Synergistic effect between sulfur vacancies and S-scheme heterojunctions in WO3/VS-Zn3In2S6 for enhanced photocatalytic CO2 reduction in H2O vapor.

Converting CO2 into CO, CH4, and other hydrocarbons using solar energy presents a viable approach for addressing energy shortages. In this study, photocatalysts with S-deficient WO3/Zn3In2S6 (WO3/VS-ZIS) S-scheme heterojunctions have been successfully synthesized. Under UV-vis light irradiation, 20 %WO3/VS-ZIS demonstrated significantly improved CO2 reduction activity and CH4 selectivity. Detailed characterization and density functional theory (DFT) calculations reveal that the enhanced performance is due to the synergistic optimization of the S-scheme heterojunction and sulfur vacancies (VS) for CO2 reduction. The presence of VS aids in the adsorption and activation of CO2 and enhances the separation of charge carriers. The 2D/2D S-scheme heterostructure assembled with WO3 nanosheets not only accelerates the migration and separation of photoexcited charge carriers but also improves the adsorption of H2O and the formation of VS, thereby increasing the adsorption and activation of CO2 and facilitating the protonation of CO* to produce CH4. This study clarifies the synergistic effect of VS and S-scheme heterostructures in improving photocatalytic performance, offering valuable insights into the photoactivation process of CO2 at VS in S-scheme heterojunctions.

On-demand green/red light-responsive self-doped SnO2 nanoparticles for single/multi-color transitioning fabrics.

Semiconductor/redox-based dual light-induced color switching systems (LCSs) with a visible light response at different wavelengths are highly sought after for efficient redox reactions. In this work, Sn2+ self-doped SnO2 has been designed as nanophotocatalysts for preparing visible light-responsive inks/fabrics with single/multi-color abilities. The self-doping of SnO2 nanoparticles results in the formation of oxygen vacancies due to charge compensation effects leading to electron-driven photoreduction and photooxidation of LSC inks. By mixing SnO2-x nanoparticles dispersions with specific redox-sensitive dyes can lead to the creation of well-designed sets of visible light-responsive semiconductor-driven LCS systems with both single-color (RGB) and multi-color (violet and green) changes. The exposure of LCS inks to green (550 nm) light culminates in the rapid photoreduction of the inks to decolorized state, while red (660 nm) light initiates the photooxidation in air. The combination of the LCS inks with -OH-rich polymers can be coated on the hydrophobic surface of the layered fabric to produce photo-responsive fabrics with single/multi-color response. The interaction of green light with the semiconductor-driven LCS systems allows the remote photo-printing of different images/letters on the LCS fabrics. Spontaneous erasure can be achieved by red light with high stability and repeatability (>35 cycles). The research in this paper provides new perspectives and insights for the development of new color-changing materials with potential applications as light-activated sensors and display units.

TiF bridged IL-CuCQDs-F/TiO2 inverse opal composite for boosting CO2 visible-photo reduction via slow photon effect.

Photocatalytic reduction of CO2 exhibits unsatisfactory photocatalytic performance owing to the inefficient separation of photogenerated electron-hole pairs, low CO2 capture efficiency and limited visible light absorption on most photo-catalysts. Herein, TiF bridged IL-CuCQDs-F/TiO2 inverse opal composite (IO-CFTi) was constructed for boosting CO2 visible-photo reduction via slow photo effect. In this work, ethylenediaminetetraacetic acid (EDTA(Cu)) and imidazole ionic liquid 1-(2-Hydroxyethyl)-3-methylimidazolium tetrafluoroborate ([HOEtMIM][BF4]) were employed to confine grow of IL-CuCQDs-F within TiO2 inverse opal supporter via TiF bonds connection. Unique IL-CuCQDs-F efficiently expended light absorption towards visible region, and the confined growth of IL-CuCQDs-F within the TiO2 inverse opal cavity achieved the photoelectric conversion and efficient CO2 capture. Moreover, their TiF bonding interface of IO-CFTi assisted photogenerated electron transportation from TiO2 to CO2 for its reduction in this system. Consequently, IO-CFTi achieved a substantially increased CO production rate of 78.1 µmol·h-1·g-1 with 98 % selectivity. This improved performance in CO2 photoreduction positions the nanocomposite as a promising material for preservation of the environment and conversion of energy.

Tailoring d­Band Center of Single-Atom Nickel Sites for Boosted Photocatalytic Reduction of Diluted CO2 from Flue Gas.

