Strong Visible Light Absorption Research Articles

The Critical Role of Anharmonic Lattice Dynamics for Macroscopic Properties of the Visible Light Absorbing Nitride Semiconductor CuTaN2

AbstractTernary nitride semiconductors are rapidly emerging as a promising class of materials for energy conversion applications, offering an appealing combination of strong light absorption in the visible range, desirable charge transport characteristics, and good chemical stability. In this work, it is shown that finite‐temperature lattice dynamics in CuTaN2 – a prototypical ternary nitride displaying particularly strong visible light absorption – exhibit a pronounced anharmonic character that plays an essential role in defining its macroscopic optoelectronic and thermal properties. Low‐frequency vibrational modes that are Raman‐inactive from symmetry considerations of the average crystal structure and unstable in harmonic phonon calculations are found to appear as intensive Raman features near room temperature. The atomic contributions to the anharmonic vibrations are characterized by combining Raman measurements with molecular dynamics and density functional theory calculations. This analysis reveals that anharmonic lattice dynamics have large ramifications on the fundamental properties of this compound, resulting in uniaxial negative thermal expansion and the opening of its bandgap to a near‐optimal value for solar energy harvesting. The atomic‐level understanding of anharmonic lattice dynamics, as well as the finding that they strongly influence key properties of this semiconductor at room temperature, have important implications for design of new functional materials, especially within the emerging class of ternary nitride semiconductors.

NOx degradation by cement mortar containing B-TiO2/MgAl-CLDH under visible light: Experimental and modeling

In this paper, an advanced photocatalyst, B-TiO2/MgAl-CLDH, was synthesized and applied in cement mortar. The photocatalytic NOx degradation ability of cement mortar containing B-TiO2/MgAl-CLDH under different initial NOx concentrations and flow rates was investigated. The results show that B-TiO2/MgAl-CLDH has stronger visible light absorption, lower recombination rate of electron-hole pairs and narrower optical band gap than commercial nano-TiO2 (P25), resulting in enhanced NOx removal efficiency. Specifically, the maximum NOx degradation ratio of B-TiO2/MgAl-CLDH is 23.4% within 30 min, which is about 5 times that of P25. For photocatalytic mortar, the initial NOx concentration (from 1.0 ppm to 2.0 ppm) and flow rate (from 1 L/min to 3 L/min) were positively correlated with NOx removal amount, while negatively correlated with NOx removal ratio. Based on the internal molecular diffusion properties of NOx, Langmuir-Hinshelwood and the power law kinetic models were used to predict the NOx degradation ability of photocatalytic mortar. The modeling of NOx degradation process presents a reliable prediction of the NOx removal ability of photocatalytic mortar, serving as a valuable tool for assessing the mortar’s NOx removal effectiveness for policymakers and engineers.

Revealing the lattice engineering of Delafossite in core–shell CuRhO2@CuGaO2 heterostructure for efficient visible light photocatalytic activity

The establishment of heterojunctions at phase interfaces represents a pivotal strategy for enhancing photocatalytic performance. However, the inferior interfacial contact caused by the mismatch of crystal structure or lattice parameters seriously hampers the rapid and smooth migration of charge carriers in traditional heterojunctions. In this work, a tightly integrated Delafossite-based core–shell CuRhO2@CuGaO2 heterojunction was judiciously designed and constructed via a hydrothermal approach. Experimental and density-functional theory calculation results co-unravel that the built-in electric field is established in the lattice-matched heterogeneous interfaces, thereby providing smooth interface charge separation and transfer via the Z-scheme pathways. Benefitting from the heterojunction effect and unique core–shell coupling architecture, the strong visible light absorption and fast spatial charge transfer are realized in the CuRhO2@CuGaO2 heterostructure. The photocurrent density of the CuRhO2@CuGaO2 heterojunction is nearly 1.25 and 3.75 times those of pristine CuRhO2 and CuGaO2, respectively. As a result, the CuRhO2@CuGaO2 heterostructure reveals an excellent photocatalytic degradation rate of tetracycline hydrochloride, achieving a 3.02 and 2.38-fold improvement than those of the CuRhO2 and CuGaO2, respectively. This work is expected to pave the way for novel insights into the design of efficient heterojunction photocatalysts to steer the rapid photocarrier flows across the heterointerface.

