Zhi Liu

A short-range internal electric field in a biomimetic nucleus–cytoplasm configuration synchronizes CO* spillover and H* coupling to promote CHO* formation for selective CO ₂ photomethanation.

Co ₃ S ₄ quantum dots/NiAl-LDH creates dual confinement for CO ₂ photoreduction. An interfacial electric field enriches electrons at hydroxyl sites, lowers the COOH* barrier, and boosts CO evolution 17.8-fold over NiAl-LDH.

Selective control of CO ₂ photoreduction toward CO or CH ₄ is essential for solar‐to‐fuel conversion. Reversible switching between these two products remains challenging because conventional photocatalysts cannot adjust charge behavior with temperature, and polar intermediates are insufficiently stabilized. A temperature‐adaptation photocatalytic platform that acts as a spin polarization electron pump, delivering programmable interfacial electron injection and dynamically steering CO ₂ reduction pathways in real time is reported. At low temperature, adaptive modulation increases interfacial electron accumulation at the reaction interface, extending the lifetime and reactivity of deep‐pathway intermediates without altering catalyst composition. Consequently, product selectivity reversibly shifts from CO at high temperature to CH ₄ at low temperature, enabling controlled access to either shallow or deep reduction products under reliably well‐defined thermal conditions. Temperature‐dependent photoluminescence and electron paramagnetic resonance demonstrate enhanced spin polarization and reduced charge recombination upon cooling, consistent with stronger interfacial electron retention. In situ infrared spectroscopy and ab initio molecular dynamics reveal that spin polarization‐selective transfer bends CO ₂ and induces C─O bond asymmetry, which facilitates CHO* formation and lowers the barrier for CO* hydrogenation to CH ₄ . Collectively, these findings establish a generalizable strategy that integrates spin polarization with temperature responsiveness to realize dynamically programmable product selectivity in solar‐driven CO ₂ conversion.

Photocatalytic conversion of CO₂ and H₂O into high‐value‐added C2 fuels remains a tough challenge, mainly due to the insufficient concentration of photogenerated electrons for the instability of C1 intermediates, which often tend to desorb easily and disable to form C─C bonds. In this work, photoreduction of CO₂‐to‐C₂H₆ is successfully achieved by introducing adjacent C, N dual‐vacancy sites within the heptazine rings of ultrathin g‐C₃N₄, which results in the opening of two neighboring heptazine rings and forms a distinctive dipole‐limited domain field (DLDF) structure. In situ X‐ray photoelectron spectra and in situ fourier transform infrared spectra provide direct evidence of the rapid accumulation and transformation of C1 intermediates, especially CO^* and CHO^*, within the DLDF. Ab initio molecular dynamics further substantiates the role of DLDF in promoting C–C coupling between CO^* and CHO^*, through the analysis of interaction trajectories and energy changes of their central atoms, ultimately achieving a high yield of C₂H₆ up to 57.86 µmol g⁻¹ h⁻¹. It is for the first time to propose the concept of DLDF for significant advancement in photoreduction of CO₂‐to‐C2 fuel with the evident breakthrough to address the challenge of coupling carbon‐containing intermediates between active sites, offering new insights for the design of C–C coupling sites in single‐component photocatalysts.

Photocatalytic CO₂ reduction technology is of great importance to alleviate energy crisis and environmental pollution; however, it remains a serious challenge due to the fast recombination of carriers. In this study, we report a three-dimensional structure of a ZnIn₂S₄/Au/CdS composite photocatalyst for the CO₂ reduction reaction, where Au nanoparticles (NPs) are evenly anchored on the surface of ZnIn₂S₄ by photodeposition and Au NPs are wrapped around by CdS. In ZnIn₂S₄/Au/CdS composite photocatalysts, Au NPs act as a bridge to construct a "semiconductor-metal-semiconductor" tandem electron transfer mechanism (ZnIn₂S₄ → Au → CdS) heterojunction, which greatly promotes the transfer of photogenerated electrons. It is worth noting that Au NPs, as a local surface plasmon resonance (LSPR) effect excited source to generate excited-state electrons, further improve the photoreduction CO₂ activity. Under UV-vis light irradiation, the CO yield of ZnIn₂S₄/Au/CdS can reach 63.07 μmol·g^-1·h^-1, which is higher than that of 6.37 μmol·g^-1·h^-1 for pure ZnIn₂S₄, 0.93 μmol·g^-1·h^-1 for CdS, 8.9 μmol·g^-1·h^-1 for ZnIn₂S₄/CdS, 31.04 μmol·g^-1·h^-1 for ZnIn₂S₄/Au, and 5.37 μmol·g^-1·h^-1 for CdS/Au. In addition, the ternary ZnIn₂S₄/Au/CdS composite photocatalyst has good cyclic stability. This study broadens the idea of designing photocatalysts with good carrier separation efficiency.

Ni-/Fe-based materials are promising electrocatalysts for the oxygen evolution reaction (OER) but usually are not suitable for the hydrogen evolution reaction (HER). Herein, a durable and bifunctional catalyst consisting of Ni-FeO_x and FeNi₃ is prepared on nickel foam (Ni-FeO_x/FeNi₃/NF) by in situ solution combustion and subsequent calcination to accomplish efficient alkaline water splitting. Density functional theory (DFT) calculation shows that the high HER activity is attributed to the strong electronic coupling effects between FeO_x and FeNi₃ in the Janus nanoparticles by modulating ΔG_H* and electronic states. Consequently, small overpotentials (η) of 71 and 272 mV in HER and 269 and 405 mV in OER yield current densities (j) of 50 and 1000 mA cm^-2, respectively. The catalyst shows outstanding stability for 280 and 200 h in HER and OER at a j of ∼50 mA cm^-2. Also, the robustness and mechanical stability of the electrode at an elevated j of ∼500 mA cm^-2 are excellent. Moreover, Ni-FeO_x/FeNi₃/NF shows excellent water splitting activities as a bifunctional catalyst as exemplified by j of 50 and 500 mA cm^-2 at cell voltages of 1.58 and 1.80 V, respectively. The Ni-FeO_x/FeNi₃/NF structure synthesized by the novel, simple, and scalable strategy has large potential in commercial water electrolysis, and the in situ combustion method holds great promise in the fabrication of thin-film electrodes for different applications.