Photocatalytic CO2 Reduction Activity Research Articles

Covalent OrganicFramework with Donor1-Acceptor-Donor2 Motifs Regulating Local Charge of Intercalated Single Cobalt Sites for Photocatalytic CO2 Reduction to Syngas.

Covalent organic framework (COF) has attracted increasing interest in photocatalytic CO2 reduction, but it remains a challenge to achieve high conversion efficiency owing to the insufficient active site and fast charge recombination. Rationally optimizing the electronic structures of COF to regulate the local charge of active sites precisely is the key point to improving catalytic performance. Herein, intercalated single Co sites coordinated by imine-N motifs have been designed by using trinuclear copper-based imine-COFs with distinct electronic moieties via a molecular engineering strategy. It is confirmed that the charge delivery property and local charge distribution of these heterometallic frameworks can be profoundly influenced by electronic structures. Among these featured structures with mixed-state copper clusters, Co/Cu3-TPA-COF stands out for an exceptional photocatalytic CO2 reduction activity and tunable syngas (CO/H2) ratio by changing various bipyridines. Experimental and theoretical results indicate that interlayer Co-imine N motifs on the donor1-acceptor-donor2 structures facilitate the formation of a highly separated electron-hole state, which effectively induces the oriented electron transfer from dual electron donors to Co centers, achieving an enhanced CO2 activation and reduction. This work opens up an avenue for the design of high-performance COF-based catalysts for photocatalytic CO2 reduction.

Boosting Solar‐Driven CO2 Conversion to Ethanol via Single‐Atom Catalyst with Defected Low‐Coordination Cu‐N2 Motif

In this paper, we report a high‐performance carbon nitride supported Cu single‐atom catalyst featuring defected low‐coordination Cu‐N2 motif (Cu‐N2‐V). Lead many recently reported photocatalysts and its Cu‐N3 and Cu‐N4 counterparts, Cu‐N2‐V exhibits superior photocatalytic activity for CO2 reduction to ethanol, delivering 69.8 μmol g‐1 h‐1 ethanol production rate, 97.8% electron‐based ethanol selectivity, and a yield of ~10 times higher than Cu‐N3 and Cu‐N4. Revealed by the extensive experimental investigation combined with the DFT calculation, the superior photoactivity of Cu‐N2‐V stems from its unique defected Cu‐N2 configuration. Firstly, Cu in Cu‐N2‐V exist in Cu+/Cu2+ dual valence states, although predominantly in Cu+. The Cu+ sites support CO2 activation and the Cu+/Cu2+ sites are conducive for strong *CO adsorption and subsequent *CO‐*CO dimerization enabling C‐C coupling. Secondly, the Cu sites in Cu‐N2‐V are rich in electrons and thus highly active. Together they dictate the rate‐determining step on CO2 photoreduction to ethanol and lower the Gibbs free energy change. Furthermore, the defected configuration also promotes light adsorption and charge separation efficiency. Collectively, these make Cu‐N2‐V an effective and high‐performance catalyst for solar‐driven CO2 conversion to ethanol. This study also reveals the valence state change of Cu in Cu‐N2‐V during the CO2 photoreduction reaction.

Boosting Solar-Driven CO2 Conversion to Ethanol via Single-Atom Catalyst with Defected Low-Coordination Cu-N2 Motif.

In this paper,we report a high-performance carbon nitride supported Cu single-atom catalyst featuring defected low-coordination Cu-N2 motif (Cu-N2-V). Lead many recently reported photocatalysts and its Cu-N3 and Cu-N4 counterparts, Cu-N2-V exhibits superior photocatalytic activity for CO2 reduction to ethanol, delivering 69.8 μmol g-1 h-1 ethanol production rate, 97.8% electron-based ethanol selectivity, and a yield of ~10 times higher than Cu-N3 and Cu-N4. Revealed by the extensive experimental investigation combined with the DFT calculation, the superior photoactivity of Cu-N2-V stems from its unique defected Cu-N2 configuration. Firstly, Cu in Cu-N2-V exist in Cu+/Cu2+ dual valence states, although predominantly in Cu+. The Cu+ sites support CO2 activation and the Cu+/Cu2+ sites are conducive for strong *CO adsorption and subsequent *CO-*CO dimerization enabling C-C coupling. Secondly, the Cu sites in Cu-N2-V are rich in electrons and thus highly active. Together they dictate the rate-determining step on CO2 photoreduction to ethanol and lower the Gibbs free energy change. Furthermore, the defected configuration also promotes light adsorption and charge separation efficiency. Collectively, these make Cu-N2-V an effective and high-performance catalyst for solar-driven CO2 conversion to ethanol. This study also reveals the valence state change of Cu in Cu-N2-V during the CO2 photoreduction reaction.

