The exploration of robust titanium-based metal-organic framework (MOF) photocatalysts for efficient CO₂ reduction is of critical significance but remains challenging. Herein, a hierarchically porous titanium-MOF (hMUV-10) anchored with ultrafine Pd nanoparticles was rationally designed via a convenient one-step in-situ water-etching strategy. The hierarchical MUV-10 structure provided abundant sites for the anchoring of Pd nanoparticles on the outside and inside of MOFs. The optimized Pd/hMUV-10 demonstrated an ultrahigh CO production rate of 65.9 mmol g⁻¹ h⁻¹ under light irradiation at 350°C, approximately two orders of magnitude higher than the state-of-the-art MOF-based catalysts and surpassed most reported inorganic semiconductor-based catalysts. The CO production rate under a relatively mild temperature of 200°C also reached as high as 3.36 mmol g⁻¹ h⁻¹, and negligible activity decay was observed during continuous cycling measurement under 350°C. Theoretical calculations suggested that Pd enhanced CO₂ adsorption ability and reduced the energy barrier for CO₂ reduction, thereby leading to a highly improved CO yield from photothermal CO₂ reduction.

探索稳定的钛基金属有机骨架 (MOF) 光催化剂以高效还原 CO ₂具有重要意义，但仍具有挑战性。在此，通过方便的一步原位水蚀刻策略合理设计了一种锚定有超细 Pd 纳米颗粒的分级多孔钛-MOF (hMUV-10) 。分层的 MUV-10 结构为 Pd 纳米粒子在 MOF 的外部和内部的锚定提供了丰富的位点。^{优化的 Pd/hMUV-10 表现出 65.9 mmol g −1} h ⁻¹的超高 CO 生产率在 350°C 的光照射下，比最先进的基于 MOF 的催化剂高约两个数量级，并超过大多数报道的无机半导体基催化剂。在 200°C 相对温和的温度下，CO 产率也高达 3.36 mmol g ^-1 h ^-1，并且在 350°C 下连续循环测量期间观察到可忽略的活性衰减。理论计算表明，Pd 增强了 CO _{2吸附能力并降低了 CO 2}还原的能垒，从而大大提高了光热 CO ₂还原的 CO 产率。