Photocatalytic Conversion Research Articles

Enhancing Photocatalytic CO2 Conversion through Oxygen-Vacancy-Mediated Topological Phase Transition.

Weak adsorption of gas reactants and strong binding of intermediates present a significant challenge for most transition metal oxides, particularly in the realm of CO2 photoreduction. Herein, we demonstrate that the adsorption can be fine-tuned by phase engineering of oxide catalysts. An oxygen vacancy mediated topological phase transition in Ni-Co oxide nanowires, supported on a hierarchical graphene aerogel (GA), is observed from a spinel phase to a rock-salt phase. Such in situ phase transition empowers the Ni-Co oxide catalyst with a strong internal electric field and the attainment of abundant oxygen vacancies. Among a series of catalysts, the in situ transformed spinel/rock-salt heterojunction supported on GA stands out for an exceptional photocatalytic CO2 reduction activity and selectivity, yielding an impressive CO production rate of 12.5 mmol g-1 h-1 and high selectivity of 96.5 %. This remarkable performance is a result of the robust interfacial coupling between two topological phases that optimizes the electronic structures through directional charge transfer across interfaces. The phase transition process induces more Co2+ in octahedral site, which can effectively enhance the Co-O covalency. This synergistic effect balances the surface activation of CO2 molecules and desorption of reaction intermediates, thereby lowering the energetic barrier of the rate-limiting step.

Photocatalytic Conversion of Lignin Models into Functionalized Aromatic Molecules Initiated by the Proton-Coupled Electron Transfer Process.

A mild and efficient method for lignin β-O-4 cleavage and functionalization was achieved via photocatalysis. This protocol exhibits a broad scope of lignin models and excellent compatibility of functionalization reagents, constructing a series of functionalized lignin-based aromatic compounds. Highly selective formation of alkyl radical species through a proton-coupled electron transfer and β-scission process provides the opportunity to form new C-C and C-N bonds by reaction with electrophilic reagents.

Surface Functionalization and Defect Construction of SnO2 with Amine Group for Enhanced Visible‐Light‐Driven Photocatalytic CO2 Reduction

AbstractPhotocatalytic CO2 reduction to hydrocarbon fuels through solar energy provides a feasible channel for reducing CO2 emission and resource depletion. Nevertheless, severe charge recombination and high energy barrier limit the CO2 reduction efficiency. Herein, a surface amine‐functionalized SnO2 with oxygen vacancies (A‐Vo‐SnO2) is fabricated to achieve visible‐light‐driven photocatalytic CO2 reduction. Specifically, amino groups modified onto the surface of the catalyst can provide more active sites to promote the adsorption of CO2. Meanwhile, the synchronously induced oxygen defect level reduces the band‐gap energy and expands the light‐absorption region from UV light to visible light. The oxygen vacancies can modulate the electronic structure and work as the separation centers of spatial charges, thus promoting the interfacial charge transfer efficiency and providing more catalytic sites, as evidenced by experimental observation and theoretical calculation. As expected, this A‐Vo‐SnO2 exhibits a CH4 evolution rate of 17.27 µmol g−1 h−1 without adding sacrificial agent and co‐catalyst, much higher than 5.98 µmol g−1 h−1 of pure SnO2. This work can provide significant inspiration for the design of defect engineering based on visible‐light‐driven photocatalysts towards photocatalytic CO2 conversion.

Efficient photocatalytic biomass-alcohol conversion with simultaneous hydrogen evolution over ultrathin 2D NiS/Ni-CdS photocatalyst

