Regulating the Electronic Structure of Pd Nanoparticles on NH3‐pretreated Nano‐flake TiO2 for Efficient Hydrogenation of Nitrile Butadiene Rubber

IF 3.8 3区化学 Q2 CHEMISTRY, PHYSICAL

ChemCatChem Pub Date : 2024-08-31 DOI:10.1002/cctc.202401226

Shidong Wang, Benwei Fan, Bingqing Ge, Hongwei Zhang, Cejun Hu, Qinyan Cui, Xiaojun Bao, Pei Yuan

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引用次数: 0

Abstract

The heterogeneous selective hydrogenation of nitrile butadiene rubber (NBR) is an efficient method to generate high value‐added hydrogenated NBR. Nevertheless, the inherent large molecular size and high spatial hindrance of polymers lead to poor activity and metal loss. Herein, we report a simple support ammonia pretreatment strategy for the synthesis of efficient N‐doped Pd catalyst and applied for the NBR hydrogenation. The results reveal that N doping enhances electrons transfer from the support to Pd more effectively than oxygen‐rich vacancy carrier, thereby substantially enhancing the electron cloud density and stability of the Pd sites. The formation of more electron‐rich Pd sites not only significantly enhances the adsorption‐activation ability of C=C and H2, but also lowers the apparent activation energy of the reaction. As a result, the Pd/N‐TiO2‐R demonstrates best activity with a hydrogenation degree (HD) of 98% and a TOF value of 335 h‐1, significantly higher than that of Pd/TiO2‐R (HD=83%, 282 h‐1) and Pd/TiO2 (HD=74%, 204 h‐1). This strategy will provide new inspiration to improve the activity and stability of Pd/TiO2 catalysts for the hydrogenation of unsaturated polymers.

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调节 NH3 预处理纳米片 TiO2 上钯纳米粒子的电子结构以实现丁腈橡胶的高效氢化

丁腈橡胶（NBR）的异构选择性氢化是生成高附加值氢化丁腈橡胶的有效方法。然而，聚合物固有的大分子尺寸和高空间阻碍会导致活性差和金属损失。在此，我们报告了一种用于合成高效 N 掺杂钯催化剂的简单支撑氨预处理策略，并将其应用于丁腈橡胶氢化。研究结果表明，与富氧空位载流子相比，N掺杂能更有效地促进电子从载体向钯的转移，从而大幅提高钯位的电子云密度和稳定性。更多电子富集钯位点的形成不仅能显著增强 C=C 和 H2 的吸附活化能力，还能降低反应的表观活化能。因此，Pd/N-TiO2-R 表现出最佳活性，氢化度（HD）达 98%，TOF 值为 335 h-1，明显高于 Pd/TiO2-R（HD=83%，282 h-1）和 Pd/TiO2（HD=74%，204 h-1）。这一策略将为提高 Pd/TiO2 催化剂在不饱和聚合物氢化过程中的活性和稳定性提供新的启示。

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来源期刊

ChemCatChem 化学-物理化学

CiteScore

8.10

自引率

4.40%

发文量

511

审稿时长

1.3 months

期刊介绍： With an impact factor of 4.495 (2018), ChemCatChem is one of the premier journals in the field of catalysis. The journal provides primary research papers and critical secondary information on heterogeneous, homogeneous and bio- and nanocatalysis. The journal is well placed to strengthen cross-communication within between these communities. Its authors and readers come from academia, the chemical industry, and government laboratories across the world. It is published on behalf of Chemistry Europe, an association of 16 European chemical societies, and is supported by the German Catalysis Society.