Unveiling the role of proton concentration in dinuclear metal complexes for boosting photocatalytic CO2 reduction

The reaction kinetics of photocatalytic CO2 reduction is highly dependent on the transfer rate of electrons and protons to the CO2 molecules adsorbed on catalytic centers. Studies on uncovering the proton effect in catalysts on photocatalytic activity of CO2 reduction are significant but rarely reported. In this paper, we, from the molecular level, revealed that the photocatalytic activity of CO2 reduction is closely related to the proton availability in catalysts. Specifically, four dinuclear Co(II) complexes based on Robson-type ligands with different number of carboxylic groups (-nCOOH; n = 0, 2, 4, 6) were designed and synthesized. All these complexes show photocatalytic activity for CO2 reduction to CO in a water-containing system upon visible-light illumination. Interestingly, the CO yields increase positively with the increase of the carboxylic-group number in dinuclear Co(II) complexes. The one containing -6COOH shows the best photocatalytic activity for CO2 reduction to CO, with the TON value reaching as high as 10,294. The value is 1.8, 3.4, and 7.8 times higher than those containing -4COOH, -2COOH, and -0COOH, respectively. The high TON value also makes the dinuclear Co(II) complex with -6COOH outstanding among reported homogeneous molecular catalysts for photocatalytic CO2 reduction. Control experiments and density functional theory calculation indicated that more carboxylic groups in the catalyst endow the catalyst with more proton relays, thus accelerating the proton transfer and boosting the photocatalytic CO2 reduction. This study, at a molecular level, elucidates that more carboxylic groups in catalysts are beneficial for boosting the reaction kinetics of photocatalytic CO2 reduction.

Spin polarization in Fe-doped CsPbBr3 perovskite nanocrystals for enhancing photocatalytic CO2 reduction

Spin manipulation offers an effective strategy to enhance photocatalytic activity in metal halide perovskites by suppressing the recombination of photo-excited electrons. However, the scope of the magnetic dopant inducing spin polarization is still limited. Here, we introduce synergetic strategies to polarize the spin in photo-excited electrons and boost their photocatalytic activity for CO2 reduction. We dope iron cation (Fe2+) into CsPbBr3 perovskite nanocrystals (PNCs). Fe ions induce paramagnetism, fostering spin polarization within the Fe-doped CsPbBr3 PNCs (Fe-CsPbBr3 PNCs) under magnetic fields. The magnetic compositions in PNC tend to stabilize the spin polarized electrons within the PNC, mitigate the recombination of photo-excited electrons and enhance the redox reaction for photocatalytic CO2 reduction. The synergistic effects of magnetic element doping and the application of magnetic fields resulted in a photocatalytic CO2 reduction of 133.04 g−1, which is 1.68-fold increase compared to the Fe-PNC without a magnetic field. This work provides a simple and environmentally friendly approach to CO2 reduction based on PNCs.

