Hydroesterification of olefins with alcohols and CO is an attractive approach to synthesize value-added carboxylic esters. The current manufactures are mainly based on the use of homogeneous catalytic systems, and developing a heterogeneous process enabling cost-effective catalyst separation is of potential interest, particularly for higher olefins. In this contribution, we reported a robust porous organic polymer-supported palladium catalyst that exhibited excellent hydroesterification performance approaching that of the homogeneous counterpart. In addition, the catalyst shows remarkable adaptability for a broad range of substrates (both olefins and alcohols) and recyclability. The catalysts are thoroughly characterized by a spectrum of characterization techniques including N₂ sorption, SEM, TEM, HAADF-STEM coupled with elemental mapping, FTIR with CO probe, XPS, and solid-state ³¹P NMR. Based on these, the good catalytic performance can be attributed to the high surface area, highly dispersed active metal species, and the strong coordination bonds between palladium center and the exposed phosphorous ligands in Porous organic polymer (POPs) frame. The ICP-OES and hot filtration test further indicate that the reaction truly proceeds in a heterogeneous manner, thus exhibiting great potential for industrial applications.

烯烃与醇和CO的加氢酯化是合成增值羧酸酯的一种有吸引力的方法。当前的制造商主要基于均相催化系统的使用，开发一种能够实现经济高效的催化剂分离的非均相工艺具有潜在的意义，特别是对于高级烯烃而言。在这一贡献中，我们报道了一种坚固的多孔有机聚合物负载的钯催化剂，该催化剂表现出了优异的加氢酯化性能，接近于同类催化剂。此外，该催化剂对各种底物（烯烃和醇类）均显示出显着的适应性和可回收性。通过包括N ₂在内的多种表征技术对催化剂进行了全面表征吸附，SEM，TEM，HAADF-STEM结合元素图谱，带CO探针的FTIR，XPS和固态³¹ P NMR。基于这些，良好的催化性能可归因于高表面积，高度分散的活性金属种类以及钯中心与多孔有机聚合物（POP）框架中暴露的磷配体之间的强配位键。ICP-OES和热过滤测试进一步表明，反应确实以异质方式进行，因此具有巨大的工业应用潜力。