Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis
Ultrasmall amorphous zirconia nanoparticles catalyse polyolefin hydrogenolysis
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DOI：
10.1038/s41929-023-00910-x
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发表时间：
2023-02
期刊：
影响因子：
37.8
通讯作者：
Shaojiang Chen;A. Tennakoon;Kyung-Eun You;A. L. Paterson;Ryan D. Yappert;S. Alayoglu;Lingzhe Fang;Xun Wu;T. Y. Zhao;Michelle P. Lapak;Mukunth Saravanan;Ryan A. Hackler;Yi-Yu Wang;Long Qi;M. Delferro;Tao Li;Byeongdu Lee;B. Peters;K. Poeppelmeier;S. C. Ammal;C. Bowers;Frédéric A. Perras;Andreas Heyden;A. Sadow;Wenyu Huang
中科院分区：
文献类型：
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作者：
Shaojiang Chen;A. Tennakoon;Kyung-Eun You;A. L. Paterson;Ryan D. Yappert;S. Alayoglu;Lingzhe Fang;Xun Wu;T. Y. Zhao;Michelle P. Lapak;Mukunth Saravanan;Ryan A. Hackler;Yi-Yu Wang;Long Qi;M. Delferro;Tao Li;Byeongdu Lee;B. Peters;K. Poeppelmeier;S. C. Ammal;C. Bowers;Frédéric A. Perras;Andreas Heyden;A. Sadow;Wenyu Huang
碳-碳键断裂反应适用于解构脂肪族烃聚合物并回收塑料废物中的固有能量和碳值，通常由金属纳米颗粒或空气敏感的有机金属催化。用作这些催化剂载体的金属氧化物通常被认为是惰性的。在这里，我们展示了地球上丰富的、不可还原的氧化锆催化聚烯烃的氢解，其活性可与贵金属纳米颗粒相媲美。为了利用这种不寻常的反应性，我们的催化结构将超小的无定形氧化锆纳米粒子定位在两个介孔二氧化硅熔融片晶之间。大分子通过径向介孔从本体转移到高活性氧化锆颗粒，其中链经历选择性氢解裂解成以 C18 为中心的狭窄分布。计算表明，不饱和表面位点的 Zr(O)2 原子模型的 Zr-O 键上的 C-H 键异解作用产生烃基锆，该烃基通过 β-烷基消除而裂解 C-C 键。
Carbon–carbon bond cleavage reactions, adapted to deconstruct aliphatic hydrocarbon polymers and recover the intrinsic energy and carbon value in plastic waste, have typically been catalysed by metal nanoparticles or air-sensitive organometallics. Metal oxides that serve as supports for these catalysts are typically considered to be inert. Here we show that Earth-abundant, non-reducible zirconia catalyses the hydrogenolysis of polyolefins with activity rivalling that of precious metal nanoparticles. To harness this unusual reactivity, our catalytic architecture localizes ultrasmall amorphous zirconia nanoparticles between two fused platelets of mesoporous silica. Macromolecules translocate from bulk through radial mesopores to the highly active zirconia particles, where the chains undergo selective hydrogenolytic cleavage into a narrow, C18-centred distribution. Calculations indicated that C–H bond heterolysis across a Zr–O bond of a Zr(O)2adatom model for unsaturated surface sites gives a zirconium hydrocarbyl, which cleaves a C–C bond via β-alkyl elimination.