Construction of a photo-assisted peroxymonosulfate activation system comprised of iron phthalocyanine/O-doped carbon nitride for efficient tetracycline removal

The integration of peroxymonosulfate (PMS) activation and photocatalysis is an effective advanced oxidation technology for the degradation of water pollutants. In this study, iron phthalocyanine (FePc) is successfully loaded onto O-doped porous carbon nitride (OCN) forming a catalyst working in photo-assisted PMS activation. OCN is a metal-free light absorber with strong visible light absorption, while FePc could serve as a photosensitizer and PMS activator. At the same time, the construction of FePc/OCN heterojunction can form the strong internal electric field for charge migration between FePc and OCN. As a result, complete tetracycline (TC) removal within 30 min can be achieved over optimal FePc/OCN catalyst in the presence of light and PMS. Systematic controlled experiments were also carried out to reveal the effect of pH, anion, and aqueous matrix. Cyclic stability test and Fe leaching experiments indicate that the synthesized FePc/OCN is relatively stable and shows the potential in practical application. Furthermore, a comprehensive investigation was conducted on the reactive species generated during the reaction process as well as the degradation pathways of the target pollutants. This work aims to provide new insights into the design of efficient catalysts for photo-assisted PMS activation.

COF/In2S3 S-Scheme Photocatalyst with Enhanced Light Absorption and H2O2-Production Activity and fs-TA Investigation.

Photocatalytic hydrogen peroxide (H2O2) synthesis from water and O2 is an economical, eco-friendly, and sustainable route for H2O2 production. However, single-component photocatalysts are subjected to limited light-harvesting range, fast carrier recombination, and weak redox power. To promote photogenerated carrier separation and enhance redox abilities, an organic/inorganic S-scheme photocatalyst is fabricated by in situ growing In2S3 nanosheets on a covalent organic framwork (COF) substrate for efficient H2O2 production in pure water. Interestingly, compared to unitary COF and In2S3, the COF/In2S3 S-scheme photocatalysts exhibit significantly larger light-harvesting range and stronger visible-light absorption. Partial density of state calculation, X-ray photoelectron spectroscopy, and femtosecond transient absorption spectroscopy reveal that the coordination between In2S3 and COF induces the formation of mid-gap hybrid energy levels, leading to smaller energy gaps and broadened absorption. Combining electron spin resonance spectroscopy, radical-trapping experiments, and isotope labeling experiments, three pathways for H2O2 formation are identified. Benefited from expanded light-absorption range, enhanced carrier separation, strong redox power, and multichannel H2O2 formation, the optimal composite shows an impressive H2O2-production rate of 5713.2µmol g-1 h-1 in pure water. This work exemplifies an effective strategy to ameliorate COF-based photocatalysts by building S-scheme heterojunctions and provides molecular-level insights into their impact on energy level modulation.

DFT evaluation the photo-catalytic performance of g-C3N4 dots/ZnO with O/S doping

To develop the high-performance g-C3N4-based photo-catalysts and understand the mechanism of photo-catalytic degradation of volatile organic compounds (VOCs), we evaluated the photo-catalytic performance and corresponding catalytic mechanisms of g-C3N4 dots/ZnO (CNZO) systems using density functional theory (DFT) calculations. Our results showed that the combination of g-C3N4 dots and ZnO monolayer has a appropriate band gap and strong visible light absorption, significantly enhancing photoelectron excitation and immigration. We also observed that O/S doping exerted a significant impact on the band structure and interfacial coupling, thereby increasing the number of photoelectrons that move from the valence band (VB) of ZnO monolayer to the conduction band (CB) of g-C3N4 dots, thereby enhancing the separation of photo-generated electron-hole pairs in O/S-CNZO. Furthermore, the suitable CB and VB positions of O/S-CNZO encourage the adsorption of surface H2O and O2 molecules, leading to the generation of ·OH and ·O2− radicals crucial in VOCs degradation. This work introduces new approaches and perspectives for constructing novel photo-catalysts. Additionally, it involves a theoretical evaluation of the photo-catalytic performance of O/S-CNZO.

