Electrochemical CO₂ conversion into fuels is highly desirable to achieve carbon artificial cycles. Among electrocatalyst candidates, earth-abundant tin is subject to unsatisfied efficiency and selectivity. In this work, atomically-dispersed Sn nanoclusters modified with the trace of sulfur doping are proposed to efficiently electroreduce CO₂ to C₁ chemicals. This electrocatalyst is in situ derived from bis(benzene-1,2-dithiolato). It exhibits a high Faradaic efficiency (90%) for carbonaceous products at a moderate overpotential (0.75 V). Importantly, it is exploited for the formate formation with unprecedented partial current density (90 mA cm⁻²) and long-term stability (50 h) using the flow cell, better than most Sn-based catalysts. Electrochemical experiments and theoretical calculations manifest the promoting effect of trace sulfur on Sn nanoclusters, which stabilizes the *HCOOH intermediate and favors CO₂ electroreduction. Hence, it emphasizes the importance of dopants and charge modulating for performance enhancement. This work unfolds a promising candidate for Sn electrocatalysts towards CO₂ electroreduction.

电化学CO ₂转化为燃料对于实现碳人工循环是非常理想的。在候选电催化剂中，地球上丰富的锡的效率和选择性不令人满意。在这项工作中，提出了用微量硫掺杂改性的原子分散的 Sn 纳米团簇，以有效地将 CO ₂电还原为 C ₁化学品。该电催化剂原位衍生自双（苯-1,2-二硫醇）。它在中等过电位 (0.75 V) 下对碳质产品表现出高法拉第效率 (90%)。重要的是，它被用于以前所未有的部分电流密度（90 mA cm ^-2) 和使用流通池的长期稳定性 (50 小时)，优于大多数 Sn 基催化剂。电化学实验和理论计算表明微量硫对Sn纳米团簇的促进作用，稳定*HCOOH中间体并有利于CO ₂电还原。因此，它强调了掺杂剂和电荷调制对于性能增强的重要性。这项工作为用于 CO ₂电还原的Sn 电催化剂提供了一个有希望的候选者。