Photocatalytic reduction of diluted CO2 from anthropogenic sources holds tremendous potential for achieving carbon neutrality, while the huge barrier to forming *COOH key intermediate considerably limits catalytic effectiveness. Herein, via coordination engineering of atomically scattered Ni sites in conductive metal-organic frameworks (CMOFs), we propose a facile strategy for tailoring the d­band center of metal active sites towards high-efficiency photoreduction of diluted CO2. Under visible-light irradiation in pure CO2, CMOFs with Ni-O4 sites (Ni-O4 CMOFs) exhibits an outstanding rate for CO generation of 13.3 µmol h-1 with a selectivity of 94.5%, which is almost double that of its isostructural counterpart with traditional Ni-N4 sites (Ni-N4 CMOFs), outperforming most reported systems under comparable conditions. Interestingly, in simulated flue gas, the CO selectivity of Ni-N4 CMOFs decreases significantly while that of Ni-O4 CMOFs is mostly unchanged, signifying the supremacy for Ni-O4 CMOFs in leveraging anthropogenic diluted CO2. In-situ spectroscopy and density functional theory (DFT) investigations demonstrate that O coordination can move the center of the Ni sites' d-band closer to the Fermi level, benefiting the generation of *COOH key intermediate as well as the desorption of *CO and hence leading to significantly boosted activity and selectivity for CO2-to-CO photoreduction.

UV light promoted dihydrolipoic acid and its alanine derivative directed rapid synthesis of stable gold nanoparticles and their catalytic activity.

In general, colloidal gold nanoparticles (AuNPs) have been synthesized in heated or boiling water containing HAuCl4 precursor with sodium citrate as reducing stabilizing reagent. Although temperature plays a driving for synthesis of AuNPs, elevated temperature in thermal reduction method causes aggregation of the AuNPs. The preferential, rapid and strong binding of dihydro-lipoic acid and its derivatives on surface of AuNPs via thiol - Au chemistry promote the production of very stable AuNPs. In this study, we have developed citric acid (CA), dihydrolipoic acid (DHLA) and DHLA-Alanine (DHLA-Ala) directed rapid synthesis of ultra-stable AuNPs, DHLA@AuNPs and DHLA-Ala@AuNPs, under the UV (311 nm) irradiation at room temperature (RT: 25 °C) in around 10 min (min). CA is used as a potential reducing agent to expedite both reduction of Au3+ ion and AuNP formation, DHLA and DHLA-Ala act as stabilizing agents by replacing CA molecules on surface of AuNPs in order to produce quite stable AuNP. It is worthy to mention that reduction of Au3+ ion, formation and surface stabilization of AuNPs are consequently occurred in one step. We also investigated how experimental parameters including reaction time and temperature, pH of reaction solution, affect formation of the AuNPs. The effects of salt concentration and storage temperature were studied to show stability of the AuNPs. The synthesized DHLA@AuNPs and DHLA-Alanine@AuNPs were characterized via UV-Vis spectrophotometer (UV-Vis), scanning transmission electron microscope (STEM), dynamic light scattering (DLS) and Zeta potential (ZT) devices. The reduction of 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) was efficiently catalyzed by the AuNPs in the presence of sodium borohydride in aqueous solution.

Enabling Interfacial Lattice Matching by Selective Epitaxial Growth of CuS Crystals on Bi2WO6 Nanosheets for Efficient CO2 Photoreduction into Solar Fuels.

Photocatalytic CO2 reduction serves as an important technology for value-added solar fuel production; however, it is generally limited by interfacial charge transport. To address this limitation, a two-dimensional/two-dimensional (2D/2D) p-n heterojunction CuS-Bi2WO6 (CS-BWO) with highly connected and matched interfacial lattices was designed via a two-step hydrothermal tandem synthesis strategy. The integration of CuS with BWO created a robust interface electric field and provided fast charge transfer channels due to the work function difference, as well as highly connected and matched interfacial lattices. The p-n heterojunction promoted electron transfer from the Cu to Bi sites, leading to coordination of Bi sites with high electronic density and low oxidation state. The Bi sites in BWO nanosheets facilitated the adsorption and activation of CO2, and generation of high-coverage key intermediate b-CO32-, while broad light-harvesting CuS (CS) provide abundant photoinduced electrons that were injected into the conduction band of BWO for CO2 photoreduction reaction. Remarkably, the p-n heterojunction CS-BWO exhibited CO and CH4 yields of 135.7 and 62.5 µmol g-1, respectively, which were significantly higher than those of CS, BWO, and physical mixture CS-BWO nanosheets. This work provided an innovative design strategy for developing high-activity heterojunction photocatalyst for converting CO2 into value-added solar fuels.

