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[Display omitted] Confronting the challenge of climate change necessitates innovative approaches for the reduction of CO 2 emissions. Metal-support interaction has been widely demonstrated to enable greatly improved performances in thermal-catalytic, photocatalytic and electrocatalytic CO 2 reduction. However, its applicability and specifically its role in the emerging piezo-electrocatalytic CO 2 reduction are unknown, severely hampering the utilizations of piezo-electrocatalysis in CO 2 conversion. Herein, by adopting Au particles supported on ZnO (Au/ZnO) as a paradigm, it is found that the metal-support interaction can remarkably improve the separation and transfer of piezo-carriers and enhance CO 2 adsorption. As a result, Au/ZnO demonstrates a substantially boosted activity for piezo-electrocatalytic CO 2 reduction and the optimal sample exhibits a 37.3% increase in CO yield compared to the pristine ZnO. The integration of metal-support interactions opens a new avenue to the design of advanced piezo-electrocatalysts for CO 2 reduction. [ABSTRACT FROM AUTHOR]

• Strong metal–oxygen hybridization was successfully incorporated in Ag cluster /TiO 2. • Ag cluster /TiO 2 shows a high photocatalytic CH 4 generation activity and selectivity. • Ag–O hybridization effectively optimizes photogenerated carrier dynamics. • Ag–O hybridization promotes the multiple-proton–electron coupling transfer process. Selective photocatalytic reduction of CO 2 to CH 4 is one of the most efficient ways to achieve carbon neutralization. However, the formation of methane remains a challenge due to the slow multiple-proton-coupled electron transfer process and the involvement of various C1 intermediates. Herein, an Ag cluster /TiO 2 catalyst with Ag-O hybridization was synthesized by supporting Ag clusters on anatase phase TiO 2 microspheres for photocatalytic CO 2 methanation. The Ag cluster /TiO 2 sample presents an electron selectivity of 86 % for CH 4 production with a yield of 25.25 μmol g–1 h−1. Mechanistic study reveals that Ag clusters accelerate the separation and migration of photogenerated carriers, and enhance the adsorption of CO 2. Moreover, the Ag-O hybridization promotes the multiple-proton–electron coupling transfer process by effectively stabilizing intermediates and facilitating *CO hydrogenation to *CHO, resulting in selective CO 2 reduction to CH 4. This work provides a new insight into the development of selective photocatalytic conversion of CO 2 to methane by constructing supported cluster catalysts. [ABSTRACT FROM AUTHOR]

• A novel direct Z-Scheme C-TiO 2 /β-Bi 2 O 3 heterojunction was fabricated by in situ assembling the two energy-band-matched semiconductors together. • The optimal C-TiO 2 /β-Bi 2 O 3 hybrid shows an obviously enhanced photocatalytic CO generation activity of 31.07 μmol g−1 h−1, which is among the highest reported levels over TiO 2 -based heterojunction photocatalysts. • In situ experimental techniques and theoretical calculations uncover that the enhanced photocatalytic activity is ascribed to C doping and the formation of direct Z–Scheme heterojunction, which effectively promotes the separation of photogenerated carriers. Rational fabricating advanced photocatalysts to recycle CO 2 into solar fuel is one of the most promising approaches to simultaneously address energy shortages and global warming. TiO 2 has been widely used in photocatalytic CO 2 reduction due to its abundant reserves, non-toxicity and harmlessness etc. However, it remains significantly challenging for practical applications due to the fast electron-hole recombination. Herein, we design a direct TiO 2 based Z-Scheme heterojunction by self-assembly of C-doped TiO 2 nanoparticles on 3D hierarchical petal of flower-like β-Bi 2 O 3 (C-TiO 2 /β-Bi 2 O 3). In situ electron paramagnetic resonance tests, in situ X-ray photoelectron spectroscopy and theoretical calculations reveal that electrons are transferred from β-Bi 2 O 3 to C-TiO 2 due to the formation of Z-Scheme heterojunction, which greatly accelerates the separation of photogenerated carriers to promote efficient CO 2 photoreduction. Ultimately, the optimal heterojunction shows significantly enhanced photocatalytic activity for CO 2 reduction to CO (31.07 μmol g–1 h−1) compared to the pure TiO 2 (3.28 μmol g–1 h−1) without using any photosensitizers and sacrificial agents. This work provides a unique insight to design direct Z-Scheme heterojunctions and delivers a promising photocatalyst for overcoming global warming and energy-supply issues. [ABSTRACT FROM AUTHOR]

• Iron doping strategy is introduced in sintering-synthesized Bi 5 O 7 I photocatalysts. • Charge localization induced by iron doping greatly enhanced CO 2 capture capacity. • Multifunctional improvement of carrier dynamics and surface reaction is achieved. • In situ DRIFT and DFT simulation uncover the mechanisms of CO 2 photoreduction. The bismuth-rich bismuth oxyhalide materials exhibit prominent photocatalytic CO 2 reduction (PCR) performance owing to the considerable negative conduction band potential and unique intrinsic internal electric field. However, it possesses poor capture ability of CO 2 molecule due to the intrinsically weak adsorption, greatly limiting its further PCR improvement. Herein, we modulate the spatial charge redistribution over hierarchically Bi 5 O 7 I micro-flower through a facile and cost-efficient iron doping strategy, achieving significantly enhanced CO 2 capture capacity. Mechanistic studies indicate that the promoted adsorption ability originates from the localized electrons around the doped Fe sites. Benefiting from the resultant unique electronic structures, the Fe doped Bi 5 O 7 I micro-flowers also exhibit remarkably improved harvest of visible light and promoted charge separation and transfer capability, thus finally achieving a notably boosted photocatalytic CO evolution rate of 12.02 μmol·g−1·h−1 without any sacrifice agents. [ABSTRACT FROM AUTHOR]