CN107973289B - 一种硫掺杂石墨烯催化材料及其制备方法 - Google Patents
一种硫掺杂石墨烯催化材料及其制备方法 Download PDFInfo
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Abstract
本发明公开了一种硫掺杂石墨烯催化材料及其制备方法,其由如下质量百分比的原料组分通过水热合成法制成:石墨粉0.20~0.85wt%、硝酸钠0.30~0.60wt%、高锰酸钾1.50~2.60wt%、浓硫酸14.00~18.50wt%、过硫酸盐0.01~0.07wt%、双氧水24.00~30.00wt%,余量为水,其中硫原子以边缘负载的单一形态负载于由碳六元环组成石墨烯结构中。本发明可满足材料在经济成本及机理研究方面的多方位需求,无论在科学研究还是催化产业应用方面均具有广阔前景。
Description
技术领域
本发明属于石墨烯催化剂技术领域,具体涉及一种硫掺杂石墨烯催化材料及其制备方法。
背景技术
2004年,石墨烯材料成功制备以来,因其具有大比表面积、高机械强度与柔韧性、强导电能力等特性成为电极材料的主要基体之一。石墨烯材料的特殊结构,使其既有金属材料的特性(消失的费米面)又有半导体材料的特性(零能隙)。目前,以石墨烯为基体的催化材料已经应用于光催化、电催化、化学催化等领域。然而,由于石墨烯材料的非先天性能带间隙,导致其存在易堆叠,易导致负载颗粒团聚与边缘负载等缺陷。
杂原子掺杂石墨烯催化材料能够改善现有石墨烯材料的电磁、物理化学、光学、结构及催化特性。就硫掺杂位置而言,其掺杂形态可以区分为边缘负载硫、表面吸附硫及片层连接硫。其中边缘负载是硫原子或硫氧基团位于石墨烯结构的边缘,取代一个碳原子和两个碳原子相连进行sp2杂化,由于C-S()和C-C()键的键长相差较大,导致掺杂硫原子与碳原子所处平面产生约的高度差,形成非平面结构的杂化。另外,当硫原子吸附于石墨烯材料表面,与两个碳原子相连,可以形成表面吸附型掺杂。硫原子可以分别与石墨烯材料边缘碳原子相连,形成八元环结构,成为两层石墨烯结构的连接桥梁。现阶段进行硫原子的石墨烯掺杂研究中,无法有效控制单一形态的硫掺杂,掺杂材料多以边缘负载硫、表面吸附硫及片层连接硫的复合形态而存在,导致对于各形态掺杂硫的催化活性及功能无法进行区分。
发明内容
本发明的目的在于克服现有技术缺陷,提供一种硫掺杂石墨烯催化材料及其制备方法。
本发明的另一目的在于提供上述硫掺杂石墨烯催化材料的制备方法。
本发明的技术方案如下:
一种硫掺杂石墨烯催化材料,由如下质量百分比的原料组分通过水热合成法制成:石墨粉0.20~0.85wt%、硝酸钠0.30~0.60wt%、高锰酸钾1.50~2.60wt%、浓硫酸14.00~18.50wt%、过硫酸盐0.01~0.07wt%、双氧水24.00~30.00wt%,余量为水,其中硫原子以边缘负载的单一形态负载于由碳六元环组成石墨烯结构中。
在本发明的一个优选实施方案中,由如下质量百分比的原料组分通过水热合成法制成:石墨粉0.25~0.84wt%、硝酸钠0.30~0.55wt%、高锰酸钾1.51~2.55wt%、浓硫酸14.22~18.21wt%、过硫酸盐0.01~0.05wt%、双氧水24.38~29.96wt%,余量为水。
进一步优选的,所述过硫酸盐为过一硫酸钠或过二硫酸钠和过硫酸铵。
一种上述硫掺杂石墨烯催化材料的制备方法,包括如下步骤:
(1)称取各原料组分;
(2)将浓硫酸、石墨粉、硝酸钠和水溶液置于0~5℃的冰浴中充分混合溶解后,缓慢加入高锰酸钾,恒温反应0.5~2h,得混合溶液;
本发明的有益效果是:
(1)本发明的硫掺杂石墨烯催化材料的制备方法简单易行,制备原料价廉易得,在适当的反应条件下调控硫原子的负载量与负载形态,规避硫的复合形态掺杂带来的多形态硫相互影响、各自功能与作用混杂不清的问题,为充分揭示各形态掺杂硫的功能及作用原理提供了重要技术手段。
(2)本发明的硫掺杂石墨烯催化材料在常温常压条件下,可单独或与其他半导体材料、贵金属材料复合使用,具有良好的光催化、电催化及化学催化活性。
(3)本发明可满足材料在经济成本及机理研究方面的多方位需求,无论在科学研究还是催化产业应用方面均具有广阔前景。
附图说明
图1为本发明实施例1硫掺杂石墨烯催化材料/Pt/TiO2复合材料的穿透式电子显微镜图。
图2为本发明实施例1硫掺杂石墨烯/Pt/TiO2复合材料的电催化氧化扑热息痛效率图。
图3为本发明实施例1的硫掺杂石墨烯材料的化学催化氧化染料效率图。
具体实施方式
以下通过具体实施方式结合附图对本发明的技术方案进行进一步的说明和描述。
实施例1
本发明的反应设计路径如下所示:
在设计反应过程中,过二硫酸钠经过热活化后产生硫酸根自由基,产生的活性基团随后与石墨烯表面羧酸基团反应,形成石墨型或吡啶型掺杂的碳结构,而后进行脱羰作用形成稳定的边缘负载结构。此外,硫掺杂结构还可以与其他含氧官能基团反应造成氧化石墨的还原,并连接于石墨烯结构的边缘,拉大石墨烯结构的层与层间隙,抑制石墨烯的π-π堆积,从而得到更为平滑的单层石墨烯结构。具体包括如下步骤:
(1)称取各原料组分:石墨粉0.25~0.84wt%、硝酸钠0.30~0.55wt%、高锰酸钾1.51~2.55wt%、浓硫酸14.22~18.21wt%、过硫酸盐0.01~0.05wt%、双氧水24.38~29.96wt%,余量为水,过硫酸盐为过一硫酸钠或过二硫酸钠和过硫酸铵;
(2)将浓硫酸、石墨粉、硝酸钠和水溶液置于0~5℃的冰浴中充分混合溶解后,缓慢加入高锰酸钾,恒温反应0.5~2h,得混合溶液;
硫掺杂石墨烯/Pt/TiO2复合材料电催化活性测试:
硫掺杂石墨烯/Pt/TiO2复合材料制备:将上述硫掺杂石墨烯催化材料与氯铂酸溶液、TiO2(P25)在超声条件下充分混匀,室温下缓慢加入硼氢化钠溶液进行Pt的还原负载,所得的粉末经离心过滤收集,在60℃条件下烘干备用。
电催化氧化实验是在一个开放的圆柱形250毫升玻璃容器中进行的,将硫掺杂石墨烯/Pt/TiO2复合材料粘附在1.5cm×1.5cm的碳布上作为阳极,以铜片(1.5cm×1.5cm)作为阴极,两个电极之间的距离设置为1厘米。在室温下,将200ppm的扑热息痛溶液作为目标污染物。在电解过程中,磁搅拌器连续不断地搅动溶液,实验电流由p12阳极极化装置(OuYa中兴技术)进行控制。
硫掺杂石墨烯/Pt/TiO2复合材料的微观形态如图1所示。硫掺杂石墨烯材料电催化活性测试结果如图2所示,由图2可以看出,在一定范围内增加硫掺杂量可以提高扑热息痛降解的催化效率,但当过量的硫原子加入石墨烯框架时,这种促进效应就会减弱。研究显示,当硫的掺杂量从0At%增加到0.027At%时,扑热息痛在60min的去除率为90%,进一步提升硫的掺杂量至0.044%时,扑热息痛在60min的去除率为83%。这一现象是由于硫原子的掺杂在石墨烯边缘产生了大量的活性位点,但是过量的硫掺杂会影响共价石墨烯电子系统的电荷平衡,并干扰电荷再分配。
上述硫掺杂石墨烯材料化学催化活性测试:
化学催化氧化实验将200mL浓度为10ppm的RBk5染料溶液置于烧杯内,以一定的比例添加氧化剂过硫酸氢钾,再迅速投入一定量的硫掺杂石墨烯材料,按每5min一次的取样间隔进行取样,每次取样体积约2.5mL,样品采用0.22μm一次性针头滤器过滤。再利用紫外-可见分光光度计(UV-VIS,U-3900,日本Hitachi公司)于600nm处对水样中残留的RBk5染料的浓度进行测量,平均每组实验的时间跨度为30min左右。
上述硫掺杂石墨烯材料化学催化活性测试结果如图3所示,由图3可以看出,硫掺杂石墨烯材料对于过硫酸氢钾有非常良好的催化活性,在不同硫掺杂比例条件下,材料对于染料的催化降解效率在40min内均可以达到95%以上。其中硫掺杂比为0.57At%时,体系有较高的降解效率,仅25min就可将染料全部去除。随着硫掺杂比的增加,降解效率缓慢降低,当掺杂比为1.23At%、2.48At%、4.59At%时,反应到40min的去除率分别为97.50%、96.80%、95.83%。
以上所述,仅为本发明的较佳实施例而已,故不能依此限定本发明实施的范围,即依本发明专利范围及说明书内容所作的等效变化与修饰,皆应仍属本发明涵盖的范围内。
Claims (3)
1.一种硫掺杂石墨烯催化材料,其特征在于:由如下质量百分比的原料组分通过水热合成法制成:石墨粉0.20 ~0.85wt%、硝酸钠0.30~0.60 wt%、高锰酸钾1.50~2.60 wt%、浓硫酸14.00~18.50 wt%、过硫酸盐0.01~0.07wt%、双氧水24.00~30.00wt%,余量为水,其中硫原子以边缘负载的单一形态负载于由碳六元环组成石墨烯结构中, 所述过硫酸盐为过一硫酸钠或过二硫酸钠和过硫酸铵;
其制备方法包括如下步骤:
(1)称取各原料组分;
(2)将浓硫酸、石墨粉、硝酸钠和水溶液置于0~5℃的冰浴中充分混合溶解后,缓慢加入高锰酸钾,恒温反应0.5~2 h,得混合溶液;
(3)将上述混合溶液置于90~100℃的油浴中,恒温反应0.5~1h后,再加入双氧水去除氧化剂残余;
(4)将步骤(3)所得的物料在室温下搅拌均匀,缓慢加入过硫酸盐,充分混合后,封入高压反应釜中进行反应,反应时间为1.3~6.2 h,反应温度为90~130℃,即得所述硫掺杂石墨烯催化材料。
2.如权利要求1所述的一种硫掺杂石墨烯催化材料,其特征在于:由如下质量百分比的原料组分通过水热合成法制成:石墨粉0.25 ~0.84wt%、硝酸钠0.30~0.55 wt%、高锰酸钾1.51~2.55 wt%、浓硫酸14.22~18.21 wt%、过硫酸盐0.01~0.05wt%、双氧水24.38~29.96wt%,余量为水。
3.如权利要求1所述的一种硫掺杂石墨烯催化材料,其特征在于:所述步骤(4)中的反应时间为1.5~6 h,反应温度为100~120℃。
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