Dual-Function Femtosecond Laser: ß-TCP Structuring and AgNP Synthesis via Photoreduction with Azorean Green Tea for Enhanced Osteointegration and Antibacterial Properties.

ß-Tricalcium phosphate (ß-TCP) is a well-established biomaterial for bone regeneration, highly regarded for its biocompatibility and osteoconductivity. However, its clinical efficacy is often compromised by susceptibility to bacterial infections. In this study, we address this limitation by integrating femtosecond (fs)-laser processing with the concurrent synthesis of silver nanoparticles (AgNPs) mediated by Azorean green tea leaf extract (GTLE), which is known for its rich antioxidant and anti-inflammatory properties. The fs laser was employed to modify the surface of ß-TCP scaffolds by varying scanning velocities, fluences, and patterns. The resulting patterns, formed at lower scanning velocities, display organized nanostructures, along with enhanced roughness and wettability, as characterized by Scanning Electron Microscopy (SEM), optical profilometry, and contact angle measurements. Concurrently, the femtosecond laser facilitated the photoreduction of silver ions in the presence of GTLE, enabling the efficient synthesis of small, spherical AgNPs, as confirmed by UV-vis spectroscopy, Transmission Electron Microscopy (TEM), and Fourier Transform Infrared Spectroscopy (FTIR). The resulting AgNP-embedded ß-TCP scaffolds exhibited a significantly improved cell viability and elongation of human bone marrow mesenchymal stem cells (hBM-MSCs), alongside significant antibacterial activity against Staphylococcus aureus (S. aureus). This study underscores the transformative potential of combining femtosecond laser surface modification with GTLE-mediated AgNP synthesis, presenting a novel and effective strategy for enhancing the performance of ß-TCP scaffolds in bone-tissue engineering.

Single-Atom Electron Pumps Over Transition Metal Chalcogenides Boosting Photocatalysis.

Cocatalyst is of paramount significance to provide fruitful active sites for suppressing the spatial charge recombination toward boosted photocatalysis. Up to date, exploration of robust and stable cocatalysts is remained challenging. Inspired by the intrinsic merits of single-atom catalysts (SACs), such as distinctive electronic structure and high atomic utilization efficiency, single-atom/transition metal chalcogenides (TMCs) is utilized as a model to synthesize CdS-Pd single-atom catalyst (CdS-PdSA) heterostructures. This demonstrates the precise anchoring of isolated metal single-atom catalysts (SACs) onto TMCs through a simple yet effective wet-chemical strategy. The resulting heterostructures exhibit significantly enhanced and stable photocatalytic activity for selective anaerobic organic transformations and hydrogen production under visible light. This enhancement is primarily inferred due to the role of Pd SACs as electron pumps, which directionally trap the electrons photoexcited over CdS, accelerating the spatial charge separation and prolonging the carrier lifespan. The charge transport route and photocatalytic mechanism are elucidated. This work underscores the potential of SACs as cocatalysts in heterogeneous photocatalysis, offering valuable insights for the rational design of atomic-level cocatalysts for solar-to-chemical energy conversion and beyond.

Triggering Asymmetric Layer Displacement Polarization and Redox Dual-Sites Activation by Inside-Out Anion Substitution for Efficient CO2 Photoreduction.

Sluggish bulk charge transfer and barren catalytic sites severely hinder the CO2 photoreduction process. Seeking strategies for accelerating charge dynamics and activating reduction and oxidation sites synchronously presents a huge challenge. Herein, an inside-out chlorine (Cl) ions substitution strategy on the layered polar Bi4O5Br2 is proposed for achieving layer structure-dependent polarization effect and redox dual-sites activation. Cl ions in the bulk phase shrink the halogen layer interspace by 8‰, triggering asymmetric [Bi4O5]2+ layer displacement polarization, prolonging the average photocharge lifetime to 201.8 ps. Meanwhile, surface substituted Cl ions enhance the electron-donating capability of neighboring Bi atoms, activating the intrinsic Bi reduction sites, and increasing H2O molecule adsorption on nearby intrinsic O oxidation site (cal. by 0.105 eV), also self-donating as an alien oxidation site. Besides, Cl upshifts the p-band center closer to the Fermi level, facilitating the reactant adsorption. Therefore, the energy barrier for CO2 activation and rate-limiting *COOH intermediate formation steps are significantly decreased. Without cocatalysts and sacrificial reagents, inside-out Cl-substituted Bi4O5Br2 delivers a remarkable CO2-to-CO photoreduction rate of 50.18 µmol g-1 h-1, being one of the state-of-the-art catalysts. This finding offers insights into exploiting polarization at the molecular-level and enhances understanding of catalytic site activation.

