Nowadays, charge separation and efficient solar-light absorption are the main challenges in the photoreduction of CO 2 . Although significant efforts have been made to overcome these issues, including the use of cocatalysts and doping, photocatalysts still suffer from low photocatalytic activity and stability. Herein, the localized surface plasmonic resonance (LSPR) effect of Au nanoparticles deposited into the zeolitic imidazolate framework (ZIF-67) was investigated for the photoreduction of CO 2 . Different Au loadings in ZIF were prepared and their effects were studied on photocatalytic performance. Plasmonic Au nanoparticles (PNPs) in the size range of 30−40 nm improved visible-light absorption, enhanced charge separation, and played an important role in selectivity. A volcano relationship of plasmonic Au NPs with methanol and ethanol generation was found, along with the deposition of plasmonic Au nanoparticles. A total yield of 2.5 mmol g −1 h −1 of methanol and 0.5 mmol g −1 h −1 of ethanol were obtained, which are the highest values compared to those reported in other studies. Finally, our results revealed that Au PNPs have a significant impact on the selectivity and photocatalytic activity of ZIF-67 for the photoreduction of CO 2 and could be a promising alternative toward designing plasmonic reticular materials.

The release of large volumes of anthropogenic CO2 coupled with growing exploitation of fossil fuels has led to very serious issues such as global warming and energy crisis in the...

Photocatalytic reduction of CO 2 into useful feedstocks has attracted more attention in recent decades. However, the effective and selective conversion of CO 2 to the desired product always remains a major challenge in photocatalysis, which relies on the appropriate band edge potential and efficient separation of photogenerated charge carriers in the photocatalysts. In this direction, herein we report the construction of a keto-enamine covalent organic framework (COF) incorporated with reduced graphene oxide with increasing concentrations, rGO x @TpPa-1 (x = 5%, 10%, 15%, and 20%), by the in situ assembling technique to significantly boost up the charge separation thereby to improve the efficiency CO 2 photoreduction. The developed rGO 15 @TpPa-1 nanocomposite showed remarkable efficiencies toward photocatalytic CO 2 reduction under visible light irradiation, which yielded the CO at a rate up to ∼200 μmol g −1 h −1 and with a selectivity of 89%, which was 1.57 and 6.97 times higher as compared to the bare COF and rGO counterparts, respectively. The series of control experiments demonstrated that both TpPa-1 and rGO counterparts have a significant synergistic impact on the selectivity and efficiency toward photoreduction of CO 2 . Under optimized conditions, rGO 15 @TpPa-1 exhibited an apparent quantum yield of 0.5% at 420 nm, which is one of the few notable values reported in the literature. The covalent interactions between TpPa-1 and rGO facilitated the formation of band edges with required potential and thereby an improved charge separation along with rapid migration of charge carriers to the surface toward the selective reduction of CO 2 to CO, which is validated by the 13 C labeling. This work could be a promising approach toward energy applications for the potential development of COFs and their analogous structures.

Zeolitic imidazolate frameworks (ZIFs) are promising photocatalysts for CO2 reduction due to their proper energy band structure and crystalline properties. However, CO2 conversion is still low due to the serious...

Solar‐light harvesting materials currently represent a hot topic in catalysis due to the several applications where they can be used. Among the recent strategies to enhance the photocatalytic performance of semiconductor materials, plasmonic metals are trending. Coupling plasmonic metal nanoparticles with a semiconductor material can give unique synergistic effects and properties. Especially when reticular materials, like metal organic frameworks, are used to generate these plasmonic nanocomposites. Herein, a brief introduction to the localized surface plasmon resonance and reticular materials design and fabrication is given. Also, the advantages of plasmonic with reticular nanostructures are discussed. The following highlights summarize recent advances in sunlight‐driven plasmonic reactions (CO2 photoreduction, water depollution, gas sensing, and optical reactions). Theoretical and experimental approaches are discussed, regarding mechanistic phenomena of nanocomposites with reticular materials and surface plasmon metals. A proper discussion and perspective of the remaining challenges and future opportunities for plasmonic metals with reticular materials in the field of photocatalysis is given in the overview and conclusion.

