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[Display omitted] • An effective strategy has been established by doping Ce into Cu NPs to tune the electronic state of Cu. • It attains the faradaic efficiency of C 2 H 4 as high as 53% with a current density of 150 mA/cm2. • Such performance is about 2.8-fold increase when compared with Cu NPs. • The electronic structure regulation and defective sites facilitate highly efficient C 2 H 4 production from CO 2 electroreduction. Coupling another metal element tends to produce catalytic controls of high activity and selectivity. However, this action is still poorly explored to improve the selectivity of the electroreduction of CO 2 to C 2 H 4 with high energy density. Herein, Ce-doped Cu nanoparticles (Ce-Cu NPs) are synthesized by one-step co-reduction method and presented a preferable example that promotes selective transformation of CO 2 to C 2 H 4 in a flow-cell configuration. Thereinto, high faradaic efficiency (FE) of C 2 H 4 for Ce-Cu-2 NPs could reach 53% with the current density of 150 mA cm−2, which is 2.8 times higher than that of Cu NPs. The outstanding performance mainly stems from tailoring the doped-Ce content shrinks particle sizes and forms oxygen defects due to the electron effect of nearby Ce atoms, boosting local electronic re-distribution of Cu. Meanwhile, in-situ Raman spectroscopies evidenced that the doping of Ce can enhance Cu site to bond *CO, which were beneficial to C–C coupling and thus endowed the catalyst with the superior catalytic performance in CO 2 electroreduction toward C 2 H 4. [ABSTRACT FROM AUTHOR]

C@Fe 2 C/TiO photocatalytic CO 2 realizes C–C coupling to produce C2 fuel mainly due to the formation of a Z-scheme heterojunction between Fe 2 C and TiO, which changes the electron transmission path, and the CO* generated by TiO induces the production of C2. [Display omitted] • A novel C@Fe 2 C/TiO ternary composite catalyst is prepared. • The catalyst exhibits high activity under simulated sunlight with main-product of C 2 H 4. • The catalyst could be excited by NIR lights. CO 2 conversion is of great industrial importance in reducing green-house effect and reusing carbon-resource. Most studies are focused on the thermocataltic CO 2 conversion, which usually performs over noble metal catalysts at high temperature and pressure. Recently, photocatalytic CO 2 conversion has caused increasing attention owing to the energy save, low-cost and clean reaction route. The key problem is to design photocatalysts high activity and strong durability. Here, we choose to prepare a novel C@Fe 2 C/TiO ternary composite catalyst by reducing organic compounds under an ammonia atmosphere. During CO 2 reduction reaction in aqueous solution, the catalyst exhibits high activity under simulated sunlight with main-product of C 2 H 4 (35.483 μmol g-1h−1). Even irradiating with near-infrared lights, the catalytic conversion still proceeds successfully, but the main-product turns to be CH 4 (18.315 μmol g-1h−1). Based on the chanracterizations and DFT calculation, the high activity could be attributed to the cooperation between the Fe 2 C catalyst toward C 2 H 4 and the TiO 2 photocatalyst. Specially, C@Fe 2 C/TiO could be excited by NIR lights owing to the narrow-energy band gap. More importantly, the photoelectrons could be easily separated from holes owing to the presence of the Z-scheme heterojunctions, leading to the enhanced photocatalytic activity. This work provides new insights to understand the CO 2 reduction reaction mechanism to develop photocatalysts. [ABSTRACT FROM AUTHOR]