可控碳改性Pd/TiO<sub>2</sub>用于直接合成双氧水:非均相界面对催化性能的影响

引用本文: 严伟, 孙睿, 李蒙, 李力成, 杨祝红, 花泽林, 陆小华, 刘畅. 可控碳改性Pd/TiO₂用于直接合成双氧水:非均相界面对催化性能的影响[J]. 催化学报, 2020, 41(2): 312-321. doi: S1872-2067(19)63412-1 shu

Citation: Wei Yan, Rui Sun, Meng Li, Licheng Li, Zhuhong Yang, Zelin Hua, Xiaohua Lu, Chang Liu. Heterogeneous interfacial engineering of Pd/TiO₂ with controllable carbon content for improved direct synthesis efficiency of H₂O₂[J]. Chinese Journal of Catalysis, 2020, 41(2): 312-321. doi: S1872-2067(19)63412-1 shu

可控碳改性Pd/TiO₂用于直接合成双氧水:非均相界面对催化性能的影响

严伟 ^a, ,
孙睿 ^a, ,
李蒙 ^a, ,
李力成 ^b, ,
杨祝红 ^a, ,
花泽林 ^b, ,
陆小华 ^a, ,
刘畅 ^a,

a 南京工业大学化学工程学院, 材料化学工程国家重点实验室, 江苏南京 210009;
b 南京林业大学化学工程学院, 木质纤维素功能材料创新研究中心, 江苏南京 210037
基金项目:
国家自然科学基金（21878143，21476106，21838004）；海外及港澳学者合作研究基金（21729601）；材料化学工程国家重点实验室基金（ZK201702）；江苏省高等学校重点学科建设（PAPD）.

摘要: 双氧水（H₂O₂）是一种重要的绿色氧化剂，广泛应用于纺织、医疗、废水处理、军事等重要领域.目前，H₂O₂的工业生产以蒽醌法为主，该法设备投资大、运行成本高，同时工艺涉及大量的有机溶液，活性中间体蒽醌也会发生缓慢降解，产生有毒副产物.与蒽醌法相比，通过负载型贵金属催化剂催化H₂与O₂反应直接合成H₂O₂，过程绿色环保且生产工艺简单，引起了各界广泛关注.然而，从热力学上分析，H₂和O₂更容易反应生成H₂O，H₂O₂只是该反应的中间产物，会继续发生加氢和直接分解反应生成H₂O，导致H₂和O₂的低效利用，开发高H₂O₂选择性且高反应效率的催化剂已成为氢氧直接合成H₂O₂研究的重点与难点.目前大部分研究策略旨在通过调控或影响反应中心结构、价态来抑制H₂O₂的副反应，进而提升H₂O₂的选择性和反应效率；尽管已取得了良好的进展，但仍需发展新的调控策略来满足工业应用的要求.
本课题组前期研究表明，促使H₂O₂从催化剂上脱附可以有效地提升H₂O₂的选择性和产率.相比于针对反应中心的调控，不稳定的H₂O₂从催化剂上快速脱附同样起到抑制H₂O₂参与副反应的作用.为此，本文提出一种炭量可控的非均一界面改性方法，以常规的Pd/TiO₂作为研究对象，借助各种结构表征，发现炭物种在TiO₂表面呈非均一分散状态，而且改性对于催化剂的几何结构影响较小；另外，催化剂表面的疏水性会随着碳含量的增加而增加，导致其与H₂O₂间的吸附能相应变小.反应结果显示，表面非均一的炭化改性技术可以显著提升Pd/TiO₂催化剂的H₂O₂选择性和产率.通过构效关系分析，可知这种改性技术可以保持Pd颗粒与TiO₂间相互作用的同时，还可以促进H₂O₂的快速脱附，进而提升改性Pd/TiO₂催化剂的H₂O₂直接合成效率.该改性方法简单、易控，可拓展应用到其他类型催化剂的H₂O₂直接合成性能调控与改进.

关键词:

English

Heterogeneous interfacial engineering of Pd/TiO₂ with controllable carbon content for improved direct synthesis efficiency of H₂O₂

a State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 210009, Jiangsu, China;
b College of Chemical Engineering, Innovation Research Center of Lignocellulosic Functional Materials, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
Received Date: 28 March 2019
Revised Date: 22 May 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21878143, 21476106, 21838004), Joint Re-search Fund for Overseas Chinese Scholars and Scholars in Hong Kong and Macao Young Scholars (21729601), the fund of State Key Laboratory of Materials-Oriented Chemical Engineering (ZK201702), and the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

Abstract: Series of heterogeneous interfacial engineered TiO₂ (C-TiO₂) with controllable carbon content were facilely synthesized by incipient-wet impregnation using glucose and subsequent thermal carbonization. The obtained C-TiO₂ were used as catalytic supports to load Pd nanoparticles for H₂O₂ direct synthesis from H₂ and O₂. The as-prepared samples were systematically studied by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), air isothermal microcalorimeter, temperature-programmed reduction of H₂ (H₂-TPR), and so on. The catalytic results showed that H₂O₂ productivity and H₂O₂ selectivity of Pd/C-TiO₂ firstly rose with increasing carbon content and then declined. Pd/C-TiO₂ catalyst with 1.89 wt% of carbon content showed the best catalytic performance that had 61.2% of selectivity and 2192 mmol H₂O₂/g_Pd/h of productivity, which were significantly better than those of pristine Pd/TiO₂ (45.2% and 1827 mmol H₂O₂/g_Pd/h). Various characterization results displayed that the carbon species were heterogeneously dispersed on TiO₂ surface. Moreover, no obvious geometric transformation in supports and Pd nanoparticles were observed among different catalysts. The superficial hydrophobicity of Pd/C-TiO₂ was gradually promoted with increasing carbon content, which led to the corresponding decrease in adsorption energy of H₂O₂ with catalysts. According to structure-performance relationship analyses, the heterogeneous interfacial engineering of carbon could maintain the interaction of Pd nanoparticles with TiO₂ and simultaneously accelerate the H₂O₂ desorption. Both factors further determined the excellent H₂O₂ direct synthesis performance of Pd/C-TiO₂.

Key words:

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可控碳改性Pd/TiO₂用于直接合成双氧水:非均相界面对催化性能的影响

English

Heterogeneous interfacial engineering of Pd/TiO₂ with controllable carbon content for improved direct synthesis efficiency of H₂O₂

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可控碳改性Pd/TiO2用于直接合成双氧水:非均相界面对催化性能的影响

English

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可控碳改性Pd/TiO₂用于直接合成双氧水:非均相界面对催化性能的影响

Heterogeneous interfacial engineering of Pd/TiO₂ with controllable carbon content for improved direct synthesis efficiency of H₂O₂

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