The photocatalytic conversion of biomass into high-value chemicals, coupled with simultaneous hydrogen (H2) evolution, leveraging the electrons and holes generated by solar energy, holds great promise for addressing energy demands. In this study, we constructed a dual functional photocatalytic system formed by NiS loaded on Ni doped two-dimensional (2D) CdS nanosheet (NiS/Ni-CdSNS) heterostructure for visible-light-driven H2 evolution and ethanol oxidation to acetaldehyde. Remarkably, the 2D NiS/Ni-CdSNS exhibited significant activity and selectivity in both photocatalytic H2 evolution and ethanol oxidation, achieving yields of 7.98 mmol g−1 h−1 for H2 and 7.33 mmol g−1 h−1 for acetaldehyde. The heterogeneous interface of the composite facilitated efficient charge separation, while NiS provided abundant sites for proton reduction, thereby promoting the overall dual-functional photocatalytic activity. Density functional theory calculations further reveal that both Ni doping and NiS loading can reduce the reaction energy barrier of ethanol oxidation of free radicals, and NiS/Ni-CdSNS composite materials exhibit stronger ethanol C-H activation ability to generate key intermediate •CH(OH)CH3 on the surface. This work serves as a valuable guide for the rational design of efficient dual functional photocatalytic systems that combine H2 evolution with the selective conversion of organic compounds into high-value chemicals.

Ag Nanoparticle-Decorated GaN/β-Ga2O3 Core–Shell Nanowires as Catalysts for Highly Efficient CO2-to-CO Photocatalytic Conversion

Ag Nanoparticle-Decorated GaN/β-Ga₂O₃ Core–Shell Nanowires as Catalysts for Highly Efficient CO₂-to-CO Photocatalytic Conversion

Indium Doped Gan Porous Micro‐Rods Enhanced CO2 Reduction Driving By Solar Light

AbstractPhotocatalytic CO2 reduction plays an important role in solar energy storage and carbon balance. GaN as an III‐V semiconductor material has received extensive attention in the field of photocatalysis. In this study, the porous indium‐doped GaN (In/GaN) micro‐rods are synthesized successfully by a facile hydrothermal method and subsequent controlled atmosphere heat treatment. Photocatalytic CO2 reduction performance of In/GaN is higher than that of pure GaN due to the In doping improves the light absorption efficiency. The primary products are CO and CH4. Among the samples, 3%‐In/GaN exhibits the highest catalytic activity as well as stability and reusability. The yield rates of CO and CH4 can be reached 50.2 and 14.6 µmol · g−1 · h−1, respectively. Furthermore, density functional theory (DFT) calculations reveal that the bandgap is narrowed and the adsorption energy of CO2 molecules is improved by In doping. Moreover, the N‐vacancy detected by electron paramagnetic resonance (EPR) increases with the In doping, resulting in an increase in the number of unpaired electrons, which is conducive to carrier transport. This work provides a new study In/GaN prepared by simple method for the light‐driven photocatalytic conversion of CO2 to high‐value‐added products.

Enhancing Photocatalytic CO2 Conversion through Oxygen‐Vacancy‐Mediated Topological Phase Transition

Weak adsorption of gas reactants and strong binding of intermediates present a significant challenge for most transition metal oxides, particularly in the realm of CO2 photoreduction. Herein, we demonstrate that the adsorption can be fine‐tuned by phase engineering of oxide catalysts. An oxygen vacancy mediated topological phase transition in Ni‐Co oxide nanowires, supported on a hierarchical graphene aerogel (GA), is observed from a spinel phase to a rock‐salt phase. Such in‐situ phase transition empowers the Ni‐Co oxide catalyst with a strong internal electric field and the attainment of abundant oxygen vacancies. Among a series of catalysts, the in‐situ transformed spinel/rock‐salt heterojunction supported on GA stands out for an exceptional photocatalytic CO2 reduction activity and selectivity, yielding an impressive CO production rate of 12.5 mmol g‐1h‐1 and high selectivity of 96.5%. This remarkable performance is a result of the robust interfacial coupling between two topological phases that optimizes the electronic structures through directional charge transfer across interfaces. The phase transition process induces more Co2+ in octahedral site, which can effectively enhance the Co‐O covalency. This synergistic effect balances the surface activation of CO2 molecules and desorption of reaction intermediates, thereby lowering the energetic barrier of the rate‐limiting step.

Construction of Monoatomic-Modified Defective Ti4+αTi3+1-αO2-δ Nanofibers for Photocatalytic Oxidation of HMF to Valuable Chemicals.

