The exploration of highly efficient materials for the degradation of chemical warfare agents has been a longstanding task for preventing human exposure. Herein, we report a series of metal−organic frameworks (MOFs) M-TCPP-La based on metallo-tetra(4-carboxyphenyl)porphyrin and La III , which were applied to selectively oxidize 2-chloroethyl ethyl sulfide (CEES, a sulfur mustard simulant) as heterogeneous photocatalysts. After irradiation from a commercial blue light-emitting diode (LED), both superoxide ion and singlet oxygen were generated by M-TCPP-La and involved in selective oxidization of CEES to 2-chloroethyl ethyl sulfoxide (CEESO). Notably, a very short half lifetime (2.5 min) was achieved using Fe-TCPP-La as the photocatalyst. In comparison to currently utilizing singlet oxygen and hydrogen peroxide as oxidizing agents, this work employing both singlet oxygen and superoxide ion represents a new and effective strategy of detoxification of mustard gas.

Water oxidation to molecular oxygen is indispensable but a challenge for splitting H 2 O. In this work, a series of Cobased metal−organic cages (MOCs) for photoinduced water oxidation were prepared. MOC-1 with both bis(μ-oxo) bridged dicobalt and Co−O (O from H 2 O) displays catalytic activity with an initial oxygen evolution rate of 80.4 mmol/g/h and a TOF of 7.49 × 10 −3 s −1 in 10 min. In contrast, MOC-2 containing only Co−O (O from H 2 O) in the structure results in a lower oxygen evolution rate (40.8 mmol/g/h, 4.78 × 10 −3 s −1 ), while the amount of oxygen evolved from the solution of MOC-4 without both active sites is undetectable. Isotope experiments with or without H 2 18 O as the reactant successfully demonstrate that the molecular oxygen was produced from water oxidation. Photophysical and electrochemical studies reveal that photoinduced water oxidation initializes via electron transfer from the excited [Ru(bpy) 3 ] 2+ * to Na 2 S 2 O 8 , and then, the cobalt active sites further donate electrons to the oxidized [Ru(bpy) 3 ] 3+ to drive water oxidation. This proof-of-concept study indicates that MOCs can work as potential efficient catalysts for photoinduced water oxidation.

As a creation platform for multifunctional materials, crystalline metal-organic framework (MOF) can integrate different chromophores through reticular chemistry to adjust their spatial arrangement and intermolecular interaction, in turn achieving the...