Search Results (151)

Photocatalytic reduction of carbon dioxide (CO₂) into high-value multicarbon products, such as ethylene (C₂H₄), remains a significant challenge due to the difficult C-C coupling process. Potassium poly(heptazine imide) (K-PHI) is a promising photocatalyst, yet efficiently exchanging its interlayer cations to tune catalytic selectivity without causing structural degradation is difficult. Herein, an efficient and green supercritical CO₂ (SC CO₂) assisted ion-exchange strategy was developed to successfully prepare a series of mono-/di-/trivalent cation-doped M-PHI photocatalysts (M = H⁺, Na⁺, Sr⁺, Ca²⁺, Co²⁺, Fe³⁺). Systematic characterizations confirmed that the SC-CO₂ treatment successfully achieved in-depth cation substitution without destroying the intrinsic heptazine framework, effectively regulating the interlayer structure and significantly optimizing the photoelectrochemical charge separation. Among the prepared samples, H-PHI exhibited the optimal photocatalytic CO₂ reduction performance with an outstanding selectivity toward C₂H₄ generation. Under simulated sunlight irradiation for 3 h, the yields of CO, CH₄, and C₂H₄ C₂H₄ C₂H₄ reached 3564.87, 807.32, and 40.00 μmol·g⁻¹, respectively, significantly outperforming pristine K-PHI and other metal-doped samples. Crucially, isotope-tracing experiments utilizing a SC CO₂-DCl treatment detected deuterated CH₄ and C₂H₄ products, providing direct evidence that the hydrogen in the carbon products originates from the introduced protons, thereby elucidating the precise reaction pathway for C-C coupling. This study provides a green and efficient supercritical CO₂ ion exchange strategy for the cation engineering of crystalline carbon nitride, and also offers new ideas and methods for designing high-activity photocatalysts for photocatalytic CO₂ reduction. Full article

Photocatalytic CO₂ reduction to high-value-added C₂+ products is a practical route from an economic viewpoint for advancing the industrialization of CO₂ conversion. Despite significant progress in catalyst modification in recent years (such as defect engineering, heterostructure construction, and single-atom modification), the generation of C₂+ products still faces challenges due to the slow kinetics of multi-electron reactions and the high thermodynamic barrier for C-C coupling. Moreover, the severely imbalanced molar ratio of CO₂ to H₂O in the traditional liquid-phase reaction systems exacerbated the challenge to the unfavorable situation. This article summarizes various strategies to improve the yield of C₂+ products through the regulation of reaction environments, including: (1) increasing the partial pressure of CO₂ to enhance its solubility; (2) using alternative solvents like ionic liquids to reduce water content; (3) transitioning the reaction system from liquid phase to gas phase; (4) designing a three-phase (gas–liquid–solid) interface or floating photocatalysts to optimize reactant transfer and local concentration; (5) utilizing photothermal synergistic effects to enhance the reaction temperature and efficiency under concentrated light. It also discusses the role of different reactor designs in improving the reaction environment. Finally, it emphasizes that future research should pay more attention to the optimization of the reaction environment engineering in addition to catalyst design, providing new perspectives for achieving efficient and highly selective C₂+ products in CO₂ photoreduction. Full article

A type of photothermal catalyst was prepared by photoreducing cobalt ions with geopolymer/Ag₉(SiO₄)₂NO₃ (GA). The loading of Co⁰ significantly expanded the visible-light response range. Due to the photoreduction effect, the loading of Ag⁰ and Co⁰ facilitated the transfer of photogenerated electrons and strong thermal excitation, significantly enhancing the photothermal synergy effect. The photothermal catalyst achieved a CO production rate of 70.20 mmol·g_cat⁻¹·h⁻¹, and the selectivity of CO reached 97.67% at 400 °C. The CO product rate in the fifth cycle still reached 68.8 mmol·g_cat⁻¹·h⁻¹, which provided a reference for extending the functionality of photocatalysts after the photoreduction of heavy metal ions. Full article

