Rod-Shaped Au@Ce Nano-Platforms for Enhancing Photodynamic Tumor Collaborative Therapy.

Tumor photodynamic therapy (PDT) relies on intratumoral free radicals, while the limited oxygen source and the depletion of tissue oxygen may exacerbate the hypoxia. As the treatment progresses, there will eventually be a problem of insufficient free radicals. Here, it is found that Au@CeO2 nano-rods (Au@Ce NRs), assembled by gold nano-rods (Au NRs) and ceria nanoparticles (CeO2 NPs), can efficaciously absorb near-infrared light (NIR) to promote the release of oxygen and free radicals. Au@Ce NRs exhibit a higher proportion of Ce3+ (Ce2O3) after oxygen release, while Ce3+ is subsequently oxidized to Ce4+ (CeO2) by trace H2O2. Interestingly, Au@Ce NRs re-oxidized by trace H2O2 can re-releasing oxygen and free radicals again upon NIR treatment, achieving oxygenation/oxygen evolution, similar to charging/discharging. This loop maximizes the conversion of limited oxygen source into highly cytotoxic free radicals. As a result, when B16-F10 cells are treated by NIR/Au@Ce NRs, more tumor cells undergo apoptosis, consistent with the higher level of free radicals. Importantly, NIR/Au@Ce NRs successfully suppresses tumor growth and promotes the generation of epidermal collagen fibers in the transplanted tumor model. Therefore, the rod-shaped Au@Ce NRs provide an ideal platform for maximizing the utilization of intratumoral oxygen sources and improving the treatment of melanoma.

Physicochemical and photocatalytic properties of Ag2CrO4/Fe2O3/CeO2 ternary nanocomposite.

The study presents Ag2CrO4/Fe2O3/CeO2 ternary nanocomposite, based on Fe2O3/CeO2 binary composites, which demonstrated excellent photocatalytic performance in the photodegradation of methylene blue under solar irradiation. The Ag2CrO4/Fe2O3/CeO2 nanocomposites was orthorhombic, ilmenite, and cubic-fluorite phases of Ag2CrO4, Fe2O3, and CeO2, respectively, according to the XRD examination. A strong bond between Ag2CrO4, Fe2O3, and CeO2 within the nanocomposite was demonstrated by the SEM and TEM investigations. Moreover, it was discovered that the coupling of Ag2CrO4 and Fe2O3 caused a red shift and moved CeO2 absorption edge from the UV to the visible spectrum. The reason behind this is that the band gap of CeO2 reduced 2.85 to 2.69 eV and the absorbance band intensity increased in visible region. Utilizing visible light, Ag2CrO4/Fe2O3/CeO2 ternary nanocomposites exhibit enhanced photocatalytic properties (98.90%) for the degradation of methylene blue (MB) within 100 min. The long-term reliability and recyclability of the photocatalyst were explored through 3 successive cycles. An active radical quenching test was conducted to elucidate the involvement of O2 - and OH which are the primary reactive species in the photocatalytic breakdown of MB. Ag2CrO4/Fe2O3/CeO2 ternary nanocomposites displayed notable improvements in photodegradation activity, making them well suited for the effective removal of hazardous dyes present in textile effluents.

Revealing the Effect of Electronic Configuration in Cux Species on CO2 Photoreduction Characteristic Products.

As of the present time, the in-depth study of the structure-activity relationship between electronic configuration and CO2 photoreduction performance is often overlooked. Herein, a series of Cux species modified CeO2 nanodots are constructed in situ by flame spray pyrolysis (FSP) to achieve an efficient photocatalytic CO2-to-C2 conversion with an electron utilization of up to 142.5 µmol g-1. Through an in-depth study of the electronic behavior and catalytic pathways, it is found that the Cu0/Cu+ species in the coexistence state of Cu0/Cu+/Cu2+ can optimize the energy band structure, photocurrent stability, and provide a kinetic basis for the active surface catalytic reaction process that requires the conversion of multiple electrons into C2 products, which ultimately enhances the CO2-to-C2H6 photoreduction by 3.8-fold and that for CO2-to-C2H4 photoreduction by 5.2-fold. Besides, the Cu2+ species in the coexistence state of Cu0/Cu+/Cu2+ are able to regulate the electronic behavior and the choice of the catalytic pathway, enabling the transitions between CO2-to-C2H6 and CO2-to-C2H4. This work indicates that electronic configuration optimization is an effective strategy to significantly enhance the CO2 photoreduction performance and provides new ideas for the design and synthesis of high-performance heterostructure photocatalysts.

