separation of acetylene and ethylene is an important industrial process because both compounds are essential reagents for a range of chemical products and materials. Current separation approaches include the partial hydrogenation of acetylene into ethylene over a supported Pd catalyst, and the extraction of cracked olefins using an organic solvent; both routes are costly and energy consuming. Adsorption technologies may allow separation, but microporous materials exhibiting highly selective adsorption of C 2 H 2 /C 2 H 4 have not been realized to date. Here, we report the development of tunable microporous enantiopure mixed-

The conjugation of metal–organic frameworks (MOFs) into different multicomponent materials to precisely construct aligned heterostructures is fascinating but elusive owing to the disparate interfacial energy and nucleation kinetics. Herein, a promising lattice‐matching growth strategy is demonstrated for conductive MOF/layered double hydroxide (cMOF/LDH) heteronanotube arrays with highly ordered hierarchical porous structures enabling an ultraefficient oxygen evolution reaction (OER). CoNiFe‐LDH nanowires are used as interior template to engineer an interface by inlaying cMOF and matching two crystal lattice systems, thus conducting a graft growth of cMOF/LDH heterostructures along the LDH nanowire. A class of hierarchical porous cMOF/LDH heteronanotube arrays is produced through continuously regulating the transformation degree. The synergistic effects of the cMOF and LDH components significantly promote the chemical and electronic structures of the heteronanotube arrays and their electroactive surface area. Optimized heteronanotube arrays exhibit extraordinary OER activity with ultralow overpotentials of 216 and 227 mV to deliver current densities of 50 and 100 mA cm−2 with a small Tafel slope of 34.1 mV dec−1, ranking it among the best MOF and non‐noble‐metal‐based catalysts for OER. The robust performance under high current density and vigorous gas bubble conditions enable such hierarchical MOF/LDH heteronanotube arrays as promising materials for practical water electrolysis.

This review provides an overview of crucial roles that MOFs have played in constructing non-noble ORR catalysts.