Ligand modulation of active center to promote lead-free Cs2AgInCl6 photocatalytic CO2 reduction

Metal halide perovskites (MHP) are potential candidates for the photocatalytic reduction of CO2 due to their long photogenerated carrier lifetime and charge diffusion length. However, the conventional long-chain ligand impedes the adsorption and activation of CO2 molecules in practical applications. Here, a ligand modulation technology is employed to enhance the photocatalytic CO2 reduction activity of lead-free Cs2AgInCl6 microcrystals (MCs). The Cs2AgInCl6 MCs passivated by Oleic acid (OLA) and Octanoic acid (OCA) are used for photocatalytic CO2 reduction. The results show that the surface defects and electronic properties of Cs2AgInCl6 MCs can be adjusted through ligand modulation. Compared with the OLA-Cs2AgInCl6, the OCA-Cs2AgInCl6 catalyst demonstrated a significant improvement in the catalytic yield of CO and CH4. The CO and CH4 catalytic yields of OCA-Cs2AgInCl6 reached 171.88 and 34.15 µmol g−1 h−1 which were 2.03 and 12.98 times higher than those of OLA- Cs2AgInCl6, and the total electron consumption rate of OCA-Cs2AgInCl6 was 615.2 µmol g−1 h−1 which was 3.25 times higher than that of OLA-Cs2AgInCl6. Furthermore, in situ diffuse reflectance infrared Fourier transform spectra revealed the enhancement of photocatalytic activity in Cs2AgInCl6 MCs induced by ligand modulation. This study illustrates the potential of lead-free Cs2AgInCl6 MCs for efficient photocatalytic CO2 reduction and provides a ligand modulation strategy for the active promotion of MHP photocatalysts.

Zirconium induced surfaces frustrated Lewis acid-base pairs for BiOBr boosting CO2 photoreduction

Conversion of CO2 to carbon-based fuels via photocatalytic reduction, as a prospective approach, could alleviate energy shortages and environmental problems. However, the adsorption and activation of CO2 in the process of photocatalytic CO2 reduction are still great challenge. Herein, Zr isomorphous substituted BiOBr catalyst with surface frustrated Lewis acid-base pairs (SFLPs) are formed by a convenient chemical method. The photocatalytic activity of CO2 reduction for optimal Zr-BiOBr is significantly improved, with CO yield of 185.7 μmol·g−1·h−1 and CH4 of 0.7 μmol·g−1·h−1, being 9.2 - fold and 3.2 - fold higher than that of original BiOBr, respectively. It is found that zirconium is considered as Lewis acid site and lattice oxygen as Lewis base site, which could effectively boost the adsorption and activiation of CO2 molecules. This work not only demonstrates that construction of SFLPs for catalyst could be taken as an effective tactics for CO2 adsorption and activation, but also suggests a possible photocatalytic mechanism in depth.

Surface Coordination Environment Engineering on PtxCu1-x Alloy Catalysts for the Efficient Photocatalytic Reduction of CO2 to CH4.

Alloy catalysts have been reported to be robust in catalyzing various heterogeneous reactions due to the synergistic effect between different metal atoms. In this work, aimed at understanding the effect of the coordination environment of surface atoms on the catalytic performance of alloy catalysts, a series of PtxCu1-x alloy model catalysts supported on anatase-phase TiO2 (PtxCu1-x/Ti, x = 0.4, 0.5, 0.6, 0.8) were developed and applied in the classic photocatalytic CO2 reduction reaction. According to the results of catalytic performance evaluation, it was found that the photocatalytic CO2 reduction activity on PtxCu1-x/Ti showed a volcanic change as a function of the Pt/Cu ratio, the highest CO2 conversion was achieved on Pt0.5Cu0.5/Ti, with CH4 as the main product. Further systematic characterizations and theoretical calculations revealed that the equimolar amounts of Pt and Cu in Pt0.5Cu0.5/Ti facilitated the generation of more Cu-Pt-paired sites (i.e., the higher coordination number of Pt-Cu), which would favor a bridge adsorption configuration of CO2 and facilitate the electron transfer, thus resulting in the highest photocatalytic CO2 reduction efficiency on Pt0.5Cu0.5/Ti. This work provided new insights into the design of excellent CO2 reduction photocatalysts with high CH4 selectivity from the perspective of surface coordination environment engineering on alloy catalysts.

Constructing B─N─P Bonds in Ultrathin Holey g-C3N4 for Regulating the Local Chemical Environment in Photocatalytic CO2 Reduction to CO.

