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Abstract CO₂electroreduction (CO₂R) operating in acidic media circumvents the problems of carbonate formation and CO₂crossover in neutral/alkaline electrolyzers. Alkali cations have been universally recognized as indispensable components for acidic CO₂R, while they cause the inevitable issue of salt precipitation. It is therefore desirable to realize alkali‐cation‐free CO₂R in pure acid. However, without alkali cations, stabilizing *CO₂intermediates by catalyst itself at the acidic interface poses as a challenge. Herein, we first demonstrate that a carbon nanotube‐supported molecularly dispersed cobalt phthalocyanine (CoPc@CNT) catalyst provides the Co single‐atom active site with energetically localizeddstates to strengthen the adsorbate‐surface interactions, which stabilizes *CO₂intermediates at the acidic interface (pH=1). As a result, we realize CO₂conversion to CO in pure acid with a faradaic efficiency of 60 % at pH=2 in flow cell. Furthermore, CO₂is successfully converted in cation exchanged membrane‐based electrode assembly with a faradaic efficiency of 73 %. For CoPc@CNT, acidic conditions also promote the intrinsic activity of CO₂R compared to alkaline conditions, since the potential‐limiting step, *CO₂to *COOH, is pH‐dependent. This work provides a new understanding for the stabilization of reaction intermediates and facilitates the designs of catalysts and devices for acidic CO₂R. 

Correlated-electron systems have long been an important platform for various interesting phenomena and fundamental questions in condensed matter physics. As a pivotal process in these systems, d-d transitions have been suggested as a key factor toward realizing optical spin control in two-dimensional (2D) magnets. However, it remains unclear how d-d excitations behave in quasi-2D systems with strong electronic correlation and spin-charge coupling. Here, we present a systematic electronic Raman spectroscopy investigation on d-d transitions in a 2D antiferromagnet—NiPS 3 , from bulk to atomically thin samples. Two electronic Raman modes originating from the scattering of incident photons with d electrons in Ni 2+ ions are observed at ~1.0 eV. This electronic process persists down to trilayer flakes and exhibits insensitivity to the spin ordering of NiPS 3 . Our study demonstrates the utility of electronic Raman scattering in investigating the unique electronic structure and its coupling to magnetism in correlated 2D magnets.