Photothermal Conversion Boosted Photocatalytic CO₂ Reduction over S-Scheme CeO₂@Cu-TCPP: In Situ Experiments and DFT Calculations

Abstract

Herein, interfacial and defect-engineering strategies synergistically promote photocatalytic properties. Because of the matching energy levels and the close interfacial contact, the CeO 2 @ Cu-TCPP S-scheme architecture is successfully constructed via the in situ wet chemistry route. Photothermal conversion assists abundant O Vs on the CeO 2 compartment. Strong evidence of an S-scheme charge transfer path is verified by density functional theory (DFT) calculations and in situ irradiated X-ray photoelectron spectroscopy (XPS). This S-scheme heterojunction system is more deep-seated in facilitating the separation and transfer of photogenerated carriers as well as acquiring strong photoredox ability. Meanwhile, the abundant O Vs proved by XPS and electron paramagnetic resonance spectra (ESR) enhanced the light-harvesting capacity and conductivity and shortened the transfer route. As a result, this synergistic heterojunction could mostly promote photocatalytic CO 2 activation. The typical 0.25CeO 2 @ Cu-NS exhibited the best photocatalytic CO 2 RR to form CO and CH 4 (rate: 229.6 μmol•g −1 ), which is even 45.8-and 1.5-folds higher than those of pristine LA-CeO 2 (5.0 μmol•g −1 ) and Cu-TCPP (152.2 μmol•g −1 ), respectively, higher than those of other reported CeO 2 -based photocatalysts. This study presents a reinforcement and matrix prospect for domain charge behaviors to accelerate CO 2 activation.

Modulating CsPbBr3 nanocrystals encapsulated in PCN-224(Zr) for boosting full-spectrum-driven CO2 reduction: S-scheme transfer, photothermal-synergistic effect, and DFT calculations

“…As reported in the previous literature, MOFs constructed by the TCPP ligand always display good photothermal properties due to its large p-conjugated macrocycle structure of the porphyrin ligand. 24 Aer compositing with each other, the temperature of CsPbBr 3 @PCN-224(Zr)-10 could rise to 70.2 °C within 6 min, showing its excellent photothermal activity, which was due to the contribution of PCN-224(Zr). Meanwhile, the photothermal effect under UV light was also checked, as shown in Fig.…”

“…S19 † and as reported in our previous work. 24 Additionally, the band-bending induced the built-in electric eld and the photogenerated electron-holes separation, while the photothermal effect triggered the surface-defect state to provide an excellent platform for cascade electron transfer in the CsPbBr 3 @PCN-224(Zr) heterostructures, resulting in signicantly boosted CO 2 -photoreduction activity. Meanwhile, the chemical state and interfacial interaction of the obtained samples were studied by XPS measurements (Fig.…”

“…[20][21][22] More importantly, the photothermal effect from the large p-conjugated macrocycle of the porphyrin ligand could not only remarkably enhance CO 2 adsorption/activation, thus saving energy consumption, but also allow coupling thermocatalysis and photocatalysis to promote the CO 2 RR. 23,24 Taking advantage of the photothermal and light-harvesting capabilities of porphyrin-based MOFs, our team previously assembled a series of heterostructure composites for photocatalytic CO 2 RR. We also believe that integrating perovskite QDs with energy-band-matched MOFs to synergistically catalyze CO 2 photoreduction would be a good alternative method.…”

Nanostructured CeO2 photocatalysts: optimizing surface chemistry, morphology, and visible-light absorption

“…, 2H 2 O → 4H + + O 2 ) will occur at the CeO 2 VB, as demonstrated in the case of CeO 2 /LaTiO 2 N. 85 A more recent work by Zhang et al utilize CeO 2 in this role in an S-scheme photocatalyst, providing evidence of the proposed charge-transport pathway through DFT calculations and in situ XPS measurements. 86…”

A dual Z-scheme heterojunction Cu-CuTCPP/Cu2O/CoAl-LDH for photocatalytic CO2 reduction to C1 and C2 products

“…10 For example, the recently reported porphyrin-based MOF catalysts Co-TCPP-TiO 2 and CeO 2 @Cu-TCPP exhibited extraordinary catalytic activity and great research value. 11,12 The carboxylate coordinated metal oxygen clusters (M x (COO) y ) have a variety of metal atoms, and dynamic switching occurs in the structure during the catalytic reaction. The conversion of CO 2 to C–C coupled hydrocarbons requires the synergistic transfer of multiple reaction sites and electrons.…”