Achieving the regioselective hydroformylation of linear α-olefins to linear aldehydes using solid catalysts with regioselectivities comparable to the corresponding homogeneous process is a great challenge in the chemical industry. Despite the tremendous efforts devoted to this research topic, most of the reported heterogeneous metal catalysts still give considerably lower regioselectivities than well-established homogeneous metal catalysts. Here we show the design of efficient Rh-zeolite catalysts, in which subnanometre Rh clusters are selectively confined in the sinusoidal ten-membered-ring channels of MFI zeolite, for the hydroformylation of long-chain linear α-olefins (C₆–C₁₂) into linear aldehydes with very high linear-to-branched aldehyde ratios (up to 400). The exceptional catalytic performances result from the involvement of the MFI zeolite framework as a rigid solid ligand that accommodates subnanometre Rh clusters in the sinusoidal channels of the MFI zeolite.

使用固体催化剂实现直链α-烯烃区域选择性加氢甲酰化为直链醛，其区域选择性与相应的均相工艺相当，是化学工业中的巨大挑战。尽管为这一研究课题付出了巨大的努力，但大多数报道的多相金属催化剂的区域选择性仍然比成熟的均相金属催化剂低得多。在这里，我们展示了高效 Rh 沸石催化剂的设计，其中亚纳米 Rh 簇选择性地限制在 MFI 沸石的正弦十元环通道中，用于长链线性 α-烯烃（C ₆ –C ₁₂）转化为具有非常高的直链与支链醛比率（高达 400）的直链醛。卓越的催化性能源于 MFI 沸石框架作为刚性固体配体的参与，可在 MFI 沸石的正弦通道中容纳亚纳米 Rh 簇。