Boosted Solar Thermochemical Low-temperature CO2 Splitting On Pt/CeO2 By Interface Catalysis.

Solar thermochemical CO2 splitting using metal oxides is considered as a promising approach to produce solar fuels since it is capable to tap abundant sunlight directly and store solar energy in the renewable fuel. It remains a grand challenge to achieve highly efficient CO2 splitting at low temperature (<800 oC) due to insufficient activation of metal oxides for CO2.Herein, the introduction of a small amount of Pt was found to be able to greatly increase the performance of CO2 splitting with the highest peak CO production rate of about 65 mL min-1 g-1, CO productivity of about 53 mL g-1, nearly 100% CO2 conversion and long-term stability for 0.5Pt/CeO2 which exceeded most of the state-of-the-art transition metals-based oxides even at lower temperature (700 oC). This could be attributed to the addition of Pt leading to the formation of an interface (Pt0-Ov-Ce3+) after CH4 reduction, which improved CO2 activation and dissociation due to beneficial breakage of C=O bond by the cooperation of Pt0 and oxygen vacancies in the interface.

Ni-Zn/CeO2 nanocomposites for enhanced adsorptive removal of 4-chlorophenol.

Chlorophenols are one of the major organic pollutants responsible for the contamination of water bodies. This study explores the application of Ni-Zn/CeO2 nanocomposites, synthesized via the aqueous co-precipitation method, as effective adsorbents for the 4-chlorophenol removal from aqueous solutions. The nanocomposites' chemical and structural characteristics were assessed using different physical characterization methods, viz. X-ray diffraction, transmission electron microscopy, Fourier transform infrared spectroscopy, zeta potential, using a Box-Behnken design within response surface methodology, optimal conditions of pH 3, temperature 20 °C, contact time 120 min, adsorbent dosage 0.05 g, and 4-chlorophenol concentration 50 ppm are identified. Among the nanocomposites tested, NZC 20:10:70, with 20% Ni and 10% Zn, achieves enhanced performance, removing 99.1% of 4-chlorophenol within 2 h. Adsorption kinetics follow the pseudo-second-order model and equilibrium data fit the Freundlich isotherm. Thermodynamic analysis indicates an exothermic and spontaneous process. The adsorption capacity of NZC 20:10:70 shows significant enhancement, growing from 19.85 mg/g at 10 ppm to 96.33 mg/g at 50 ppm initial concentration. Physical characterization confirms NZC 20:10:70's superior properties, including a high surface area of 118.471 m2/g. Evaluating economic viability, NZC 20:10:70 demonstrates robust reusability, retaining 85% efficiency over eight regeneration cycles. These results highlight NZC 20:10:70 as a promising adsorbent for effective and sustainable chlorophenol removal in water treatment.

Optimized Ammonia-Sensing Electrode with CeO2/rGO Nano-Composite Coating Synthesized by Focused Laser Ablation in Liquid.

This study investigated the synthesis of cerium oxide (CeO2) nanoparticles (NPs) and composites with reduced graphene oxide (rGO) for the enhanced electrochemical sensing of ammonia. CeO2 NPs were prepared by the focused laser ablation in liquid (LAL) method, which enabled the production of high-purity, spherical nanoparticles with a uniform dispersion and sizes under 50 nm in a short time. The effects of varying irradiation fluence and time on the nanoparticle size, production yield, and dispersion were systematically studied. The synthesized CeO2 NPs were doped with rGO to form CeO2/rGO composites, which were drop casted to modify the glassy carbon electrodes (GCE). The CeO2/rGO-GCE electrodes exhibited superior electrochemical properties compared with single-component electrodes, which demonstrated the significant potential for ammonia detection, especially at a 4 J/cm2 fluence. The CeO2/rGO composites showed uniformly dispersed CeO2 NPs between the rGO sheets, which enhanced the conductivity, as confirmed by SEM, EDS mapping, and XRD analysis. Cyclic voltammetry data demonstrated superior electrochemical activity of the CeO2/rGO composite electrodes, with the 2rGO/1CeO2 ratio showing the highest current response and sensitivity. The CV response to varying ammonia concentrations exhibited a linear relationship, indicating the electrode's capability for accurate quantification. These findings highlight the effectiveness of focused laser ablation in enhancing nanoparticle synthesis and the promising synergistic effects of CeO2 and rGO in developing high-performance electrochemical sensors.

