Although progress has been made to improve photocatalytic CO2 reduction under visible light (λ>400 nm), the development of photocatalysts that can work under a longer wavelength (λ>600 nm) remains a challenge. Now, a heterogeneous photocatalyst system consisting of a ruthenium complex and a monolayer nickel‐alumina layered double hydroxide (NiAl‐LDH), which act as light‐harvesting and catalytic units for selective photoreduction of CO2 and H2O into CH4 and CO under irradiation with λ>400 nm. By precisely tuning the irradiation wavelength, the selectivity of CH4 can be improved to 70.3 %, and the H2 evolution reaction can be completely suppressed under irradiation with λ>600 nm. The photogenerated electrons matching the energy levels of photosensitizer and m‐NiAl‐LDH only localized at the defect state, providing a driving force of 0.313 eV to overcome the Gibbs free energy barrier of CO2 reduction to CH4 (0.127 eV), rather than that for H2 evolution (0.425 eV).

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Applications for metal-organic frameworks (MOFs) demand their assembly into threedimensional (3D) macroscopic architectures. The capability of sustaining structural integrity with considerable deformation is important to allow a monolithic material to work reliably. Nevertheless, it remains a significant challenge to introduce superplasticity in 3D MOF networks. Here, we report a general procedure for synthesizing 3D superplastic MOF aerogels inspired by the hierarchical architecture of natural corks. The resultant MOFs exhibited excellent superplasticity that can recover fully and rapidly to its original dimension after 50% strain compression and unloading for >2000 cycles. The 3D superplastic architecture is achieved by successively assembling onedimensional (1D) to two-dimensional (2D) and then 3D, in a variety of MOFs with different transition metal active sites (Co-, NiMn-, NiCo-, NiCoMn-) and organic ligands (2-thiophenecarboxylic acid and glutaric acid). Latent applications have been demonstrated for NiMn-MOF aerogels to serve as a new generation of flexible electrocatalysts for hydrogen evolution reaction (HER) from seawater splitting, which requires a low overpotential of 243 mV to achieve a current density of 10 mA⋅cm −2 . Notably, the electrocatalyst remains stable even being deformed, as the overpotential to achieve a current density of 10 mA⋅cm −2 increases slightly to 270, 264, and 258 mV after one-, two-, and threefold, respectively. In great contrast, traditional MOF powder-electrodes demonstrate significant activity decay under similar conditions. This work opens up enormous opportunities for exploring new applications of MOFs in a freestanding, structurally adaptive, and macroscopic form.

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