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Solar-driven highly-efficient photocatalytic reduction of CO2 into value-added fuels has been regarded as a promising strategy to assuage the current global warming and energy crisis, but developing highly product-selective, long-term stable and low-cost photocatalysts for C2 production remains a grand challenge. Herein, we demonstrate that two-dimensional β- and δ-phase Cu2S monolayers are promising photocatalysts for the reduction of CO2 into C2H5OH. The calculated potential-limiting steps for the CO2 reduction reaction (CO2RR) are l