Photocatalytic conversion of CO2 into beneficial raw chemicals has gained a great deal of attention for well over the recent decade due to its prospect for alleviating energy scarcity and global warming. Even though photocatalytic CO2 reduction technique has shown great promise, the successful conversion of CO2 to the intended outputs has remained a key barrier. Here, we present the design synthesis of a hollow nanospherical keto-enamine TpPa-1 covalent organic framework (COF) integrated single-atom Co-1T-MoS2 (TpPa-1/Co-1T-MoS2) composite with the appropriate band edge potential and an enhanced charge separation to improve its CO2 photoreduction efficiency under visible light irradiation. With a selectivity of 93%, the developed TpPa-1/Co-1T-MoS2 nanocomposite exhibits impressive photocatalytic CO2 reduction efficiency of up to ∼196 μmol g–1 h–1 of CO. Bare TpPa-1 and Co-1T-MoS2 both had around 1.23 and 1.6 times lower CO than TpPa-1/Co-1T-MoS2. Parametric analyses show that the TpPa-1 and Co-1T-MoS2 counterparts have a remarkable cumulative influence on the specificity and efficacy of photoreduction of CO2 to CO. TpPa-1/Co-1T-MoS2 composite is one of the handful of notable values cited in the literature, with an apparent quantum yield of 0.7% at 420 nm under ideal conditions. 13C labeling confirms that the selective conversion of CO2 to CO was facilitated by couplings between TpPa-1 and Co-1T-MoS2, which enhanced charge separation and migration to the surface. The findings show that COFs and their single-atom-based composites can be developed for next-generation photocatalytic systems and that this technology may also be interesting for other energy conversion applications.

The design of functionalized metallic nanoparticles is considered an emerging technique to ensure the interaction between metal and semiconductor material. In the literature, this interface interaction is mainly governed by electrostatic or van der Waals forces, limiting the injection of electrons under light irradiation. To enhance the transfer of electrons between two compounds, close contact or chemical bonding at the interface is required. Herein, a new approach was reported for the synthesis of chemically bonded plasmonic Au NPs/ZIF-67 nanocomposites. The structure of ZIF-67 was grown on the surface of functionalized plasmonic Au NPs using 1H-1,2,4-triazole-3thiol as the capping agent, which acted as both stabilizer of Au nanoparticles and a molecular linker for ZIF-67 formation. As a result, the synthesized material exhibited outstanding photocatalytic CO 2 reduction with a methanol production rate of 2.70 mmol h À 1 g À 1 cat under sunlight irradiation. This work emphasizes that the diligent use of capping agents, with suitable functional groups, could facilitate the formation of intimate heterostructure for enhanced photocatalytic CO 2 reduction.

Plasmonic materials (PMs) essentially equip the photocatalysts to harvest energy from visible light photons. Interestingly, these PMs also support the photocatalysts, which has been realized upon the advent of non‐noble metals‐based PMs. In this context, this study reveals an interesting feature of TiN@ZIF‐67 plasmonic composite photocatalysts towards CO2 reduction under solar irradiation. The composite is prepared via an in‐situ and direct integration process, where the plasmonic TiN nanoparticles are surface‐modified using 3‐aminopropyl‐triethoxysilane/H‐Imidazole‐2‐carbaldehyde in the former and polyvinylpyrrolidone in the latter process to construct the 1H2ImCHO‐TiN@ZIF‐67 and TiN/PVP@ZIF‐67 composites, respectively. The structural and functional properties in these composites are confirmed using XRD and FTIR spectroscopy techniques. It is observed from the TEM images that the in‐situ integration leads to deep‐surface attachments of TiN on ZIF‐67, which exerted a major impact in the CO2 photoreduction. The 1H2ImCHO‐TiN@ZIF‐67 shows the simultaneous production of ∼0.11 and 0.15 mmol g−1 h−1 of methanol and ethanol, respectively; whereas, the TiN/PVP@ZIF‐67 produces only ∼0.31 mmol g−1 h−1 of methanol. The obtained results demonstrate that developed in‐situ synthetic approach is promising for the synthesis of efficient plasmonic photocatalysts and the product formation during CO2 photoreduction can be dependent on how PMs are integrated with the host photocatalysts.