Efficiently upgrading 5-hydroxymethylfurfural (HMF) into high-value-added products, such as 2,5-diformylfuran (DFF) and 2,5-furan dicarboxylic acid (FDCA), through a photocatalytic process by using solar energy has been incessantly pursued worldwide. Herein, a series of transition-metal (TM = Ni, Fe, Co, Cu) single atoms were supported on Ti4+αTi3+1-αO2-δ nanofibers (NFs) with certain defects (Ov), denoted as TM SAC-Ti4+αTi3+1-αO2-δ NFs (TM = Ni, Fe, Co, Cu), aiming to enhance the photocatalytic conversion of HMF. A super HMF conversion rate of 57% and a total yield of 1718.66 μmol g-1 h-1 (DFF and FDCA) surpassing that of the Ti4+αTi3+1-αO2-δ NFs by 1.6 and 2.1 times, respectively, are realized when TM is Co (Co SAC-Ti4+αTi3+1-αO2-δ NFs). Experiments combined with density functional theory calculation (DFT) demonstrate that the TM single atoms occupy the Ti site of Ti4+αTi3+1-αO2-δ NFs, which plays a dominant role in the photo-oxidation of HMF. Raman, X-ray photoelectron spectroscopy (XPS), and electron paramagnetic resonance (EPR) characterizations confirm the strong electron local exchange interaction in TM SAC-Ti4+αTi3+1-αO2-δ NFs and demonstrate the substitution of Ti by the TM SACs. The projected density of states and charge density difference reveal that the strong interaction between metal-3d and O-2p orbitals forms Ti-O-TM bonds. The bonds are identified as the adsorption site, where TM single atoms on the surface of Ti4+αTi3+1-αO2-δ NFs reduce HMF molecule adsorption energy (Eads). Furthermore, the TM single atom modulates the electronic structure of TM SAC-Ti4+αTi3+1-αO2-δ NFs through electron transfer, leading to narrow band gaps of the photocatalysts and enhancing their photocatalytic performance. This study has uncovered a newer strategy for enhancing the photocatalytic attributes of semiconducting materials.

Ethyl-activated carbon nitride for efficient photocatalytic CO2 conversion

Ethyl-activated carbon nitride for efficient photocatalytic CO2 conversion

Amorphous Metallic Cobalt-Based Organophosphonic Acid Compounds as Novel Photocatalysts to Boost Photocatalytic CO2 Reduction

Photocatalytic carbon dioxide conversion is a promising method for generating carbon fuels, in which the most important thing is to adjust the catalyst material to improve the photocatalytic efficiency and selectivity to conversion products, but it is still very challenging. In order to enhance the efficiency of CO2 photoreduction, it is important to develop an appropriate photocatalyst. The present study focuses on developing a simple and effective hydrothermal reaction treatment to improve the catalytic efficiency of transition metal cobalt (Co) and organophosphonates. Photoexcited charge carriers are separated and transferred efficiently during this treatment, which enhances CO2 chemisorption. Under visible light exposure, the best performing catalyst, CoP-4, showed 2.4 times higher activity than Co3O4 (19.90 μmol h−1 g−1) for reducing CO2 into CO, with rates up to 47.16 μmol h−1 g−1. This approach provides a viable route to enhancing the efficiency of CO2 photoreduction.

Construction synergetic adsorption and activation surface via confined Cu/Cu2O and Ag nanoparticles on TiO2 for effective conversion of CO2 to CH4

High-performance photocatalysts for catalytic reduction of CO2 are largely impeded by inefficient charge separation and surface activity. Reasonable design and efficient collaboration of multiple active sites are important for attaining high reactivity and product selectivity. Herein, Cu-Cu2O and Ag nanoparticles are confined as dual sites for assisting CO2 photoreduction to CH4 on TiO2. The introduction of Cu-Cu2O leads to an all-solid-state Z-scheme heterostructure on the TiO2 surface, which achieves efficient electron transfer to Cu2O and adsorption and activation of CO2. The confined nanometallic Ag further enhances the carrier’s separation efficiency, promoting the conversion of activated CO2 molecules to •COOH and further conversion to CH4. Particularly, this strategy is highlighted on the TiO2 system for a photocatalytic reduction reaction of CO2 and H2O with a CH4 generation rate of 62.5 μmol∙g−1∙h−1 and an impressive selectivity of 97.49 %. This work provides new insights into developing robust catalysts through the artful design of synergistic catalytic sites for efficient photocatalytic CO2 conversion.