Photocatalytic reduction of CO₂ into valuable solar fuels represents a promising strategy to address both energy crises and carbon emissions. Bismuth-based semiconductors have emerged as attractive visible-light-driven photocatalysts due to their suitable band structures, layered architectures, and tunable morphologies. This review systematically summarizes recent advances in Bi-based photocatalysts for CO₂ photoreduction. First, the fundamental principles and key challenges of CO₂ photoreduction are outlined. Subsequently, the structural and electronic characteristics of typical Bi-based materials, including Bi₂O₃, Bi₂S₃, Bi₂MO₆ (M = W; Mo), BiVO₄, and BiOX (X = Cl; Br; I), are discussed. Emphasis is placed on design strategies to enhance photocatalytic performance, such as vacancy engineering, microstructure control, crystal facet engineering, heterojunction construction, cocatalyst loading, and their combinations. A comprehensive comparison of catalytic activities under various conditions is also provided. Finally, current limitations and future perspectives are highlighted, aiming to guide the rational design of efficient and stable Bi-based photocatalysts for CO₂ conversion. Full article

The solar-driven conversion of CO₂ into long-chain (C₃₊) products offers a sustainable pathway to mitigate climate change, produce carbon-neutral fuels and value-added chemicals. Over the past few decades, significant advances have been achieved in CO₂ photoreduction; however, most systems still favor C₁ products (CO, CH₄) or C₂ intermediates. However, the synthesis of C₃₊ products poses a formidable challenge due to the complex multi-electron transfer steps required for C–C bond formation. This review provides a concise overview of recent progress in solar-driven photocatalytic and photothermal CO₂ reduction, with a specific focus on the formation of C₃₊ products. The fundamental principles are discussed, including the critical role of C–C coupling mechanisms and the stepwise reaction pathways for C₃₊ products. It highlights how the extended carbon chain length significantly increases the complexity and reduces selectivity, with the suppression of side reactions being a primary research objective. Key catalytic strategies, such as the use of copper-based materials, are examined for their unique ability to facilitate these demanding transformations. Finally, the major challenges are outlined, and a future outlook for this field is provided, with an emphasis on the need for advanced catalyst design and in situ characterization to unlock the potential of solar fuels. Full article

In this study, we present the synthesis of TiO₂ nanomaterials doped with different mol% cobalt, prepared by the sol–gel method for CO₂ reduction using UV light. The nanomaterials were calcined at 400 °C for 4 h. Characterization of the nanomaterials was performed using XRD-Rietveld refinement, XPS, Raman spectroscopy, diffuse reflectance spectroscopy (DRS), SEM-EDS, TEM-HRTEM, BET area, photoluminescence, and electrochemical techniques. The results show that the incorporation of cobalt into TiO₂ modifies the structural properties, binding energies, and oxygen vacancy generation, it undergoes a shift towards the visible region, the recombination of charge carriers decreases, and the BET area is slightly modified. The photoreduction of CO₂ with the highest production of methane and ethane is with 1% mol% of cobalt in TiO₂, exhibiting values 3 and 14 times higher with respect to TiO₂, which is attributed to the efficiency in the separation of photogenerated species (e⁻/h⁺) as a consequence of the generation of energetic states that function as an electron trap and thus improve the photocatalytic activity for the photoreduction of CO₂. Full article

