Regioselectivity is a key point in hydroformylation reactions and its control is still a challenge in heterogeneous catalysis. Here, we demonstrate that regioselectivity in heterogeneous hydroformylation can be steered by a surface microenvironment around Rh clusters, which are surrounded by K species and confined within silicate-1 zeolites. The K species create a steric hindrance microenvironment on the surfaces of Rh clusters and tune the electronic properties of Rh species, mimicking the Rh–phosphine molecular complex. This microenvironment benefits the linear adsorption of olefins, realizing 83% regioselectivity to linear butyraldehyde with TOF as high as 7328 h⁻¹ in propylene hydroformylation. Other K species which reduce acidic sites can also inhibit the isomerization of long-chain olefins, thus boosting regioselectivity. The confinement structure can stabilize the K_x^{^}Rh clusters to enhance the catalyst lifetime. This work provides an alternative route for developing selective heterogeneous catalysts through steering the catalyst surface microenvironment.

区域选择性是加氢甲酰化反应的关键，其控制仍然是多相催化的挑战。在这里，我们证明了异质加氢甲酰化反应中的区域选择性可以通过Rh簇周围的表面微环境来控制，Rh簇周围被K物种包围，并被限制在硅酸盐1沸石中。K物种在Rh团簇的表面上形成了位阻微环境，并调节了Rh物种的电子特性，模仿了Rh-膦分子复合物。这种微环境有利于烯烃的线性吸附，TOF高达7328 h ^-1，实现了对线性丁醛83％的区域选择性在丙烯加氢甲酰化中。减少酸性位点的其他K种类也可以抑制长链烯烃的异构化，从而提高区域选择性。该限制结构可以稳定K _x ^{^} Rh簇，以提高催化剂寿命。这项工作为通过控制催化剂表面的微环境开发选择性多相催化剂提供了另一种途径。