Tuning Energy Transfer Pathways in Halide Perovskite-Dye Hybrids through Bandgap Engineering.

Lead halide perovskite nanocrystals, which offer rich photochemistry, have the potential to capture photons over a wide range of the visible and infrared spectrum for photocatalytic, optoelectronic, and photon conversion applications. Energy transfer from the perovskite nanocrystal to an acceptor dye in the form of a triplet or singlet state offers additional opportunities to tune the properties of the semiconductor-dye hybrid and extend excited-state lifetimes. We have now successfully established the key factors that dictate triplet energy transfer between excited CsPbI3 and surface-bound rhodamine dyes using absorption and emission spectroscopies. The pendant groups on the acceptor dyes influence surface binding to the nanocrystals, which in turn dictate the energy transfer kinetics, as well as the efficiency of energy transfer. Of the three rhodamine dyes investigated (rhodamine B, rhodamine B isothiocyanate, and rose Bengal), the CsPbI3-rose Bengal hybrid with the strongest binding showed the highest triplet energy transfer efficiency (96%) with a rate constant of 1 × 109 s-1. This triplet energy transfer rate constant is nearly 2 orders of magnitude slower than the singlet energy transfer observed for the pure-bromide CsPbBr3-rose Bengal hybrid (1.1 × 1011 s-1). Intriguingly, although the single-halide CsPbBr3 and CsPbI3 nanocrystals selectively populate singlet and triplet excited states of rose Bengal, respectively, the mixed halide perovskites were able to generate a mixture of both singlet and triplet excited states. By tuning the bromide/iodide ratio and thus bandgap energy in CsPb(Br1-xIx)3 compositions, the percentage of singlets vs triplets delivered to the acceptor dye was systematically tuned from 0 to 100%. The excited-state properties of halide perovskite-molecular hybrids discussed here provide new ways to modulate singlet and triplet energy transfer in semiconductor-molecular dye hybrids through acceptor functionalization and donor bandgap engineering.

Converting formaldehyde in methanol with MoO2 under irradiation: A pollution-free strategy for cleaning air

Direct photocatalytic reduction of toxic formaldehyde (HCHO) in value-added chemicals and fuels is promising because that not only abates the environmental pollution, but also solves the energy shortage. Herein, self-supported MoO2 and MoO3 nanoparticles growing on Mo meshes were comparatively applied to the photocatalytic conversion of HCHO. Under UV–visble lights, MoO2 reduces HCHO in methanol (CH3OH) while MoO3 oxidizes HCHO in carbon oxide and water. Their contrary photocatalytic capacities were revealed. Compared with MoO3, the lower work function of MoO2 enables an electron-rich interface, realizing a complete reduction of 30 ppm HCHO to CH3OH in 30 min. Theoretical calculations clarify that a large number of delocalized electrons on MoO2 attracts HCHO molecule and activates its CO bond, facilitating subsequent hydrogenation and reduction of HCHO to CH3OH. As for MoO3, the wider bandgap and higher potential of valence band govern the photocatalytic oxidation of HCHO.