Photocatalytic reduction of CO₂ into value-added chemicals offers a sustainable route to mitigate greenhouse gas emissions while producing renewable fuels. However, conventional TiO₂-based systems suffer from limited visible-light activity and inefficient reactor configurations. Here, we developed electrospun polyacrylonitrile (PAN) membranes embedded with TiO₂-Cu₂O heterojunction nanoparticles and integrated them into a custom crossflow photocatalytic membrane reactor. The reactor employed bifacial illumination using a solar simulator (front) and a xenon/mercury lamp (back), each calibrated to 1 Sun (100 mW·cm⁻²). Membrane morphology was characterized by SEM, and chemical composition was confirmed by XPS. Photocatalytic performance was evaluated in CO₂-saturated 0.5 M potassium bicarbonate solution under continuous flow. The PAN/ TiO₂-Cu₂O membrane exhibited a methanol production rate of approximately 300 μmol·g⁻¹·h⁻¹ under dual-light illumination, outperforming single illumination, PAN-TiO₂, and PAN controls. Enhanced activity is attributed to extended visible-light absorption, improved charge separation at the TiO₂-Cu₂O heterojunction, and optimized photon flux through bifacial illumination. The electrospun architecture provided high surface area and porosity, facilitating CO₂ adsorption and catalyst dispersion. Combining heterojunction engineering with bifacial reactor design significantly improves solar-driven CO₂ conversion. This approach offers a scalable pathway for integrating photocatalysis and membrane technology into sustainable fuel synthesis. Full article

In this study, we report a reproducible in situ photochemical method for the simultaneous synthesis of metallic and hybrid metal/metal oxide nanoparticles (NPs) within a UV–curable polymer matrix. A series of epoxy diacrylate-based formulations (BEA) was prepared, consisting of Epoxy diacrylate, Di(Ethylene glycol)ethyl ether acrylate (DEGEEA), and Phenylbis (2,4,6-trimethylbenzoyl) phosphine oxide (BAPO), which served as a Type I photoinitiator. These formulations were designed to enable the simultaneous photopolymerization and photoreduction of metal precursors at various Ag⁺/Co²⁺ ratios, resulting in nanocomposites containing in situ-formed Ag NPs, cobalt oxide NPs, and hybrid Ag–Co₃O₄ nanostructures. The photochemical, magnetic, and dielectric properties of the resulting nanocomposites were evaluated in comparison with those of the pure polymer using UV–Vis and Fourier Transform Infrared Spectroscopy (FT-IR), Photo-Differential Scanning Calorimetry (Photo-DSC), Thermogravimetric Analysis (TGA), Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Impedance Analysis, and Vibrating Sample Magnetometry (VSM). Photo-DSC studies revealed that the highest conversion values were obtained for the BEA-Ag₁Co₁, BEA-Co, and BEA-Ag₁Co₂ samples, demonstrating that the presence of Co₃O₄ NPs enhances polymerization efficiency because of cobalt species participating in redox-assisted radical generation under UV irradiation, increasing the number of initiating radicals and leading to faster curing and higher final conversion. On the other hand, the Ag NPs, due to the SPR band formation at around 400 nm, compete with photoinitiator absorbance and result in a gradual decrease in conversion values. Crystal structures of the NPs were confirmed by XRD analyses. The dielectric and magnetic characteristics of the nanocomposites suggest potential applicability in energy-storage systems, electromagnetic interference mitigation, radar-absorbing materials, and related multifunctional electronic applications. Full article

With the dual challenges of global energy scarcity and worsening environmental issues, the efficient and selective conversion of CO₂ into CH₄-an environmentally friendly fuel with high energy density—offers considerable application potential. In this study, a 2D-Cu₂O/carbon nitride (2D-Cu₂O/CN) heterojunction catalyst was successfully prepared. Notably, 2D-Cu₂O/CN shows enhanced light absorption capacity, reduced charge-transfer resistance, and efficient separation of photogenerated electron–hole pairs. It exhibits a CH₄ yield of 14.1 μmol·g⁻¹·h⁻¹, 4-fold higher than that of CN. This study provides a feasible approach for the design of high-efficiency photocatalysts for CO₂ reduction to CH₄. Full article