Combined Role of {001} Facet-Enriched Morphology and Gold Nanoparticle Deposition on Anatase TiO2 Photoactivity.

The interplay on anatase TiO2 photoactivity between particle morphology and gold nanoparticles (NPs) deposition, via either deposition-precipitation (DP) or photodeposition (P), is here investigated by evaluating the photoactivity of Au modified anatase (Au/TiO2) nanocrystals with either a pseudospherical shape or a nanosheet structure in both reduction and oxidation test reactions. The presence of Au NPs on the anatase surface only slightly affects its photoactivity in Cr(VI) reduction, which is kinetically limited by the anodic half-reaction, whereas a larger exposure of highly oxidant {001} facets is beneficial for overcoming this rate-determining step. In the photocatalytic oxidation of both formic acid, proceeding through a direct mechanism, and rhodamine B (RhB) on surface fluorinated photocatalysts, occurring through a hydroxyl-radical-mediated mechanism, the presence of gold NPs produces a significant photoactivity increase only with spherically shaped photocatalysts, mainly exposing {101} facets. These results are rationalized in light of the preferential migration of photogenerated, oppositely charged carriers toward different crystal facets. In fact, when the Au/TiO2 material mainly exposes the more oxidant {001} facets, where photoproduced holes preferentially migrate, recombination between these latter and the electrons captured by Au NPs is favored. Instead, Au NPs on {101} facets efficiently capture photopromoted electrons, preferentially migrating toward such facets with a consequent improvement of photoproduced charge separation.

Tannic Acid Selective Modulation Defects to Enhance the Photocatalytic CO2 Reduction Activity of Layered Double Hydroxides.

Recently, layered double hydroxides (LDH) have shown great potential in photoreduction of CO2 owing to its flexible structural adjustability. In this study, the mild acidic property of tannic acid (TA) is exploited to etch the bimetal LDH to create abundant vacancies to gain the coordination unsaturated active centers. Based on the different chelating abilities of TA to various metal ions, the active metals are remained by selective chelation while the inert metals are removed during the etching process of bimetal LDH. Furthermore, selective chelating with metal ions not only increases the percentage of highly active metals but also compensates for the structural damage caused by the etch, which achieves a scalpel-like selective construction of vacancies. The NiAl-LDH etched and functionalized by TA for 3 h exhibits superior photo-reduction of CO2 performance without co-catalysts and photo-sensitizers, which is 14 times that of the pristine NiAl-LDH. The fact that many bimetal LDHs can be functionalized by TA and exhibit significantly improved photocatalytic efficiency is confirmed, suggesting this strategy is generalized to functionalize double- or multi-metal LDH. The method provided in this work opens the door for polyphenol-functionalized LDHs to enhance their ability for light-driven chemical transformations.

Chalcogen bonds enable efficient photoreduction of sulfur-containing heterocycles.

Chalcogen bonding interactions have attracted significant attention in a broad chemistry community, with a particular focus on their ability to stabilise the key transition states in various organic synthetic routes. In this work, we demonstrate that they can also be harnessed in selective photoredox reactions, which cannot be otherwise achieved with alternative approaches to photoreduction. We demonstrate this concept through the photoreduction of the sulfur-containing DNA nucleoside precursor thioanhydrouridine to 2'-deoxy-thiouridine, revealing the previously unrecognized role of bisulfide in this process. Based on quantum chemical simulations, we identify a stable chalcogen-bonding complex of the hydrosulfide anion and thionhydrouridine (HS-…S contacts), which enables directional photoinduced electron transfer, resulting in the formation of non-canonical DNA nucleoside. We also disprove the possibility that photoreduction of thioanhydronucleosides could be initiated by hydrated electrons generated from irradiated bisulfide anions which do not interact with the chromophore. Finally, we show that selective photoreduction mediated by chalcogen bonds can only occur for chromophores, which exhibit sufficiently long excited-state lifetimes in the locally-excited states to undergo transition to the productive charge transfer state. These findings can be further used in the design of similar photoredox reactions which can employ the potential of chalcogen bonding interactions.