Ligand-mediated exciton dissociation and interparticle energy transfer on CsPbBr3 perovskite quantum dots for efficient CO2-to-CO photoreduction

Perovskite quantum dots (PQDs) hold immense potential as photocatalysts for CO2 reduction due to their remarkable quantum properties, which facilitates the generation of multiple excitons, providing the necessary high-energy electrons for CO2 photoreduction. However, harnessing multi-excitons in PQDs for superior photocatalysis remains challenging, as achieving the concurrent dissociation of excitons and interparticle energy transfer proves elusive. This study introduces a ligand density-controlled strategy to enhance both exciton dissociation and interparticle energy transfer in CsPbBr3 PQDs. Optimized CsPbBr3 PQDs with the regulated ligand density exhibit efficient photocatalytic conversion of CO2 to CO, achieving a 2.26-fold improvement over unoptimized counterparts while maintaining chemical integrity. Multiple analytical techniques, including Kelvin probe force microscopy, temperature-dependent photoluminescence, femtosecond transient absorption spectroscopy, and density functional theory calculations, collectively affirm that the proper ligand termination promotes the charge separation and the interparticle transfer through ligand-mediated interfacial electron coupling and electronic interactions. This work reveals ligand density-dependent variations in the gas-solid photocatalytic CO2 reduction performance of CsPbBr3 PQDs, underscoring the importance of ligand engineering for enhancing quantum dot photocatalysis.

Efficient CO2 photoreduction enabled by the one-dimensional (1D) porous structured NiTiO3 nanorods

In this study, porous, and hollow nanorods of NiTiO3 (NiTiO3 NRs-p: 2–3 μm in length and 400 nm in diameter) are successfully prepared using an ethylene glycol-mediated approach at room temperature (25 °C), followed by calcination at 700 °C in air environment. Their rough surfaces and accumulated holes are advantageous for adsorption and subsequent photoreduction of carbon dioxide (CO2) under UV–vis irradiation. The NiTiO3 NRs-p exhibit superior performance in terms of photoconversion of CO2 (purity 99.999 %, 100 mL/min) into gaseous CO (57.833 μmolg−1 h−1) and CH4 (24.33 μmolg−1 h−1) with an overall CO2 selectivity (SCO2) of 89 %. In contrast, the solid NiTiO3 nanorods (NiTiO3 NRs) exhibit moderate performance in CO2 reduction, producing CO (30.33 μmolg−1 h−1) and CH4 (11.50 μmolg−1 h−1) with a CO2 selectivity of SCO2 = 60 %. NiTiO3 NRs-p exhibits superior photocatalytic activity against CO2 over other NiTiO3 morphologies with similar physical and chemical properties (such as nanoparticles (NPs) and nanofibers (NFs). This enhancement in photocatalytic activity can be attributed to the porous texture and hollow rod-like structure of NiTiO3 NRs-p, which provides a larger number of active sites to promote rapid mass transport. This unique one-dimensional (1D) structure also facilitates the separation of photogenerated electron-hole pairs, as demonstrated experimentally. This study opens a new room for a simple and facile routes for the photocatalytic conversion of CO2 into solar fuels.

Donor–π–acceptor conjugated microporous polymers for photocatalytic organic conversion with photogenerated carrier separation ability by an embedded electric field along the molecular chain

Photogenerated electron-hole pairs in conjugated microporous polymers (CMPs) recombine easily, thus donor-acceptor (D-A) structure was reported to promote the separation of photogenerated carriers, while the inevitable relationship behind them has not been established. Herein, a series of D–π–A type CMPs (Dz-B-CMP, Pz-B-CMP, and Py-B-CMP) were designed and constructed from carbazole (donor) and six-membered nitrogenous ring (acceptor). The photocatalytic performance of the prepared CMPs was evaluated in the reaction between o-phenylenediamine and benzaldehyde. Satisfactorily, Py-B-CMP exhibited the excellent photocatalytic activity with benzimidazole yield of 95.5%, and a wide range of substrate adaptability and outstanding recycling stability. Further theoretical calculations demonstrated that the excellent activity of Py-B-CMP was attributed to the built-in electric field along the molecular chain. This endowed Py-B-CMP with a powerful driving force for the separation and migration of photogenerated carriers, resulting in a remarkable photocatalytic performance. Additionally, a possible photocatalytic synthesis mechanism of benzimidazole was proposed.

Nitrogen-Doped Titanium Dioxide for Selective Photocatalytic Oxidation of Methane to Oxygenates.

