C3N4溶于去离子水和甲醇的混合溶剂中，持续超声30分钟；然后将四氯金酸的乙醇溶液滴入上述溶液中，在密封光反应器中倒入上述混合溶液，在连续搅拌混合溶液的过程中注入5分钟的高纯度N2去除溶解O2；用氙灯作为模拟太阳光光源照射，整个光沉积过程持续注入N2；随后用大量去离子水抽滤清洗光催化剂，并将其干燥，得到样品g-C3N4-Au；
(3)制备g-C3N4-Au-Pt/PtO：
将g-C3N4-Au溶于去离子水和甲醇的混合溶剂中，持续超声30分钟；然后将氯铂酸的乙醇溶液滴入上述溶液中，之后进行与上述(2)同样的步骤，得到样品g-C3N4-Au-Pt/PtO。
3.根据权利要求1所述的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，其特征在于：所述步骤(1)中尿素的用量为10g，所述煅烧的温度为500℃，煅烧时间4h，升温速率为10℃/min。
4.根据权利要求1所述的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，其特征在于：所述氙灯为300W，照射时间为30min。
5.根据权利要求1所述的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，其特征在于：所述甲醇的纯度≥99.5％，g-C3N4、去离子水和甲醇的质量比为1:250:40，g-C3N4混合溶剂的浓度为0.036M；g-C3N4-Au、去离子水和甲醇的质量比为1:250:40，g-C3N4-Au混合溶剂的浓度为0.0115M。
6.根据权利要求1所述的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，其特征在于：所述步骤(2)中Au相对于g-C3N4的质量百分比为0.3％-1.0％。
7.根据权利要求1所述的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，其特征在于：所述步骤(3)中Pt相对于g-C3N4的质量百分比为0.3％-1.0％。
8.根据权利要求1所述的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂的制备方法，其特征在于：所述四氯金酸的乙醇溶液的浓度为0.1M，氯铂酸的乙醇溶液的浓度为0.1M。
9.一种根据权利要求1-8任一项所述的制备方法制备得到的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂。
10.一种根据权利要求1-8任一项所述的制备方法制备得到的Au-Pt/PtO三元助催化剂痕量负载g-C3N4光催化剂在光催化水分解产氢上的应用。
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Non-Patent Citations (2)
| Title |
|---|
| JING JIANG.ETAL: "Au/PtO nanoparticle-modified g-C3N4 for plasmon-enhanced photocatalytic hydrogen evolution under visible light", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| SHIJING LIANGA.ETAL,: "Au and Pt co-loaded g-C3N4 nanosheets for enhanced photocatalytichydrogen production under visible light irradiation", 《APPLIED SURFACE SCIENCE》 * |
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