The proton-coupled electron transfer process (PCET) plays a crucial role in both natural and artificial photosynthesis, including CO fixation chemistry. However, difficulties in capturing the transient intermediates generated during the protonation process impede the clarification of the fundamental mechanism behind photocatalytic CO reduction. Herein, we report a general killing two birds with one stone strategy by spatially confining Au nanorods within a typical porphyrin metal-organic framework (MOF). Interestingly, 2.4-fold increase in CH/CO selectivity and 12-fold increase in CH production were observed after loading of Au nanorods, indicative of a strengthened protonation process in the photocatalytic CO reduction. More importantly, the plasmonic effect from Au nanorods simultaneously boosted the in situ Raman signals of *CO and *CHO intermediates on the Au-O-Zr active site. The evident protonation process was further clarified in a control H/D kinetic isotope experiment. This work highlights the significance of successive protonation steps for boosting CH production in photocatalytic CO reduction.
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