Photocatalytic conversion of methane (CH4) to value-added chemicals using H2O as the oxidant under mild conditions is a desired sustainable pathway for synthesizing commodity chemicals. However, controlling product selectivity while maintaining high product yields is greatly challenging. Herein, we develop a highly efficient strategy, based on the precise control of the types of nitrogen dopants, and the design of photocatalysts, to achieve high selectivity and productivity of oxygenates via CH4 photocatalytic conversion. The primary product (methanol) is obtained in a high yield of 159.8 μmol·g-1·h-1 and 47.7% selectivity, and the selectivity of oxygenate compounds reached 92.5%. The unique hollow porous structure and substituted nitrogen sites of nitrogen-doped TiO2 synergistically promote its photo-oxidation performance. Furthermore, in situ attenuated total reflectance Fourier transform infrared spectroscopy provides direct evidence of the key intermediates and their evolution for producing methanol and multicarbon oxygenates. This study provides insights into the mechanism of photocatalytic CH4 conversion.

Experimental and computational study on removal of nitric oxide using NH2-MIL-125: Revisiting removal mechanism

The NH2-MIL-125 (NM-125) or modified NM-125 materials are used for photocatalytic removal of nitric oxide (NO). Most researchers attributed few NO2 emission during NO photocatalysis to high selectivity towards the formation of nitrate ions due to the neglect of the principle of electroneutrality and pore structure of NM-125. This may cause misleading photocatalytic mechanism of NO removal. Herein, this work proposes a new mechanism behind NO removal using NM-125 based on experimental investigations and theoretical calculations. First, experimentally, the highest NO removal efficiency of 88.54 % with negligible NO2 emission occurs at the anhydrous condition. In addition, in-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) measurements verify the presence and accumulation of NO2 as product during photocatalytic conversion of NO. Furthermore, density functional theory (DFT) calculations and grand canonical Monte Carlo (GCMC) computations demonstrate that there exist strong interactions between NO2 and -NH2 group within pores. Few NO2 is detected during experiments is probably due to its subsequent adsorption in the pores of NM-125. The new NO removal mechanism including photocatalytic conversion NO into NO2 and subsequent NO2 adsorption in the pores of NM-125 is thus proposed. This work provides a deeper insight into photocatalytic NO removal over NM-125 and its variants.

Confined bismuth single atoms and nanoparticles dual-sites constructed via reverse etching for CO2 photoreduction to CH4

Synchronizing the directional photogenerated transfer of electrons and regulating the CO2 photocatalytic reduction process are key to achieving the efficient and highly selective photocatalytic reduction of CO2. The design of highly-dispersed active sites and the efficient collaboration of multiple sites are of great importance in attaining the above target. Herein, a reverse etching route was first proposed to confine Bi single atoms and nanoparticles as dual-sites for assisting CO2 photoreduction on TiO2, avoiding the mutual masking of the active sites. The Synergism of the dual-sites achieves the hydrodeoxygenation of * COOH and ushers the directional conversion of CO2 to CH4. Highly dispersed single Bi atoms could induce the transfer of photogenerated electrons, enhance CO2 absorption, and further provide active sites for reducing CO2 to *COOH intermediates. Besides, appropriate Bi nanoparticles could promote the separation and transfer of photogenerated and inhibit the formation of hydroxyl groups; more importantly, they could promote the release of protons, which would further accelerate the conversion of *COOH to CH4. After being integrated, the optimized dual-Bi/TiO2 catalyst achieves a CH4 generation rate of 103.89 μmol·g−1·h−1 with an impressive selectivity of 96.87 % as well as remarkable durability for photocatalytic CO2 reduction. This work provides new insights into developing robust catalysts through the artful design of synergistic catalytic sites for efficient photocatalytic CO2 conversion.

Photocatalytic Conversion of Lipid to Diesel and Syngas via Engineering the Surface Proton Transfer

Photocatalytic Conversion of Lipid to Diesel and Syngas via Engineering the Surface Proton Transfer