The lack of intrinsic active sites for photocatalytic CO2 reduction reaction (CO2RR) and fast recombination rate of charge carriers are the main obstacles to achieving high photocatalytic activity. In this work, a novel phosphorus and boron binary-doped graphitic carbon nitride, highly porous material that exhibits powerful photocatalytic CO2 reduction activity, specifically toward selective CO generation, is disclosed. The coexistence of Lewis-acidic and Lewis-basic sites plays a key role in tuning the electronic structure, promoting charge distribution, extending light-harvesting ability, and promoting dissociation of excitons into active carriers. Porosity and dual dopants create local chemical environments that activate the pyridinic nitrogen atom between the phosphorus and boron atoms on the exposed surface, enabling it to function as an active site for CO2RR. The P-N-B triad is found to lower the activation barrier for reduction of CO2 by stabilizing the COOH reaction intermediate and altering the rate-determining step. As a result, CO yield increased to 22.45µmolg-1h-1 under visible light irradiation, which is ≈12 times larger than that of pristine graphitic carbon nitride. This study provides insights into the mechanism of charge carrier dynamics and active site determination, contributing to the understanding of the photocatalytic CO2RR mechanism.

Harnessing In2O3 as an electron aggregator to assist BiOBr nanosheets for enhanced photocatalytic CO2 reduction activity

The advancement of catalysts featuring high carrier separation efficiency enhances photocatalytic reduction performance. This study employed a simple hydrothermal method to anchor In2O3 nanoparticles onto the surface of two-dimensional BiOBr nanosheets, constructing a type-II heterostructure that improves the photocatalytic reduction capability. The composites of 0D/2D In2O3/BiOBr underwent XPS, TPR, and MS characterization, validating the formation of a type-II heterostructure. In2O3 functioned as an electron-aggregating active site that extracted photogenerated electrons from the surface of BiOBr. As a result, the efficiency of charge separation is markedly increased. The results of the CO2 reduction test indicate that In2O3-modified BiOBr exhibits superior photocatalytic activity compared to pure BiOBr, with 2 % In2O3/BiOBr exhibiting the highest reduction performance. The CO yield achieved was 9.81 µmol·g−1·h−1, which is 5.33 times higher than that of pure BiOBr and 42.65 times higher than that of pure In2O3. These findings offer future potential for the application of In2O3 as an electron-accumulating material to enable the photocatalytic reduction of CO2.

Local spatial polarization induced efficient electron transfer in fluorinated borocarbonitride for boosting CO2 photoreduction

CO2 photoreduction into highly value-added chemicals over metal-free h-BCN has emerged as a promising strategy to address the issue of global warming. However, the serious carrier recombination caused by disordered charger transfer has limited its practical application. To circumvent this issue, fluorine modified h-BCN were synthesized using a facile heat treatment method. The surface halogenation created local spatial polarized electric field, which facilitated the local charge separation and transmission efficiency. Among them, BCN-F-4 exhibited the best photocatalytic CO2 reduction activitiy with CO and CH4 yield of 25.38 and 14.11 µmol g−1h−1, respectively. The turnover number (TON) of BCN-F-4 reached up to 163.6 μmol g−1h−1, 4.4 times that of BCN. Both theoretical simulation and experimental analysis demonstrated a strong covalent interaction between the F atoms and the h-BCN matrix, which gain deep understanding of the mechanism of prominent photocatalytic CO2 reduction activity boosted by surface halogenation.

Enhanced photocatalytic CO2 reduction activity using a Bi4V2O11/single-walled carbon nanotube/g-C3N4 S-scheme heterojunction

A novel Bi4V2O11/single-walled carbon nanotube (SWNT)/g-C3N4 S-scheme heterojunction photocatalyst is prepared using an in situ solvothermal growth method. Heterostructures are constructed by coupling the defective semiconductor Bi4V2O11 with ultrathin porous g-C3N4 nanosheets. To improve the photocatalytic CO2 reduction activity, oxygen defects are used to enhance electron capture and CO2 adsorption, the S-scheme heterojunction is used to improve the separation efficiency of the photogenerated carriers and SWNTs are used to form high-speed electron transport channels. The experimental results indicate that the maximum CO formation rate of Bi4V2O11/SWNT/g-C3N4 is 18.6 μmol h−1 g−1, which is 2.7 and 2.4 times that of the ultrathin porous g-C3N4 nanosheets and Bi4V2O11 heated for 15 h, respectively, and 3.4 times that of standard g-C3N4. This work provides a vital reference point for the in situ construction of S-scheme heterojunctions with defects.