Photostability and visible-light-driven photoactivity enhancement of hierarchical C@ZnCdS/ZnS/MoS2

Zinc cadmium sulfide solid (Zn x Cd1−x S) related composites received great attention in photocatalytic hydrogen production because of their tunable bandgap and strong visible light absorption range. But sulfide-based metal materials commonly suffer from photo-corrosion issues. It is very important to construct the photocatalysts with high efficient activity and photostability for H2 production. Herein, we successively prepared ZnCdS/ZnS (ZCS/ZS) heterostructures, ZnCdS/ZnS/MoS2 (ZCS/ZS/M) heterostructures decorated ZCS/ZS with MoS2 quantum dots, then we obtained x-C@ZCS/ZS and x-C@ZCS/ZS/M heterostructures encapsulated ZCS/ZS and ZCS/ZS/M with carbon layer. The performance of the photocatalytic hydrogen production showed that sample 0.05-C@ZCS/ZS/M has a remarkable photocatalytic H2 evolution rate of 15.231 mmol·h−1·g−1 with noble metal-free co-catalysts. This rate was approximately 21 times higher than that of the pristine ZCS/ZS photocatalyst. The optimized sample reveals an excellent stability, without activity losses after 10 h. The improved photocatalytic activity can be attributed to the unique heterojunction structure formed by ZCS/ZS and MoS2. Additionally, the carbon films played a crucial role in providing excellent stability by spatially separating the sites for redox reactions, thereby inhibiting the recombination of photo-generated electron–hole pairs.

Ligand-Induced Synthesis of Highly Stable NM88(DB)@COF-JLU19 Composite: Accelerating Electron Flow for Visible-Light-Efficient Degradation of Tetracycline Hydrochloride.

In recent years, the response of new porous materials to visible light and their potential applications in wastewater treatment has received extensive attention from the scientific community. Metal Organic Frameworks (MOFs) and Covalent Organic Frameworks (COFs) have been the focus of attention due to their strong visible light absorption, high specific surface area, well-regulated pore structures, and diverse topologies. In this study, a novel MOF@COF composite with a high surface area, high crystallinity, and structural stability was obtained using the covalent bond formation strategy from COF-JLU19 and NH2-MIL-88B(Fe). Under visible light irradiation, the degradation of tetracycline hydrochloride by this material reached more than 90% within 10 min and was completely degraded within 30 min, which exceeded the degradation rate of individual materials. Remarkably, the catalytic activity decreased by less than 5% even after five degradation cycles, indicating good structural stability. The excellent photocatalytic performance of the NM88(DB)@COF-JLU19 hybrids was attributed to the formation of covalent bonds, which formed a non-homogeneous interface that facilitated effective charge separation and promoted the generation of hydroxyl radicals.

Porphyrin-Polyoxotungstate Molecular Hybrid as a Highly Efficient, Durable, Visible-Light-Responsive Photocatalyst for Aerobic Oxidation Reactions.

Organic-polyoxometalate (POM) hybrids have recently attracted considerable interest because of their distinctive properties and wide-ranging applications. For the construction of organic-POM hybrids, porphyrins are promising building units owing to their optical properties and reactivity, including strong visible-light absorption and subsequent singlet-oxygen (1O2*) generation. However, the practical utilization of porphyrins as photocatalysts and photosensitizers is often hindered by their own degradation by 1O2*. Therefore, there is a substantial demand for the development of porphyrin-derived photocatalysts with both high efficiency and durability. Herein, we present a porphyrin-polyoxotungstate molecular hybrid featuring a face-to-face stacked porphyrin dimer (I) fastened by four lacunary polyoxotungstates. Hybrid I exhibited remarkable efficiency and durability in photocatalytic aerobic oxidation reactions, and the selective oxidation of various dienes, alkenes, sulfides, and amines proceeded using just 0.003 mol % of the catalyst. Mechanistic investigations suggested that the high activity of I stems from the efficient generation of 1O2*, resulting from the heavy-atom effect of POMs. Furthermore, despite its high efficiency in 1O2* generation compared to free porphyrins, I exhibited superior durability against 1O2*-induced degradation under photoirradiation.

Embedding In2.77S4 into NCDs-(g-C3N5) hybrid materials to enhance photocatalytic hydrogen production and rhodamine B degradation by constructing electron-highways