Emerging 2D nanoscale metal oxide sensor: Semiconducting CeO2nano-sheets for enhanced formaldehyde vapor sensing.

Herein, we fabricated nanoscale 2D CeO2 sheet structure to develop a stable resistive gas sensor for detection of low concentration (ppm) level formaldehyde vapors. The fabricated CeO2 nanosheets (NSs) showed an optical band gap of 3.53 eV and cubic fluorite crystal structure with enriched defect states. The formation of 2D NSs with well crystalline phases is clearly observed from HRTEM imag-es. The NSs have been shown tremendous blue-green emission related to large oxygen defects. A VOC sensing device based on fabricated two-dimensional NSs has been developed for the sensing of different VOCs. The device showed better sensing for formaldehyde compared with other VOCs (2-propanol, methanol, ethanol, and toluene). The response was found to be 4.35, with the response and recovery time of 71 s and 310 s, respectively. The device showed an increment of the recovery time (71 s to 100 s) with the decrement of the formaldehyde ppm (100 ppm to 20 ppm). Theoretical fit-tings provided the detection limit of formaldehyde ≈ 8.86 ± 0.45 ppm with sensitivity of 0.56 ± 0.05 ppm-1. The sensor device showed good reproducibility with excellent stability over the study period of 135 days, with a deviation of 1.8 % for 100 ppm formaldehyde. The average size of the NSs (≈ 24 nm) calculated from HRTEM observation showed lower value than the calculated Debye length (≈ 44 nm) of the charge accumulation during VOCs sensing. Different defect states, interstitial and surface states in the CeO2 NSs as observed from the Raman spectrum and emission spectrum are responsible for the formaldehyde sensing. This work offers an insight into 2D semiconductor-based oxide materi-al for highly sensitive and stable formaldehyde sensors. .

Influence of Rare-Earth Doping Content and Type on Phase Transformation and Transport Properties in Highly Doped CeO2.

Rare-earth doped CeO2 materials find extensive application in high-temperature energy conversion devices such as solid oxide fuel cells and electrolyzers. However, understanding the complex relationship between structural and electrical properties, particularly concerning rare-earth ionic size and content, remains a subject of ongoing debate, with conflicting published results. In this study, we have conducted comprehensive long-range and local order structural characterization of Ce1-xLnxO2-x/2 samples (x ≤ 0.6; Ln = La, Nd, Sm, Gd, and Yb) using X-ray and neutron powder diffraction, Raman spectroscopy, and electron diffraction. The increase in the rare-earth dopant content leads to a progressive phase transformation from a disordered fluorite structure to a C-type ordered superstructure, accompanied by reduced ionic conductivity. Samples with low dopant content (x = 0.2) exhibit higher ionic conductivity in Gd3+ and Sm3+ series due to lower lattice cell distortion. Conversely, highly doped samples (x = 0.6) exhibit superior conductivity for larger rare-earth dopant cations. Thermogravimetric analysis confirms increased water uptake and proton conductivity with increasing dopant concentration, while the electronic conductivity remains relatively unaffected, resulting in reduced ionic transport numbers. These findings offer insights into the relationship between transport properties and defect-induced local distortions in rare-earth doped CeO2, suggesting the potential for developing new functional materials with mixed ionic oxide, proton, and electronic conductivity for high-temperature energy systems.

Molecularly imprinted polymer-based electrochemical sensor for rapid detection of masked deoxynivalenol with Mn-doped CeO2 nanozyme as signal amplifier.