The increasing atmospheric concentration of CO₂ is a major contributor to global climate change, underscoring the urgent need for effective strategies to convert CO₂ into value-added products. In this sense, a composite was successfully synthesized by combining clinoptilolite zeolite (CZ) with varying amounts of copper oxide (CuO-1% and 10%) for CO₂ photoreduction. The composites were characterized using insightful techniques, including XRD, nitrogen physisorption, DRS, and SEM. The results confirmed the incorporation and dispersion of CuO within the CZ support. The XRD analysis revealed characteristic crystalline CuO peaks. Despite the low surface area (<15 m²·g⁻¹) and macroporous nature of the samples, EDS imaging revealed an effective and homogeneous dispersion of CuO, indicating efficient surface distribution. UV–Vis diffuse reflectance spectroscopy revealed band gap energies of 3.30 eV (CZ), 3.38 eV (1%-CuO/CZ), and 1.75 eV (10%-CuO/CZ), highlighting the pronounced electronic changes resulting from CuO incorporation. Photocatalytic tests conducted under UVC irradiation (λ = 254 nm) revealed that 10%-CuO/CZ exhibited the highest CO and CH₄ production, 35 µmol·g⁻¹ and 3.6 µmol·g⁻¹, respectively. The composite also delivered the highest CO productivity (5.91 µmol·g⁻¹·h⁻¹), approximately 3.5 times that of pristine CZ, in addition to achieving the highest CH₄ productivity (0.60 µmol·g⁻¹·h⁻¹). Furthermore, turnover frequency (TOF) analysis normalized per Cu site revealed that CuO incorporation not only enhances total productivity but also improves the intrinsic catalytic efficiency of the active copper centers. Overall, the synthesized composites demonstrate promising potential for CO₂ photoreduction, driven by synergistic structural, electronic, and morphological features. Full article

The development of versatile photocatalysts is crucial for comprehensive solutions to the intertwined challenges of the energy crisis and environmental pollution. This study presents a novel Bi₃TiNbO₉/Bi₂MoO₆ (BTNO/BMO) heterojunction fabricated via a solvothermal method. Advanced characterization techniques verified the successful synthesis of the as-integrated BTNO/BMO heterostructure. The BTNO/BMO composite exhibited superior performance in multiple applications: efficient degradation of tetracycline reaching 90.2%, removal of gaseous nitric oxide (NO), and photocatalytic reduction of carbon dioxide (CO₂) to carbon monoxide (CO) with a yield of 51.3 μmol·g⁻¹. The constructed Type-II heterojunction demonstrated a remarkable ability to suppress charge recombination, thereby significantly enhancing the photocatalytic activity. This work highlights the dual-functional capability of the BTNO/BMO heterojunction for simultaneous environmental purification and fuel production, providing a promising material platform and a strategic design concept for sustainable technological development. Full article

The photocatalytic reduction of CO₂ in aqueous media offers a sustainable route for solar-to-fuel conversion, yet remains challenged by CO₂’s thermodynamic stability and kinetic inertness, low solubility, and competitive hydrogen evolution. Here, we investigate the interplay between ionic liquids (ILs), photocatalyst supports, and additive composition in directing product selectivity among CO, CH₄, and H₂. Using imidazolium acetate as a benchmark, we demonstrate that ILs not only pre-activate CO₂ but can also undergo decomposition pathways under illumination, notably Kolbe-type reactions leading to methane formation from acetate rather than from CO₂. Comparative studies of Pd-decorated TiO₂ and g-C₃N₄ nanosheets reveal distinct behaviors driven by their interfacial interactions with the imidazolim-based ionic liquid: weak interaction with TiO₂ strongly promotes hydrogen evolution, whereas strong coupling with g-C₃N₄ synergizes with C₁C₄ImOAc to trigger acetate-derived Kolbe reactivity. The systematic evaluation of alternative salts confirms the determinant role of anion basicity and medium-pH-basic anions facilitate CO₂ activation, whereas weakly basic or non-coordinating anions favor water splitting. Overall, these results clarify the dual role of ionic liquids as both CO₂ activators and sacrificial agents, and highlight design principles for improving product selectivity and efficiency in aqueous CO₂ photoreduction systems. Full article