Symmetry-Engineered BINOL-Based Porous Aromatic Frameworks for H2O2 Production via Artificial Photosynthesis and In Situ Degradation of Pharmaceutical Pollutants.

Accomplishing visible light-driven H2O2 production at millimolar concentrations is practically challenging, particularly for organic semiconductors. In this context, achieving a maximum H2O2 production rate of 31.60 mmol·g-1·h-1 by using porous aromatic frameworks (PAFs) represents a significant accomplishment. We report the unusual photoactivity of tetraphenylmethane-BINOL-linked PAFs in triplet oxygen activation to facilitate the generation of reactive oxygen species (ROS), as confirmed by their optical and electrochemical responses, despite the absence of a conventional chromophoric moiety. Moreover, an in situ BINOL formation strategy was used to synthesize these PAFs during polymerization in contrast to the reported protocols involving chiral BINOLs as precursors. The as-synthesized polymers had a capsule-like morphology (for TPM-BINOL-6), high thermal stability up to 348 °C, and a high Brunauer-Emmett-Teller (BET) surface area of up to 1382 m2/g (for TPM-BINOL-4). Interestingly, they showed sunlight-driven production of H2O2 via an oxygen reduction reaction of up to 17.05 mmol·g-1·h-1 in 1:10 isopropanol in water for TPM-BINOL-6, which was quantified by titration with ceric sulfate. It also exhibited exemplary photocatalytic efficiency with an H2O2 production rate of 6.65 mmol·g-1·h-1 in seawater. Interestingly, the H2O2 production rate reached a maximum of 18.03 mmol·g-1·h-1 with an SCC efficiency of 4.5% under an AM 1.5G solar simulator and apparent quantum yield (AQY) of 15.8% (at λ = 456 nm) for TPM-BINOL-6 in ethanol:water = 1:10. Moreover, the exceptionally high H2O2 production rate of 31.60 mmol·g-1·h-1 was achieved in 1:1 ethanol in water under 50 W blue LED light. Furthermore, these PAFs generated adequate ROS, which were utilized in the photocatalytic degradation of tetracycline via the superoxide intermediate. Additionally, the as-formed H2O2 was further channelized in the pollution abatement catalytic system for the fast degradation of ciprofloxacin (within 4 h) and the reduction of toxic oxometallate Cr(VI) within 10 min, which is one of the earliest reports of utilizing photosynthesized H2O2 for environmental detoxification.

Controlled Fabrication of Wafer-Scale, Flexible Ag-TiO2 Nanoparticle-Film Hybrid Surface-Enhanced Raman Scattering Substrates for Sub-Micrometer Plastics Detection.

As an important trace molecular detection technique, surface-enhanced Raman scattering (SERS) has been extensively investigated, while the realization of simple, low-cost, and controllable fabrication of wafer-scale, flexible SERS-active substrates remains challenging. Here, we report a facile, low-cost strategy for fabricating wafer-scale SERS substrates based on Ag-TiO2 nanoparticle-film hybrids by combining dip-coating and UV light array photo-deposition. The results show that a centimeter-scale Ag nanoparticle (AgNP) film (~20 cm × 20 cm) could be uniformly photo-deposited on both non-flexible and flexible TiO2 substrates, with a relative standard deviation in particle size of only 5.63%. The large-scale AgNP/TiO2 hybrids working as SERS substrates show high sensitivity and good uniformity at both the micron and wafer levels, as evidenced by scanning electron microscopy and Raman measurements. In situ bending and tensile experiments demonstrate that the as-prepared flexible AgNP/TiO2 SERS substrate is mechanically robust, exhibiting stable SERS activity even in a large bending state as well as after more than 200 tensile cycles. Moreover, the flexible AgNP/TiO2 SERS substrates show excellent performance in detecting sub-micrometer-sized plastics (≤1 µm) and low-concentration organic pollutants on complex surfaces. Overall, this study provides a simple path toward wafer-scale, flexible SERS substrate fabrication, which is a big step for practical applications of the SERS technique.

Isotope-Based Characterization of Soil Elemental Mercury Emissions from Historical Mercury Mining Areas: Driving Pathways and Relative Contributions.

