Biomass-derived fatty acids are promising candidates for the production of linear α-olefins (LAOs). Under irradiation, they can be facilely transformed into alkyl radicals over heterogeneous photocatalysts. However, the subsequent dehydrogenation of generated radical intermediates to produce valuable LAOs remains kinetically challenging. Here we demonstrate that CO decoration on Pd nanoparticles can promote LAO production from fatty acids by significantly lowering the energy barrier for alkyl radical intermediate dehydrogenation. 1-Undecene can be obtained from lauric acid in a yield of 46% over a Pd/TiO₂ photocatalyst. Polymerization of the synthesized 1-undecene and subsequent mechanical tests clarify its potential to be used as a renewable comonomer. Our research puts forward an efficient protocol to control the conversion of radical intermediates over heterogeneous catalytic sites for biomass upgrading.

中文翻译：

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在一氧化碳修饰的钯位点上增强自由基脱氢，用于从生物质衍生的脂肪酸中线性生产 α-烯烃


生物质衍生脂肪酸是生产线性 α-烯烃 （LAO） 的有前途的候选者。在辐照下，它们可以很容易地在非均相光催化剂上转化为烷基自由基。然而，随后对生成的自由基中间体进行脱氢以产生有价值的 LAO 在动力学上仍然具有挑战性。在这里，我们证明了 Pd 纳米颗粒上的 CO 修饰可以通过显着降低烷基自由基中间体脱氢的能垒来促进脂肪酸产生 LAO。1-十一烯可从月桂酸获得，比 Pd/TiO₂ 光催化剂收率为 46%。合成的 1-十一烯的聚合和随后的机械测试阐明了其用作可再生共聚单体的潜力。我们的研究提出了一种有效的方案来控制自由基中间体在多相催化位点上的转化，以实现生物质升级。