We propose a potential solution to the problem of severe recombination of photogenerated electron-hole pairs in composite catalysts. The g-C3N5 has better electronic properties and photocatalytic efficiency than g-C3N4, and In2.77S4 is a typically sulfur-deficient sulfide with stable structure and strong visible light absorption. However, the In2.77S4/g-C3N5 composite catalyst has severe recombination of photogenerated electron-hole pairs, which limits its performance. To solve this problem, we introduced NCDs (nitrogen-doped carbon dots) into g-C3N5 to prepare hybrid material, which subsequently combined with In2.77S4. The high-efficiency S-scheme In2.77S4/NCDs-(g-C3N5) heterojunction was prepared by electrostatic self-assembly to prevent the thermal decomposition of g-C3N5. Photocatalytic experiments show that In2.77S4/NCDs-(g-C3N5) composite has excellent photodegradation efficiency of rhodamine B (94.23 %), high photocatalytic H2 production (7134 μmol·g−1h−1), and good reusability in the visible light. The H2 evolution rate of In2.77S4/NCDs-(g-C3N5) composite is about 30.10, 3.89 and 3.08 folds than In2.77S4, g-C3N5 and In2.77S4/g-C3N5, respectively. The photoluminescence spectroscopy (PL) and the time-resolved fluorescence decay (TRF) indicated a substantial reduction in photogenerated carrier recombination of In2.77S4/NCDs-(g-C3N5) compared to In2.77S4/g-C3N5. Taking advantage of the high conductivity of NCDs, the electron-highways were constructed in heterojunctions, which accelerates the interfacial depletion of useless electron-hole pairs and reserved more strong redox carriers. In addition, we inferred a possible energy band structure for In2.77S4/NCDs-(g-C3N5) heterojunction based on the energy band bending theory. This work provides an expandable idea for improving the utilization efficiency of photogenerated carriers by constructing electron-highways in heterojunctions.

Visible-light absorption of indium oxide thin films via Bi3+ doping for visible-light-responsive photocatalysis

In2O3 is commonly used as a photocatalyst for hydrogen energy storage. However, it has the disadvantage of a large optical bandgap (3.7 eV), resulting in low absorption of visible light, which corresponds to 50 % of sunlight energy. Band engineering is an efficient method to add visible-light responsivity to wide-bandgap In2O3. In this study, the band engineering of In2O3 was performed by incorporating bismuth to obtain an intermediate band that could absorb visible light. Thin films of In2O3 doped with bismuth (IBO) were grown using mist chemical vapor deposition (CVD), and their optical properties were investigated. Transmittance measurements showed that the IBO thin film exhibited absorption in the visible light region of 400–700 nm, indicating that the introduction of bismuth created an intermediate band in the bandgap of In2O3. IBO thin films with platinum as a co-catalyst could almost completely degrade methylene blue under visible light (420 nm) irradiation for 72 h. Thus, the incorporation of bismuth into In2O3 via mist CVD and the strong absorption of visible light owing to its intermediate band were demonstrated. This study demonstrates that IBO thin films with large absorption in the visible-light region are promising materials for visible-light-responsive photocatalysts.

Oxidation-state sensitive light-induced dynamics of Ruthenium-4H-Imidazole complexes.

Oxidized molecular states are key intermediates in photo-induced redox reactions, e. g., intermolecular charge transfer between photosensitizer and catalyst in photoredox catalysis. The stability and longevity of the oxidized photosensitizer is an important factor in optimizing the respective light-driven reaction pathways. In this work the oxidized states of ruthenium(II)-4H-imidazole dyes are studied. The ruthenium complexes constitute benchmark photosensitizers in solar energy interconversion processes with exceptional chemical stability, strong visible light absorption, and favourable redox properties. To rationalize the light-induced reaction in the oxidized ruthenium(III) systems, we combine UV-vis absorption, resonance Raman, and transient absorption spectroelectrochemistry (SEC) with time-dependent density functional theory (TDDFT) calculations. Three complexes are compared, which vary with respect to their coordination environment, i. e., combining an 4H-imidazole with either 2,2'-bipyridine (bpy) or 2,2';6'2"-terpyridine (tpy) coligands, and chloride or isothiocyanate ligands. While all oxidized complexes have similar steady state absorption properties, their excited state kinetics differ significantly; the study thus opens the doorway to study the light-driven reactivity of oxidized molecular intermediates in intermolecular charge transfer cascades.

Identification of Crucial Photosensitizing Factors to Promote CO2 -to-CO Conversion.