Deoxynivalenol-3-glucoside (D3G), the masked form of the important mycotoxin deoxynivalenol (DON), displays potential toxicity but is difficult to control owing to the lack of rapid detection methods. Herein, an innovative molecularly imprinted polymer (MIP)-based electrochemical sensor was developed for the rapid detection of D3G. MIP, an efficient recognition element for D3G, was electropolymerized using o-phenylenediamine based on a surface functional monomer-directing strategy for the first time. CeO2, which contains both Ce3+ and Ce4+ oxidation states, was introduced as a nanozyme to catalyze H2O2 reduction, while Mn doping generated more oxygen vacancies and considerably improved the catalytic activity. Mn-CeO2 also served as a promising substrate material because of its large surface area and excellent conductivity. Under optimal conditions, a good linear relationship was observed for D3G detection over the concentration range of 0.01-50 ng/mL. The proposed sensor could detect D3G down to 0.003 ng/mL with excellent selectivity, even distinguishing its precursor DON in complex samples. The sensor exhibited acceptable stability with high reproducibility and accuracy, and could successfully determine D3G in grain samples. To the best of our knowledge, this is the first electrochemical sensing platform for rapid D3G detection that can easily be expanded to other masked mycotoxins.

Exploring the Impact of Oxygen Vacances in Co/Pr-CeO2 Catalysts on H2 Production via the Water-Gas Shift Reaction.

In this study, we utilized various Pr-doped CeO2 catalysts (Pr=5, 10, 20, and 30 wt.%) as a support medium for the dispersion of cobalt (Co) nanoparticles, aiming to investigate the impact of oxygen vacancies on the water-gas shift (WGS) reaction. Different characterization techniques were employed to understand the insights into the structure-activity relationship governing the performance of Pr doped ceria supported Co catalysts towards WGS reaction. Our findings reveal that Co/Pr-CeO2 catalysts at optimum Pr loading (10 wt.%) exhibit a superior CO conversion (88%) facilitated by the presence of more oxygen vacancies induced by Pr doping into the CeO2 lattice, as opposed to the performance of the pure Co/CeO2 catalytic system. It was also found that the highest activity was obtained at increased intrinsic oxygen vacancies and strong synergy between Co and Pr/CeO2 support, fostering more favorable CO activation at the interfacial sites, thus accounting for the observed enhanced activity.

Engineering Asymmetric Strain within C-Shaped CeO2 Nanofibers for Stabilizing Sub-3 nm Pt Clusters against Sintering.

Ultrafine noble metals have emerged as advanced nanocatalysts in modern society but still suffer from unavoidable sintering at temperatures above 250 °C (e.g., Pt). In this work, closely packed CeO2 grains were confined elegantly in fibrous nanostructures and served as a porous support for stabilizing sub-3 nm Pt clusters. Through precisely manipulating the asymmetry of obtained nanofibers, uneven strain was induced within C-shaped CeO2 nanofibers with tensile strain at the outer side and compressive strain at the inner side. As a result, the enriched oxygen vacancies significantly improved adhesion of Pt to CeO2, thereby boosting the sinter-resistance of ultraclose sub-3 nm Pt clusters. Notably, no aggregation was observed even after exposure to humid air at 750 °C for 12 h, which is far beyond their Tammann temperature (sintering onset temperature, below 250 °C). In situ HAADF-STEM observation revealed a unique sintering mechanism, wherein Pt clusters initially migrate toward the grain boundaries with concentrated stain and undergo slight coalescence, followed by subsequent Ostwald ripening at higher temperatures. Moreover, the sinter-resistant Pt/C-shaped CeO2 effectively catalyzed soot combustion (over 700 °C) in a durable manner. This work provides a new insight for developing sinter-resistant catalysts from the perspective of strain engineering within nano-oxides.

Facet-dependent diversity of Pt-O coordination for Pt 1 /CeO 2 catalysts achieved by oriented atomic deposition.

The surface chemistry of CeO2 is dictated by the well-defined facets, which exert great influence on the supported metal species and the catalytic performance. Here we report Pt1/CeO2 catalysts exhibiting specific structures of Pt-O coordination on different facets by using adequate preparation methods. The simple impregnation method results in Pt-O3 coordination on the predominantly exposed {111} facets, while the photo-deposition method achieves oriented atomic deposition for Pt-O4 coordination into the "nano-pocket" structure of {100} facets at the top. Compared to the impregnated Pt1/CeO2 catalyst showing normal redox properties and low-temperature activity for CO oxidation, the photo-deposited Pt1/CeO2 exhibits uncustomary strong metal-support interaction and extraordinary high-temperature stability. The preparation methods dictate the facet-dependent diversity of Pt-O coordination, resulting in the further activity-selectivity trade-off. By applying specific preparation routes, our work provides an example of disentangling the effects of support facets and coordination environments for nano-catalysts.