Confined Synthesis of Noble Metal Clusters Assisted by Liquid Film for Photocatalytic CO2 Reduction.

The important concept of confined synthesis is considered a promising strategy for the design and synthesis of definable nanostructured materials with controllable compositions and specific morphology, such as highly loaded single-atom catalysts capable of providing abundant active sites for photocatalytic reactions. In recent years, researchers have been working on developing new confined reaction systems and searching for new confined spaces. Here, we present for the first time the concept of a bubble liquid film as a novel confined space. The liquid film has a typical sandwich structure consisting of a water layer, sandwiched between the upper and lower surfactant layers, with the thickness of the intermediate water layer at the micro- and nanometer scales, which can serve as a good confinement. Based on the above understanding and combined with the photodeposition method, we successfully confined synthesized Ag/TiO2, Au/TiO2, and Pd/TiO2 photocatalysts in liquid film. By HAADF-STEM, it can be seen that the noble metal morphologies are all nanoclusters of about 1 nm and are highly uniformly dispersed on the TiO2 surface. Compared with photodeposition in solution, we believe that the surfactant molecular layer restricts a limited amount of precursor to the liquid film, avoiding the accumulation of noble metals and the formation of large particle size nanoparticles. The liquid film, meanwhile, restricts the migration path of noble metal precursors, allowing for thorough in situ photodeposition and enables the complete and uniform dispersion of noble metal precursors, greatly reducing the photodeposition time. The uniform loading of the three noble metals proved the universality of the method, and the catalysts showed high activity for photocatalytic CO2 reduction. The rates of reduction of CO2 to CO over the Ag/TiO2 photocatalytic reached 230 μmol g-1 h-1.This study provides a new idea for the expansion of the confined reaction system and a reference for the study of liquid film as the confined space.

High activity and CH4 selectivity for photocatalytic CO2 reduction by Cu modified C3N4 nanotubes

The photocatalytic CO2 reduction has the problems of low selectivity of single product. Here, the preparation of Cu modified tubular C3N4 (CTN) was studied. The increase of the active site inhibits the recombination of electrons (e-) and holes (h + ) and improves the selectivity of CO2 reduction products. Finally, the CO and CH4 yields of 1.5 % CTN photocatalyst are 11.55 μmol·g−1 and 4.72 μmol·g−1, respectively, which are 5 times higher than that of tubular C3N4 photocatalyst. The selectivity of 2 % CTN to CH4 is up to 68 %, indicating that the prepared CTN photocatalyst has high CO2 reduction activity and CH4 selectivity.

Asymmetric Electron Redistribution in Niobic-Oxygen Vacancy Associates to Tune Noncovalent Interaction in CO2 Photoreduction.

The role of vacancy associates in photocatalytic CO2 reduction is an open question. Herein, the Nb─O vacancy associates (VNb─O ) are engineered into niobic acid (NA) atomic layers to tailor the CO2 photoreduction performance. The intrinsic charge compensation from O to Nb around Nb─O vacancy associates can manipulate the active electronic states, leading to the asymmetric electron redistribution. These local symmetry breaking sites show a charge density gradient, forming a localized polarization field to polarize nonpolar CO2 molecules and tune the noncovalent interaction of reaction intermediates. This unique configuration contributes to the 9.3 times increased activity for photocatalytic CO2 reduction. Meantime, this VNb─O NA also shows excellent photocatalytic activity for NO3 - -NH4 + synthesis, with NH4 + formation rate up to 3442µmol g-1 h-1 . This work supplies fresh insights into the vacancy associate design for electron redistribution and noncovalent interaction tuning in photocatalysis.

