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With the most advances made so far in terms of photocatalyst design and preparation (inorganic photoredox nanoparticles), researchers of different expertise joined together to address sustainable energy conversion. Despite notable advancements in creating exceptionally active photocatalysts, the practical scalability of these innovations is hindered by issues such as ineffective utilization of solar energy and mass transport, recombination reactions, catalyst instability, and photo corrosion of the catalyst. In this roadmap review, we brief the fundamentals, latest progress, outstanding challenges, and novel design methodology for anticorrosive photocatalysts favorable to large‐scale hydrogen production. To enable the effective scaling of photocatalysis, beyond the inherent activity of photocatalysts, a range of additional factors are considered, with a primary focus on the design of photocatalytic systems. This review underlines the significance of well‐structured photocatalyst design and evaluation for achieving reproducibility and using dependable research methodology for conducting rigorous experiments. The recommendations are directed at reducing the uncertainty surrounding the optimism presented in published research, and we spotlight our recent research advancements. Importantly, the synergistic integration of design principles and research methodologies to enhance the anti‐corrosion properties of photocatalysts may pave the way for a practical technology to utilize solar energy for large‐scale hydrogen production efficiently. This article is categorized under:Sustainable Energy > Solar Energy [ABSTRACT FROM AUTHOR]

Defect engineering through modification of their surface linkage is found to be an effective pathway to escalate the solar energy conversion efficiency of metal-organic frameworks (MOFs). Herein, defect engineering using controlled decarboxylation on the NH 2 -UiO-66 surface and integration of ultrathin NiCo-LDH nanosheets synergizes the hydrogen evolution reaction (HER) under a broad visible light regime. Diversified analytical methods including positron annihilation lifetime spectroscopy were employed to investigate the role of Zr 3+ -rich defects by analyzing the annihilation characteristics of positrons in NH 2 -UiO-66, which provides a deep insight into the effects of structural defects on the electronic properties. The progressively tuned photophysical properties of the NiCo-LDH@NH 2 -UiO-66-D-heterostructured nanocatalyst led to an impressive rate of HER (∼2458 μmol h -1 g -1 ), with an apparent quantum yield of ∼6.02%. The ultrathin NiCo-LDH nanosheet structure was found to be highly favored toward electrostatic self-assembly in the heterostructure for efficient charge separation. Coordination of Zr 3+ on the surface of the NiCo-LDH nanosheet support through NH 2 -UiO-66 was confirmed by X-ray absorption spectroscopy and electron paramagnetic resonance spectroscopy techniques. Femtosecond transient absorption spectroscopy studies unveiled a photoexcited charge migration process from MOF to NiCo-LDH which favorably occurred on a picosecond time scale to boost the catalytic activity of the composite system. Furthermore, the experimental finding and HER activity are validated by density functional theory studies and evaluation of the free energy pathway which reveals the strong hydrogen binding over the surface and infers the anchoring effect of the ultrathin layered double hydroxide (LDH) in the vicinity of the Zr cluster with a strong host-guest interaction. This work provided a novel insight into efficient photocatalysis via defect engineering at the linker modulation in MOFs.