Effect of electromigration on microstructure and properties of CeO2 nanopartical-reinforced Sn58Bi/Cu solder joints.

To mitigate the decrease in mechanical performance of Sn58Bi/Cu solder joints resulting from electromigration-induced damage. The CeO2 nanoparticles were incorporated into Sn58Bi solder by a melt-casting method, and their effects on the microstructure and properties of Sn58Bi/Cu solder joints under electromigration were investigated. The study results demonstrate that the addition of 0.125 ~ 0.5 wt% CeO2 nanoparticles refines the eutectic microstructure of Sn58Bi solder alloy. At an addition amount of 0.5 wt%, the composite solder alloy exhibits the maximum tensile strength of 68.9 MPa, which is 37% higher than that of the base solder. CeO2 nanoparticle-reinforced Sn58Bi solder can achieve excellent solderbility with Cu substrates and the joints can significantly inhibit the growth of the anodic Bi-rich layer, which is responsible for electromigration. With the extension of current stressing time, Bi-rich and Sn-rich layer are respectively formed on the anode and cathode in the joints. The intermetallic compound (IMC) layer grows asymmetrically, transitioning from a fan-shaped morphology to a flattened structure at the anode and to a thickened mountain-like morphology at the cathode. Adding the CeO2 nanoparticles helps to mitigate the decrease in mechanical performance caused by electromigration damage during current application to some extent. Over the current stressing period of 288 ~ 480 h, the fracture position shifts from the anodic IMC/Bi-rich interface to the cathodic Sn-rich/IMC interface. The fracture mechanism transitions from a brittle fracture characterized by plate-like cleavage to a ductile-brittle mixed fracture with fine dimples and cleavage.

Effect of Nanoceria Suspension Addition on the Physicochemical and Mechanical Properties of Hybrid Organic-Inorganic Hydroxyapatite Composite Scaffolds.

In the current study, the synthesis of hydroxyapatite-ceria (HAP-CeO2) scaffolds is attempted through a bioinspired chemical approach. The utilized colloidal CeO2 suspension presents antifungal activity against the Aspergillus flavus and Aspergillus fumigatus species at concentrations higher than 86.1 ppm. Three different series of the composite HAP-CeO2 suspensions are produced, which are differentiated based on the precursor suspension to which the CeO2 suspension is added and by whether this addition takes place before or after the formation of the hydroxyapatite phase. Each of the series consists of three suspensions, in which the pure ceria weight reaches 4, 5, and 10% (by mass) of the produced hydroxyapatite, respectively. The characterization showed that the 2S series's specimens present the greater alteration towards their viscoelastic properties. Furthermore, the 2S series's sample with 4% CeO2 presents the best mechanical response. This is due to the growth of needle-like HAP crystals during lyophilization, which-when oriented perpendicular to the direction of stress application-enhance the resistance of the sample to deformation. The 2S series's scaffolds had an average pore size equal to 100 µm and minimum open porosity 89.5% while simultaneously presented the lowest dissolution rate in phosphate buffered saline.

Bi/CeO2-Decorated CuS Electrocatalysts for CO2-to-Formate Conversion.

The electrocatalytic carbon dioxide (CO2) reduction reaction (CO2RR) is extensively regarded as a promising strategy to reach carbon neutralization. Copper sulfide (CuS) has been widely studied for its ability to produce C1 products with high selectivity. However, challenges still remain owing to the poor selectivity of formate. Here, a Bi/CeO2/CuS composite was synthesized using a simple solvothermal method. Bi/CeO2-decorated CuS possessed high formate selectivity, with the Faraday efficiency and current density reaching 88% and 17 mA cm-2, respectively, in an H-cell. The Bi/CeO2/CuS structure significantly reduces the energy barrier formed by OCHO*, resulting in the high activity and selectivity of the CO2 conversion to formate. Ce4+ readily undergoes reduction to Ce3+, allowing the formation of a conductive network of Ce4+/Ce3+. This network facilitates electron transfer, stabilizes the Cu+ species, and enhances the adsorption and activation of CO2. Furthermore, sulfur catalyzes the OCHO* transformation to formate. This work describes a highly efficient catalyst for CO2 to formate, which will aid in catalyst design for CO2RR to target products.

