氮掺杂碳负载Sb@PtSb<sub>2</sub>催化剂的制备及其在甘油选择性氧化反应中的应用

引用本文: 杨丽华, 何天衢, 赖楚钧, 陈平, 侯昭胤. 氮掺杂碳负载Sb@PtSb₂催化剂的制备及其在甘油选择性氧化反应中的应用[J]. 催化学报, 2020, 41(3): 494-502. doi: S1872-2067(19)63476-5 shu

Citation: Lihua Yang, Tianqu He, Chujun Lai, Ping Chen, Zhaoyin Hou. Selective oxidation of glycerol with oxygen in base-free solution over N-doped-carbon-supported Sb@PtSb₂ hybrid[J]. Chinese Journal of Catalysis, 2020, 41(3): 494-502. doi: S1872-2067(19)63476-5 shu

氮掺杂碳负载Sb@PtSb₂催化剂的制备及其在甘油选择性氧化反应中的应用

a 浙江大学化学系生物质化工教育部重点实验室, 浙江杭州 310028;
b 浙江大学化学系化学前瞻技术研究中心, 浙江杭州 310028
基金项目:
国家自然科学基金（21773206，21473155）；浙江省自然科学基金（L12B03001）.

摘要: 甘油是生物柴油生产过程中生成的副产物，随着生物柴油产量的快速增长，甘油的量也迅速增加.据估计，到2020年甘油的产量将比需求量高出6倍.因此，将过剩的甘油转化为其它更有价值的化学品具有重要意义.
在已经发表的文献中，各种碳材料负载的Pt催化剂被广泛应用于液相中甘油的选择性氧化.但是，由于Pt纳米颗粒与碳载体之间相互作用较弱，因此Pt纳米颗粒易团聚和流失，而且Pt的过度氧化和有机羧酸的强吸附也导致Pt催化剂失活.最近的研究表明，采用含氮的碳载体可以增强Pt与载体间的相互作用，这种载体还有可能将电子转移给Pt，从而有效提高Pt的分散度、活性和稳定性.与此同时，引入其它金属如Co，Cu，Bi，Sb等与Pt形成合金也能有效改善催化剂的活性和稳定性.我们在前期工作中曾经发现多壁碳纳米管（MWCNTs）负载的PtSb合金在甘油氧化反应中具有很高的活性和二羟基丙酮选择性，可以抑制C-C裂解，并提高了催化剂的稳定性.但是在MWCNTs上组装PtSb颗粒的过程繁琐且危险，需要对载体进行氧化（浓硝酸）、嫁接硫醇、浸渍金属、高温还原等，同时MWCNTs的价格也较高.
本文采用简单的热解方法将氮和锑同时引入到碳基载体中，并用此载体制备了具有核壳结构的Sb@PtSb₂/NC催化剂.首先将葡萄糖、三聚氰胺和SbCl₃混合后在氮气中于700℃热解得到含Sb和N的多孔碳载体，再通过浸渍还原法将Pt还原并负载到该载体上即得到具有核壳结构的Sb@PtSb₂/NC催化剂.该催化剂对催化甘油氧化具有较高的活性，同时具有较好的稳定性.氮气吸附表征表明，引入N和Sb都能提高载体的比表面积和孔体积，其中Sb的引入使得催化剂表面形成了多孔结构（SEM表征）.XRD、TEM和EDS表征证明了具有核壳结构的Sb@PtSb₂颗粒在载体表面上的生成.Raman光谱表明N和Sb的引入增加了碳缺陷，有可能带来新的活性位点.O₂-TPD表征表明Sb@PtSb₂/NC对氧的吸附量远高于Pt/NC，这可能归因于PtSb₂合金中Pt-Sb金属间的原子间距增大，有利于氧的吸附和表面扩散，从而显著提高了催化剂活性.XPS表征表明了从N到Pt的电子转移，而这种富含电子的Pt具有更高的活性.将制备的催化剂用于考评催化甘油氧化的活性，发现相比于Pt/NC，Sb@PtSb₂/NC催化剂催化甘油氧化具有显著增加的活性，二羟基丙酮选择性也明显提高，在60℃，0.6MPa O₂气氛下，100mg催化剂与5mL 0.2g/mL甘油水溶液反应3h得到了65.3%的甘油转化率，以及39.2%的二羟基丙酮选择性和51.8%的甘油酸选择性.这可能归因于载体比表面积的增加、更多的碳缺陷，以及PtSb₂合金的形成.使用五次后的催化剂仍保持较高的催化活性，证实了该催化剂具有较好的稳定性.

关键词:

甘油
/ 氧化
/ 无碱溶液
/ Sb@PtSb₂
/ 合金

English

Selective oxidation of glycerol with oxygen in base-free solution over N-doped-carbon-supported Sb@PtSb₂ hybrid

a Key Laboratory of Biomass Chemical Engineering of Ministry of Education, Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China;
b Center of Chemistry for Frontier Technologies, Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China
Received Date: 04 July 2019
Revised Date: 06 August 2019
Fund Project:
This work was financially supported by the National Natural Science Foundation of China (21773206 and 21473155) and Natural Science Foundation of Zhejiang Province (L12B03001).

Abstract: Selective oxidation of glycerol with molecular oxygen in base-free aqueous solutions has become a hot topic, as the rapidly increasing production of biodiesel is creating a surplus of glycerol. In this work, an N-doped-carbon-supported core-shell structured Sb@PtSb₂ hybrid catalyst was prepared via a facile synthesis route, in which a mixture of glucose, melamine, and SbCl₃ (Sb-NC) was pyrolyzed, then impregnated with Pt by immersion in an aqueous solution of H₂PtCl₆, and further treated in hydrogen flow. Characterization of the catalyst products indicated that introducing SbCl₃ can increase the surface area of the binary glucose + melamine pyrolyzed support (NC), and Sb@PtSb₂ hybrids could be formed on the surface of an Sb-NC support during hydrogen treatment at 700℃. It was found that the Sb@PtSb₂/NC catalyst was more active for the selective oxidation of glycerol in a base-free aqueous solution than Sb-free NC-supported Pt (Pt/NC). Further characterization also indicated that the promising performance of Sb@PtSb₂/NC might be attributed to its enhanced oxygen activation.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

氮掺杂碳负载Sb@PtSb₂催化剂的制备及其在甘油选择性氧化反应中的应用

English

Selective oxidation of glycerol with oxygen in base-free solution over N-doped-carbon-supported Sb@PtSb₂ hybrid

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

氮掺杂碳负载Sb@PtSb2催化剂的制备及其在甘油选择性氧化反应中的应用

English

Selective oxidation of glycerol with oxygen in base-free solution over N-doped-carbon-supported Sb@PtSb2 hybrid

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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氮掺杂碳负载Sb@PtSb₂催化剂的制备及其在甘油选择性氧化反应中的应用

Selective oxidation of glycerol with oxygen in base-free solution over N-doped-carbon-supported Sb@PtSb₂ hybrid

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