The sensitizing ability of a catalytic system is closely related to the visible-light absorption ability, excited-state lifetime, redox potential, and electron-transfer rate of photosensitizers (PSs), however it remains a great challenge to concurrently mediate these factors to boost CO2 photoreduction. Herein, a series of Ir(III)-based PSs (Ir-1-Ir-6) were prepared as molecular platforms to understand the interplay of these factors and identify the primary factors for efficient CO2 photoreduction. Among them, less efficient visible-light absorption capacity results in lower CO yields of Ir-1, Ir-2 or Ir-4. Ir-3 shows the most efficient photocatalytic activity among these mononuclear PSs due to some comprehensive parameters. Although the Kobs of Ir-3 is ≈10 times higher than that of Ir-5, the CO yield of Ir-3 is slightly higher than that of Ir-5 due to the compensation of Ir-5's strong visible-light-absorbing ability. Ir-6 exhibits excellent photocatalytic performance due to the strong visible-light absorption ability, comparable thermodynamic driving force, and electron transfer rate among these PSs. Remarkably, the CO2 photoreduction to CO with Ir-6 can achieve 91.5 μmol, over 54 times higher than Ir-1, and the optimized TONC-1 can reach up to 28160. Various photophysical properties of the PSs were concurrently adjusted by fine ligand modification to promote CO2 photoreduction.

Stacked Covalent Organic Ribbons Perpendicular to Graphene Oxide Sheets; a 1D-p-2D Design for Photocatalytic Tandem Reactions.

Development of one dimensional covalent organic frameworks (1D-COFs) with potential in light absorption and catalysis is still challenging, due to their rapid interpenetration to form 2D and 3D porous structures. Here we report a successful synthesis of imine-linked 1D covalent organic ribbons (COR), using two simple linear building blocks 1,4-Benzenediamine (Bda) and [2,2'-Bipyridine]-5,5'-dicarbaldehyde (Bpy). The obtained 1D structure with nanorod morphology could keep its physicochemical characteristic properties when it is perpendicular to the surface of graphene oxide (GO) sheets (1D-p-2D structure). Due to an AB π- π stacking and efficient charge transfer between perpendicular 1D COR and GO sheets, the obtained nanocomposite showed strong visible light absorbance (400-700 nm) with coefficient of 4.400 M-1 cm-1 and decreased recombination rate of photogenerated reactive species by 92 %. The strategy of 1D-p-2D light driven system greatly enhanced the photocatalytic activity in practical applications such as both oxidation and hydrogenation tandem reactions to a rate constant of higher than 0.02 min-1 . This study presents the first case of 1D covalent organic polymers grown perpendicularly on a carbon-based layer for boosting electron mobility through the junction between the two components.

The g-ZnO/PtSe2 S-scheme heterojunction with controllable band structure for catalytic hydrogen production

The structural, photo-electronic catalytic properties, and the biaxial strain modulation of band structure for the g-ZnO/PtSe2 S-scheme heterojunction are studied by First-principles calculation. The stability for the heterojunction is verified by negative generation energy and ab-initio molecular dynamic simulation. The photo-generated carrier motion and band structure are in accordance with the S-scheme, and the electron mobility of up to 2023 cm2/Vs is obtained in the Zigzag direction. The absorption of visible light is improved, and an absorption peak of 2.893 × 105 cm−1 at 434.337 nm is observed. Due to a higher redox potential, photocatalytic water splitting can occur in the pH range of 0∼14, and a high solar to hydrogen (STH) efficiency of 30.7 % is obtained. The over-potential of hydrogen evolution reaction (HER) (3.719 V) is lower than oxygen evolution reaction (4.128 V), which tends to proceed at the g-ZnO interface. When the strain ≥4 %, the bandgap alignment of the g-ZnO/PtSe2 heterojunction changes from a staggered gap (Type-Ⅱ) to straddling gap (Type-Ⅰ). The g-ZnO/PtSe2 heterojunction exhibits high electron mobility, high STH efficiency, strong absorption of visible light, strong HER ability, and a tunable band structure, expecting as a promising candidate material for catalytic water splitting.

Advanced Self-powered Visible-light Photodetector Based on Asymmetric Au/CsPbBr3/SmB6 Junction

As a typical all-inorganic perovskite, CsPbBr3 has strong visible-light absorption, large carrier mobility and long carrier diffusion length, suggesting it has potential applications in visible-light detection. Many attempts have been...

Strain-induced excellent photocatalytic performance in Z-scheme BlueP/γ-SnS heterostructures for water splitting.