Atomic Layer Deposition of CeO2 Film with a Novel Heteroleptic Ce(III) Complex.

In this paper, four heteroleptic Ce(III) complexes, including Ce(thd)3-phen (thd = 2,2,6,6-tetramethyl-3,5-heptanedione, phen = 1, 10-phenanthroline (1), Ce(thd)3-MEDA (MEDA = N-Methylethylenediamine (2), Ce(thd)3-MOMA (MOMA = N-(2-Methoxyethyl)methylamine (3), and Ce(thd)3-DMDE (DMDE = N,N″-dimethyl ethanol amine (4), were synthesized and characterized with 1H-NMR, elemental analysis, and X-ray single-crystal diffraction. The thermogravimetric analysis and vapor pressure results indicated that the complexing ability of a nitrogen-containing bidentate ligand with a cerium ion was stronger than that of a mixed oxygen-nitrogen-containing bidentate ligand. Complex 2 was selected as an ALD precursor to deposit a CeO2 film on a SiO2/Si (100) wafer. The self-limited deposition results demonstrated that complex 2 was a potential ALD precursor.

Phase-Engineered MoSe2/CeO2 Composites for Room-Temperature Gas Sensing with a Drastic Discrimination of NH3 and TEA Gases.

Detecting and distinguishing between hazardous gases with similar odors by using conventional sensor technology for safeguarding human health and ensuring food safety are significant challenges. Bulky, costly, and power-hungry devices, such as that used for gas chromatography-mass spectrometry (GC-MS), are widely employed for gas sensing. Using a single chemiresistive semiconductor or electric nose (e-nose) gas sensor to achieve this objective is difficult, mainly because of its selectivity issue. Thus, there is a need to develop new materials with tunable and versatile sensing characteristics. Phase engineering of two-dimensional materials to better utilize their physiochemical properties has attracted considerable attention. Here, we show that MoSe2 phase-transition/CeO2 composites can be effectively used to distinguish ammonia (NH3) and triethylamine (TEA) at room temperature. The phase transition of nanocomposite samples from semimetallic (1T) to semiconducting (2H) prepared at different synthesis temperatures is confirmed via X-ray photoelectron spectroscopy (XPS). A composite sensor in which the 2H phase of MoSe2 is predominant lacks discrimination capability and is less responsive to NH3 and TEA. An MoSe2/CeO2 composite sensor with a higher 1T phase content exhibits high selectivity for NH3, whereas one with a higher 2H phase content (2H > 1T) shows more selective behavior toward TEA. For example, for 50% relative humidity, the MoSe2/CeO2 sensor's signal changes from the baseline by 45% and 58% for 1 ppm of NH3 and TEA, respectively, indicating a low limit of detection (LOD) of 70 and 160 ppb, respectively. The composites' superior sensing characteristics are mainly attributed to their large specific surface area, their numerous active sites, presence of defects, and the n-n type heterojunction between MoSe2 and CeO2. The sensing mechanism is elucidated using Raman spectroscopy, XPS, and GC-MS results. Their phase-transition characteristics render MoSe2/CeO2 sensors promising for use in distributed, low-cost, and room-temperature sensor networks, and they offer new opportunities for the development of integrated advanced smart sensing technologies for environmental and healthcare.

Differential Activation of Alkynes between Capped and Naked Ag Nanoclusters Anchored by Highly-Open Mesoporous CeO2 for Two Coupling Reactions with CO2.