Photo-, microbial, and abiotic dark reduction of soil mercury (Hg) may all lead to elemental mercury (Hg(0)) emissions. Utilizing lab incubations, isotope signatures of Hg(0) emitted from mining soils were characterized to quantify the interplay and contributions of various Hg reduction pathways, which have been scarcely studied. At 15 °C, microbial reduced Hg(0) showed a negative mass-dependent fractionation (MDF) (δ202Hg = -0.30 ± 0.08‰, 1SD) and near-zero mass-independent fractionation (MIF) (Δ199Hg = 0.01 ± 0.04‰, 1SD), closely resembling dark reduced Hg(0) (δ202Hg = -0.18 ± 0.05‰, Δ199Hg = -0.01 ± 0.03‰, 1SD). In comparison, photoreduced Hg(0) exhibited significant MDF and MIF (δ202Hg = -0.55 ± 0.05‰, Δ199Hg = -0.20 ± 0.07‰, 1SD). In the dark, Hg isotopic signatures remained constant over the temperature range of 15-35 °C. Nonetheless, light exposure and temperature changes together altered Hg(0) MIF signatures significantly. Isotope mixing models along with Hg(0) emission flux data highlighted photo- and microbial reduction contributing 79-88 and 12-21%, respectively, of the total Hg(0) emissions from mining soils, with negligible abiotic dark reduction. Microorganisms are the key driver of soil Hg(0) emissions by first dissolving HgS and then promoting ionic Hg formation, followed by facilitating the photo- and microbial reduction of organically bound Hg. These insights deepen our understanding of the biogeochemical processes that influence Hg(0) releases from surface soils.

The Development of Metal-Free Porous Organic Polymers for Sustainable Carbon Dioxide Photoreduction.

A viable tactic to effectively address the climate crisis is the production of renewable fuels via photocatalytic reactions using solar energy and available resources like carbon dioxide (CO2) and water. Organic polymer material-based photocatalytic materials are thought to be one way to convert solar energy into valuable chemicals and other solar fuels. The use of porous organic polymers (POPs) for CO2 fixation and capture and sequestration to produce beneficial compounds to reduce global warming is still receiving a lot of interest. Visible light-responsive organic photopolymers that are functionally designed and include a large number of heteroatoms and an extended π-conjugation allow for the generation of photogenerated charge carriers, improved absorption of visible light, increased charge separation, and decreased charge recombination during photocatalysis. Due to their rigid structure, high surface area, flexible pore size, permanent porosity, and adaptability of the backbone for the intended purpose, POPs have drawn more and more attention. These qualities have been shown to be highly advantageous for numerous sustainable applications. POPs may be broadly categorized as crystalline or amorphous according to how much long-range order they possess. In terms of performance, conducting POPs outperform inorganic semiconductors and typical organic dyes. They are light-harvesting materials with remarkable optical characteristics, photostability, cheap cost, and low cytotoxicity. Through cocatalyst loading and morphological tweaking, this review presents optimization options for POPs preparation techniques. We provide an analysis of the ways in which the preparative techniques will affect the materials' physicochemical characteristics and, consequently, their catalytic activity. An inventory of experimental methods is provided for characterizing POPs' optical, morphological, electrochemical, and catalytic characteristics. The focus of this review is to thoroughly investigate the photochemistry of these polymeric organic photocatalysts with an emphasis on understanding the processes of internal charge generation and transport within POPs. The review covers several types of amorphous POP materials, including those based on conjugated microporous polymers (CMPs), inherent microporosity polymers, hyper-crosslinked polymers, and porous aromatic frameworks. Additionally, common synthetic approaches for these materials are briefly discussed.

Highly Active Photoreduction of Atmospheric-Concentration CO2 into CH3COOH over Palladium Particles on Nb2O5 Nanosheets.

The endeavor to drive CO2 photoreduction towards the synthesis of C2 products is largely thwarted by the colossal energy hurdle inherent in C-C coupling. Herein, we load active metal particles on metal oxide nanosheets to build the dual metal pair sites for steering C-C coupling to form C2 products. Taking Pd particles anchored on the Nb2O5 nanosheets as an example, the high-angle annular dark-field image and X-ray photoelectron spectroscopy demonstrate the presence of Pd-Nb metal pair sites on the Pd-Nb2O5 nanosheets. Density functional theory calculations reveal these sites exhibit a low reaction energy barrier of only 1.02 eV for C-C coupling, implying that the introduction of Pd particles effectively tailors the reaction step to form C2 products. Therefore, the Pd-Nb2O5 nanosheets achieve a CH3COOH evolution rate of 13.5 µmol g-1 h-1 in photoreduction of atmospheric-concentration CO2, outshining all other single photocatalysts reported to date under analogous conditions.