Constructing Z-scheme heterojunction photocatalysts with high solar-to-hydrogen (STH) efficiency is a practical alternative to produce clean and recyclable hydrogen energy on a large scale. This paper presents the design of stable Z-scheme blue phosphorene (BlueP)/γ-SnS heterostructures with excellent photocatalytic activities by applying strains. The first-principles calculations show that the BlueP/γ-SnS heterobilayer is a type-I heterojunction with an indirect bandgap of 1.41 eV and strong visible-light absorption up to 105 cm-1. Interestingly, biaxial strains (ε) can effectively regulate its bandgap width (semiconductor-metal) and induce the band alignment transition (type-I-type-II). Compressive and tensile strains can significantly enhance the interfacial interaction and visible-light absorption, respectively. More intriguingly, compressive strains can not only modulate the heterojunction types but also make the band edges meet the requirements for overall water splitting. In particular, the Z-scheme (type-I) BlueP/γ-SnS bilayer at -8% (-2%) strain exhibits a relatively high STH efficiency of 18% (17%), and the strained Z-scheme system (-8% ≤ ε ≤ -6%) also exhibits high and anisotropic carrier mobilities (158-2327 cm2 V-1 s-1). These strain-induced outstanding properties make BlueP/γ-SnS heterostructures promising candidates for constructing economically feasible photocatalysts and flexible nanodevices.

La/Fe bimetallic MOF-derived p-LaFeO3/n-CdS heterojunction: efficient photocatalytic degradation of organic contaminants and adsorption isotherms

Designing efficient catalysts with strong redox characteristics and high visible light absorption in the field of photocatalysis.

Bio-inspired synthesis of N-doped TiO2/C nanocrystals using jellyfish mucus with high visible-light photocatalytic efficiency.

Non-metal doping of titanium dioxide (TiO2) has been widely investigated, because it can facilely improve the optical response of TiO2 under visible light excitation in environmental pollution treatments. In the ongoing efforts, however, little consideration has been given to the use of harmful marine organisms as dopants. Here, we employed the natural mucus proteins of the large harmful jellyfish Aurelia coerulea and Nemopilema nomurai, which have frequently bloomed in East Asian marginal seas in recent decades, to synthesize mesoporous nitrogen-doped TiO2 nanocrystals modified with carbon (N-TiO2/C) by a simple hydrothermal method. These nanocrystals were composed of predominantly anatase phase and a small amount of brookite phase TiO2. Their mesoporous structures changed with the variation of the volume ratio of jellyfish mucus added to tetrabutyl titanate (TBT). At the same ratio, larger surface area and pore volume but smaller pore size were observed in N-TiO2/C nanocrystals from N. nomurai rather than A. coerulea. Nitrogen was determinately doped into the lattice of the prepared nanocrystals and the carbon species were modified on their surfaces, which narrowed the band gap, facilitated the separation of photogenerated electron-hole pairs and favored the absorption of visible light, thus improving their visible light photocatalytic activity. The photocatalytic degradation efficiency of Rhodamine B (RhB) under visible light irradiation first increased and then decreased with the gradual increase of the volume ratio of jellyfish mucus proteins to TBT. The maximum reached 97.52% in 20 min from N-TiO2/C nanocrystals synthesized using N. nomurai mucus at the volume ratio of 4 : 1, which showed a remarkably strong visible light absorption, lower band gap energy and smaller electron transfer resistance. These N-TiO2/C nanocrystals also had a relatively stable crystal structure in multiple degradation reactions. The main active species including superoxide radicals (˙O2 -), photogenerated holes (h+) and hydroxyl radicals (˙OH) were found to play a major role in the degradation process of RhB. This study highlights the potential high-value reapplication of harmful jellyfish mucus as a natural organic matrix in fabricating advanced materials with optimized functional properties.

A cryptand-like Ti-coordination compound with visible-light photocatalytic activity in CO2 storage.

A cryptand-like Ti-coordination compound, namely Ti12Cs, comprising two Ti6-salicylate cages and hosting two Cs+ ions, was synthesized by the solvothermal method. It exhibits strong visible-light absorption with an absorption band edge of 652 nm, attributed to the electron transition from salicylate ligands to Ti ions. Electrochemical impedance, visible-light transient photocurrent response, and photoluminescence spectra confirm that Ti12Cs has excellent visible-light response and charge-separation properties. Ti12Cs can be used as a heterogeneous and recyclable photocatalyst for CO2/epoxide cycloaddition, with high utilization efficiency of visible-light under mild conditions. The mechanism investigation points to a synergistic effect of photocatalysis and Lewis acid catalysis.