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Phosphane, PH3—a highly pyrophoric and toxic gas—is frequently contaminated with H2 and P2H4, which makes its handling even more dangerous. The inexpensive metal–organic framework (MOF) magnesium formate, α‐[Mg(O2CH)2], can adsorb up to 10 wt % of PH3. The PH3‐loaded MOF, PH3@α‐[Mg(O2CH)2], is a non‐pyrophoric, recoverable material that even allows brief handling in air, thereby minimizing the hazards associated with the handling and transport of phosphane. α‐[Mg(O2CH)2] further plays a critical role in purifying PH3 from H2 and P2H4: at 25 °C, H2 passes through the MOF channels without adsorption, whereas PH3 adsorbs readily and only slowly desorbs under a flow of inert gas (complete desorption time≈6 h). Diphosphane, P2H4, is strongly adsorbed and trapped within the MOF for at least 4 months. P2H4@α‐[Mg(O2CH)2] itself is not pyrophoric and is air‐ and light‐stable at room temperature. [ABSTRACT FROM AUTHOR]

Phosphane, PH 3 -a highly pyrophoric and toxic gas-is frequently contaminated with H 2 and P 2 H 4 , which makes its handling even more dangerous. The inexpensive metal-organic framework (MOF) magnesium formate, α-[Mg(O 2 CH) 2 ], can adsorb up to 10 wt % of PH 3 . The PH 3 -loaded MOF, PH 3 @α-[Mg(O 2 CH) 2 ], is a non-pyrophoric, recoverable material that even allows brief handling in air, thereby minimizing the hazards associated with the handling and transport of phosphane. α-[Mg(O 2 CH) 2 ] further plays a critical role in purifying PH 3 from H 2 and P 2 H 4 : at 25 °C, H 2 passes through the MOF channels without adsorption, whereas PH 3 adsorbs readily and only slowly desorbs under a flow of inert gas (complete desorption time≈6 h). Diphosphane, P 2 H 4 , is strongly adsorbed and trapped within the MOF for at least 4 months. P 2 H 4 @α-[Mg(O 2 CH) 2 ] itself is not pyrophoric and is air- and light-stable at room temperature., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)