Photocatalytic CO₂ reduction holds great potential for sustainable solar fuel production, yet its practical application is often limited by inefficient charge separation and poor product selectivity. The photothermal effect presents a viable strategy to address these challenges by reducing activation energies and accelerating reaction kinetics. In this work, we report a rationally designed CN-B/Ti₃C₂ heterojunction that effectively leverages photothermal promotion for enhanced CO₂ reduction. The black carbon nitride (CN-B) framework, synthesized via a one-step calcination of urea and Phloxine B, exhibits outstanding photothermal conversion, reaching 131.4 °C under 300 mW cm⁻² illumination, which facilitates CO₂ adsorption and charge separation. Coupled with Ti₃C₂ MXene, the optimized composite (3:1) achieves remarkable CO and CH₄ production rates of 80.21 and 35.13 μmol g⁻¹ h⁻¹, respectively, without any cocatalyst—representing a 2.9-fold and 8.8-fold enhancement over CN-B and g-C₃N₄ in CO yield. Mechanistic studies reveal that the improved performance stems from synergistic effects: a built-in electric field prolongs charge carrier lifetime (3.15 ns) and reduces interfacial resistance, while localized heating under full-spectrum light further promotes CO₂ activation. In situ Fourier transform infrared (FTIR) spectroscopy confirms the accelerated formation of key intermediates (*COOH and *CO). The catalyst also maintains excellent stability over 24 h. This study demonstrates the promise of combining photothermal effects with heterojunction engineering for efficient and durable CO₂ photoreduction. Full article

The photocatalytic reduction of carbon dioxide (CO₂) into energy-dense fuels using visible light provides a sustainable approach for solar-to-chemical energy transformation. Among the diverse metal molecular systems developed, ruthenium (II) (Ru(II)) complexes have emerged as promising catalysts due to their superior redox properties, strong visible light absorption, and customizable ligand structures. This review explores recent advances in Ru(II)-catalyzed CO₂ photoreduction, with particular attention given to catalyst design strategies, mechanistic pathways, and system integration methodologies. Key configurations, including photosensitizer/catalyst (PS/Cat) mixed systems, covalently bonded dyads, and hybrid/supramolecular frameworks, are evaluated in terms of efficiency, turnover numbers (TON), and selectivity. A critical analysis of challenges such as competing H₂ generation, inefficient charge transfer, and limited long-term stability is presented. Emerging trends toward the use of pincer ligands, transition metal integration, and self-photosensitizing frameworks are discussed as potential approaches for improving efficiency. Overall, this review offers insights into the structural and mechanistic features driving CO₂ photoreduction and provides perspectives for the rational design of next-generation Ru-based photocatalytic systems for efficient solar CO₂ conversion and the photocatalytic reduction of carbon dioxide (CO₂) into energy-dense fuels using visible light. Full article

Photocatalytic conversion of CO₂ to hydrocarbon fuels offers a promising pathway for sustainable renewable energy production. In this study, a ZnO/ZnFe₂O₄ composite featuring a Type-II heterojunction was synthesized through a facile one-step hydrothermal approach, significantly enhancing visible-light-driven CO₂ reduction activity. The optimized catalyst exhibits CH₄ and CO production rates that are 3.3 and 4.9 times higher, respectively, than those of pristine ZnFe₂O₄ over 6 h. This significant enhancement in photocatalytic performance is attributed to the Type-II band alignment, which not only broadens light absorption but also greatly promotes efficient charge separation. It is corroborated by a series of experimental evidence: a two-fold enhancement in photocurrent response, a 15.1% reduction in PL intensity, decreased electrochemical impedance, and an extended charge carrier lifetime. Furthermore, in situ FTIR spectroscopy confirms that the heterojunction facilitates the formation of key intermediates (specifically *COOH and HCOO⁻). This study highlights the importance of precise interface design based on a Type-II heterojunction in heterostructured composite catalysts and provides mechanistic insights for developing highly efficient CO₂ photoreduction systems. Full article