Coordination engineering of the interfacial chemical bond and sulfur vacancies modulated S‐scheme charge transfer for efficient photocatalytic CO2 reduction

Surface charge localization and poor carrier separation efficiency limited the of photocatalytic CO2 reduction (PCR) activity. Creating heterojunctions between the interfacial layers was an important strategy used to enhance catalytic activity. Here, a core-shell structure S-scheme catalyst was constructed by growing of Bi2WO6 (BWO) nanospheres on the surface of Zn0.5Cd0.5S(VS-ZCS) nanospheres with abundant sulfur defect, and which was coordinated by the interface bonding and the sulfur vacancies (VS) for efficient PCR. Meanwhile, the surface potential was 91 mV, indicating the creation of strong interface electric field (IEF). As part of the strong synergy of the Bi-S bond, IEF and VS, the improved photocatalyst exhibited high CO evolution rate of 86.16 μmol⋅g−1, which was about 9.23 fold of the pristine VS-ZCS. This was attributed to production of *COOH intermediates on the VS-ZCS/BWO surface that had been proved to be crucial for PCR generation CO. Besides, electrons quickly migrated through the formed Bi-S bonds to the catalytic sites, accelerating charge separation. The use of VS as electron traps was beneficial for regulating the localization of photogenerated charges on the surface of S-scheme heterostructure. The Bi-S bonds and VS modulated S‐scheme charge transfer for efficient photocatalytic CO2 reduction provides new insights into photocatalytic CO2 reduction.

Oxygen vacancy mediation of BiOX (X=Cl, Br) towards enhanced photocatalytic CO2 reduction activity

Surface defects in semiconductors play a significant role in modulating the performance of photocatalytic reactions. However, there is still insufficient exploration regarding the influence of defects on the photocatalytic CO2 reduction performance. In this study, we achieved controllable construction of oxygen vacancies (OVs) in BiOX (X=Cl, Br) samples through one-step solvothermal treatment in polyols by adjusting the reaction time. The introduction of OVs significantly enhanced the photocatalytic activity of BiOX (X=Cl, Br) for converting CO2 to CO. Among all the tested BiOX (X=Cl, Br) samples with OVs, BiOCl-OV-2 and BiOBr-OV-2 samples with a moderate amount of OVs exhibited the highest CO yield of 28.51 and 15.22 μmol gcat−1 after 4 hours of irradiation, respectively. Photo-/electrochemical measurements results revealed that engineering OVs into BiOX (X=Cl, Br) effectively adjusted their electronic structure, charge density and separation; however, excessive OVs may slightly degrade their photoelectrochemical properties and thus lead to reduced photocatalytic activity. Furthermore, an appropriate amount of OV was found to enhance both CO2 adsorption capacity and photo-generated electron reduction ability, thereby further promoting the overall efficiency of photocatalytic CO2 conversion. Through in situ FTIR spectra analysis, we uncovered the process of photocatalytic conversion from CO2 to CO.

Self-nitrogen-doped hierarchical porous carbon spheres as metal-free catalyst for efficient photocatalytic CO2 reduction

It is rather important to develop an efficient, stable and economical photocatalyst for solar-driven CO2 reduction. Herein, N-doped hierarchical porous carbon spheres (NPCS-F6) with metal-like activity is synthesized using acrylamide and F127 as nitrogen source and soft template, and the effective synergy between nitrogen-containing species and hierarchical pore structure makes the samples exhibit excellent CO2 reduction properties. XPS characterization illustrates that the introduced pyridine nitrogen and pyrrole nitrogen groups contribute to the increase of CO2 reduction sites on the surface of the material. N2 adsorption analysis verifies the existence of hierarchical pore structures in which micropores facilitate the exposure of more adsorption active sites, while mesopores and macropores can be used as transfer channels to connect the internal micropores and reduce the molecular diffusion resistance to improve CO2 adsorption performance. In addition, the pore structure of the samples prepared with P123 and CTAB as templates is mainly microporous, whereas carbon spheres with hierarchical pores coexisting are obtained with F127 as template. The evaluation of photocatalytic CO2 reduction activity shows that the CO yield of NPCS-F6 could reach 17.56 μmol·g−1 for 8 h, which is 1.17 times, 1.08 times and 1.07 times of the original NCS-8 (15.05 μmol·g−1), NPCS-P6 (P123 as soft template, 16.25 μmol·g−1) and NPCS-C1 (CATB as soft template, 16.39 μmol·g−1), respectively. Comprehensive characterization results are analyzed to propose a possible mechanism for photocatalytic CO2 reduction, in which photogenerated electron-hole pairs are generated inside the material under light conditions, and the photogenerated electrons are transferred to the N-6/N-5 active sites through the electron transfer channel N-Q to react with CO2 molecules adsorbed on the surface to be reduced to CO. Finally, our results provide a favorable and feasible strategy to synthesize metal-free photocatalysts for high-efficiency CO2 adsorption and targeted reduction of CO2 to CO.