Improvement of photocatalytic ammonia production of cobalt ferrite nanoparticles utilizing microporous ZSM-5 type ferrisilicate zeolite.

The development of decarbonized synthesis approaches is a critical step in the fabrication of ammonia, an indispensable chemical and a potential carbon-neutral energy carrier. In this regard, the photocatalytic production technology has gained ample attention as a sustainable alternative to energy-intensive and environmentally detrimental Haber-Bosch process. Here, we present cobalt ferrite nanoparticles supported on microporous ZSM-5 type ferrisilicate zeolite as a desirable novel photocatalyst for the ammonia generation. The zeolite introduced as a microporous support increasing the catalytically active sites. A straightforward one-pot sol-gel method was used to synthesize cobalt ferrite (CoFe2O4) and CoFe2O4/ferrisilicate (CF/FS) nanocomposites with various weight percentages (10, 25 and 50%) of CoFe2O4. The photocatalytic performances of the samples in the production of ammonia were investigated under visible light irradiation. The highest rate of NH4+ production (484.74 µmol L-1 h-1) was achieved using the CF50%/FS photocatalyst. The distribution of < 50 nm-sized CoFe2O4 nanoparticles on the surface of the zeolite, as demonstrated by TEM images, and extensive BET surface areas are presented as convincing evidences for the improved photocatalytic activity paticularly in CF50%/FS photocatalyst.

Theoretical Study on Photocatalytic Reduction of CO2 on Anatase/Rutile Mixed-Phase TiO2.

The construction of anatase/rutile heterojunctions in TiO2 is an effective way of improving the CO2 photoreduction activity. Yet, the origin of the superior photocatalytic performance is still unclear. To solve this issue, the band edges between anatase and rutile phases were theoretically determined based on the three-phase atomic model of (112)A/II/(101)R, and simultaneously the CO2 reduction processes were meticulously investigated. Our calculations show that photogenerated holes can move readily from anatase to rutile via the thin intermediated II phase, while photoelectrons flowing in the opposite direction may be impeded due to the electron trapping sites at the II phase. However, the large potential drop across the anatase/rutile interface and the strong built-in electric field can provide an effective driving force for photoelectrons' migration to anatase. In addition, the II phase can better enhance the solar light utilization of (112)A/(100)II, including a wide light response range and an intensive optical absorption coefficient. Meanwhile, the mixed-phase TiO2 possesses negligible hydrogenation energy (CO2 to COOH*) and lower rate-limiting energy (HCOOH* to HCO*), which greatly facilitate CH3OH generation. The efficient charge separation, strengthened light absorption, and facile CO2 reduction successfully demonstrate that the anatase/rutile mixed-phase TiO2 is an efficient photocatalyst utilized for CO2 conversion.

Construction of An Artificial Photosynthesis System with A Single CdS QDs-Ferritin Hybrid Molecule.

Establishing artificial photosynthesis systems in a simple but effective manner to mitigate the greenhouse effect and address the energy crisis remains challenging. The combination of photocatalysis technology with bioengineering is an emerging field with great potential to construct such artificial photosynthesis systems, but so far, it has barely been explored in this area. Herein, an artificial photocatalysis platform is constructed with high CO2 conversion and H2O splitting capability by integration of CdS QDs into the intra-subunit interface of H-type ferritin (Marsupenaeus japonicus), a natural ferroxidase through protein interface redesign. The crystal structure of the synthesized CdS QDs with engineered ferritin molecules as bio-templates confirmed the design at an atomic level. Notably, upon absorbing desirable visible light (≈420 nm), such a single CdS-ferritin hybrid molecule is able to selectively catalyze the reduction of CO2 into HCOOH (≈90%), meanwhile catalyzing the oxidation of H2O into O2 in an aqueous environment. The O2 production rate reached to 180 µmol g-1 h-1, and the HCOOH output hit almost 800 µmol g-1 h-1. This work advances the utilization of the four-helix bundle structure for crafting artificial photosynthesis systems, facilitating the seamless integration of bioengineering and photocatalysis technology.