The cyclization of 3-hydroxy alkynes and the carboxylation of terminal alkynes both with CO2 are two attractive strategies to simultaneously reduce CO2 emission and produce value-added chemicals. Herein, the differential activation of alkynes over atomically precise Ag nanoclusters (NCs) supported on Metal-organic framework-derived highly-open mesoporous CeO2 (HM-CeO2) by reserving or removing their surface captopril ligands is reported. The ligand-capped Ag NCs possess electron-rich Ag atoms as efficient π-activation catalytic sites in cyclization reactions, while the naked Ag NCs possess partial positive-charged Ag atoms as perfect σ-activation catalytic sites in carboxylation reactions. Impressively, via coupling with HM-CeO2 featuring abundant basic sites and quick mass transfer, the ligand-capped Ag NCs afford 97.9% yield of 4,4-dimethyl-5-methylidene-1,3-dioxolan-2-one for the cyclization of 2-methyl-3-butyn-2-ol with CO2, which is 4.5 times that of the naked Ag NCs (21.7%), while the naked Ag NCs achieve 98.5% yield of n-butyl 2-alkynoate for the carboxylation of phenylacetylene with CO2, which is 15.6 times that of ligand-capped Ag NCs (6.3%). Density functional theory calculations reveal the ligand-capped Ag NCs can effectively activate alkynyl carbonate ions for the intramolecular ring closing in cyclization reaction, while the naked Ag NCs are highly affiliative in stabilizing terminal alkynyl anions for the insertion of CO2 in carboxylation reaction.

Spatial-resolved and self-calibrated 3D-printed photoelectrochemical biosensor engineered by multifunctional CeO2/CdS heterostructure for immunoassay.

A spatial-resolved and self-calibrated photoelectrochemical (PEC) biosensor has been fabricated by a multifunctional CeO2/CdS heterostructure, achieving portable and sensitive detection of carcinoembryonic antigen (CEA) using a homemade 3D printing device. The CeO2/CdS heterostructure with matched band structure is prepared to construct the dual-photoelectrodes to improve the PEC response of CeO2. In particular, as the photoactive nanomaterial, the CeO2 also plays the role of peroxidase mimetic nanozymes. Therefore, the catalytic performance of CeO2 with different morphologies (e.g., nano-cubes, nano-rods and nano-octahedra) have been studied, and CeO2 nano-cubes (c-CeO2) achieve the optimal catalytic activity. Upon introducing CEA, the sandwich-type immunocomplex is formed in the microplate using GOx-AuNPs-labeled second antibody as detection antibody. As a result, H2O2 can be produced from the catalytic oxidization of glucose substrate by GOx, which is further catalyzed by CeO2 to form •OH, thus in situ etching CdS and decreasing the photocurrents. The self-calibration is achieved by the dual-channel photoelectrodes on the homemade 3D printing device to obtain the photocurrents ratio, thus effectively normalizing the fluctuations of external factors to enhance the accuracy. This integrated biosensor with a detection limit as low as 0.057 ng mL-1 provides a promising way for ultrasensitive immunoassay in clinic application in complex environments.

CeO2 nanospheres incorporated with Bi2MoO6/g-C3N4 enhanced photocatalysis towards environmental pollutant Rhodamine B removal.

We have adopted a novel CeO2/Bi2MoO6/g-C3N4-based ternary nanocomposite that was synthesized via hydrothermal technique. The physiochemical characterization of as-prepared samples was examined through various analytical techniques such as X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), field emission scanning electron microscopy (FE-SEM), transmission electron microscopy TEM, photoluminescent spectra (PL), X-ray photoelectron spectroscopy (XPS), Brunauer-Emmett-Teller (BET), and ultraviolet diffuse reflectance spectroscopy (UV-DRS) technique. In addition, the photocatalytic performance was carried out by degradation of Rhodamine B dye under visible light irradiation using this nanocatalyst. The ternary nanocomposite achieved 94% of the degradation efficiency within 100 min which is higher than the pristine and binary composites under the predetermined condition pH = 7, Rhodamine B dye = 5 mg/L, and catalyst concentration = 150 mg/L. The experimental synergetic effect of CeO2/Bi2MoO6/g-C3N4 ternary nanocomposite has been ascribed to the interfacial charge carrier migration between CeO2, Bi2MoO6, and g-C3N4. The optical absorption range of CeO2/Bi2MoO6/g-C3N4 ternary nanocomposite was enhanced, and the band gap was reduced up to 2.2 eV. In addition, scavenger trapping experiment proves that the super oxide anions (O2-.) and photogenerated holes are the major active species. The reusability and stability experiment proved the CeO2/Bi2MoO6/g-C3N4 ternary nanocomposite keeps good durability during the photocatalytic degradation process after the five successive cycles. Furthermore, based on the results, the charge carrier transfer photocatalytic mechanism was also discussed. This CeO2/Bi2MoO6/g-C3N4 ternary nanocomposite may offer the cheapest material and extend the great opportunity for clean and environmental remediation approach under the visible light irradiation.