Synthesis, Structural Characterization, Hirschfeld Surface Analysis, Density Functional Theory, and Photocatalytic CO2 Reduction Activity of a New Ca(II) Complex with a Bis-Schiff Base Ligand.

A new bis-Schiff base (L) Ca(II) complex, CaL, was synthesized by the reaction of calcium perchlorate tetrahydrate, 1,3-diamino-2-hydroxypropane, and 2-formyl phenoxyacetic acid in an ethanol-water (v:v = 2:1) solution and characterized by IR, UV-vis, TG-DTA, and X-ray single crystal diffraction analysis. The structural analysis indicates that the Ca(II) complex crystallizes in the monoclinic system, space group P121/n1, and the Ca(II) ions are six-coordinated with four O atoms (O8, O9, O11, O12, or O1, O2, O4, O6) and two N atoms (N1, N2, or N3, N4) of one bis-Schiff base ligand. The Ca(II) complex forms a tetramer by intermolecular O-H…O hydrogen bonds. The tetramer units further form a three-dimensional network structure by π-π stacking interactions of benzene rings. The Hirschfeld surface of the Ca(II) complex shows that the H…H contacts represent the largest contribution (41.6%) to the Hirschfeld surface, followed by O…H/H…O and C…H/H…C contacts with contributions of 35.1% and 18.1%, respectively. To understand the electronic structure of the Ca(II) complex, the DFT calculations were carried out. The photocatalytic CO2 reduction test of the Ca(II) complex exhibited a yield of 47.9 μmol/g (CO) and a CO selectivity of 99.3% after six hours.

Ligand Mediated Assembly of CdS Colloids in 3D Porous Metal–Organic Framework Derived Scaffold with Multi‐Sites Heterojunctions for Efficient CO2 Photoreduction

AbstractThe inclusion of colloidal particles into 3D porous constructs to realize heterostructure ensembles enhances surface interactions and energy transfer that can transform the catalytic properties of conventional catalysts. However, assembling hydrophobic colloidal nanoparticles within hydrophilic 3D porous matrices to create tailored heterostructures and catalytic properties is particularly challenging. Here, a modified ligand grafting method is presented to spontaneously assemble CdS inorganic colloidal quantum dots within a metal‐organic framework (MOF) derived porous framework for efficient photocatalytic CO2 reduction. The grafted long chain molecular ligands effectively suppress phase separation and endow a molecular‐recognition effect to form ordered assembly microstructures. The proof‐of‐concept assembly of CdS and Prussian blue analogues (PBA) derived Co3O4 facilitates a high density of heterojunctions formation, improving charge transfer and extended lifetimes of photo‐induced electrons. Consequently, CdS/Co3O4 assembly exhibits exceptionally active and stable photocatalytic CO2 reduction activity, with a CO production rate of 73.9 µmol g−1 h−1 and CO selectivity of 98.9%. Importantly, the ligand grafting method can be generalized to achieve spontaneous assembly of quantum dots within various metal organic framework derived porous scaffolds. This work provides a rational strategy for precise self‐assembly of colloidal nanoparticles within porous microstructures, allowing tailored heterointerfaces for functional materials and applications.