Tailoring free spaces around catalytic sites in a controlled way is highly attractive for improving the accessibility of reactants to catalytic sites in heterogeneous catalysis. In this paper, the free space around latent acid site (-SH) in the mesoporous shell of hollow polymeric nano-bowl was constructed through the hydrolysis of attached thiuronium/Co(OH)₂ complex and the formation/removal of Co(OH)₂ porogen in the shell. After the oxidation of –SH moiety by H₂O₂, the as-obtained hollow mesoporous bowl-like polymeric solid acid could be conveniently functionalized by 9-amino-(9-deoxy)cinchonidine (CDNH₂) via acid-base reaction to afford multifunctional nano-bowl Poly(St/SO₃H) HMOBs with 0.34 mmol g^-1 of loaded CDNH₂ and 1.77 mmol g^-1 of acid capacity. In heterogeneous acetal hydrolysis/asymmetric aldol tandem reaction, Poly(St/SO₃H-CDNH₂) HMOBs displayed moderate to excellent catalytic performances (90–95% yields, anti/syn = 81/19–95/5 and 74–97%ee anti) for the starting benzaldehyde methyl acetals bearing electron-withdrawing substituents (R = NO₂, Cl) at o, m and p-positions.

以受控的方式在催化位点附近自由空间对于提高反应物在非均相催化中对催化位点的可及性非常有吸引力。本文通过附着的硫脲鎓/ Co（OH）₂络合物的水解和Co /（OH）的形成/去除，构建了空心聚合物纳米碗中孔壳中潜酸位点（-SH）周围的自由空间。₂致孔剂在壳中。在H ₂ O ₂氧化–SH部分后，可以通过9-氨基-（9-脱氧）辛可尼定（CDNH ₂）通过酸碱反应将所得的空心中孔碗状聚合固体酸方便地官能化为提供多功能纳米碗Poly（St / SO ₃H）具有0.34mmol g ^-1的负载的CDNH ₂和1.77mmol g ^-1的酸容量的HMOB 。在非均相缩醛水解/不对称醛醇串联反应中，Poly（St / SO ₃ H-CDNH ₂）HMOB显示出中等至出色的催化性能（90-95％的收率，anti / syn  = 81 / 19-95 / 5和74-97起始苯甲醛甲基乙缩醛在o，m和p位带有吸电子取代基（R = NO ₂，Cl）的％ee anti）。