Polyoxometalate-Guanosine Monophosphate Hydrogels with Haloperoxidase-like Activity for Antibacterial Performance.

Haloperoxidases represent an important class of enzymes that nature adopts as a defense mechanism to combat the colonial buildup of microorganisms on surfaces, commonly known as biofouling. Subsequently, there has been tremendous focus on the development of artificial haloperoxidase mimics that can catalyze the oxidation of X- (halide ion) in the presence of H2O2 to form HOX. The natural intermediate HOX disrupts the bacterial quorum sensing, thus preventing biofilm formation. Herein, we report a simple method for the formation of supramolecular hydrogels through the self-assembly of Keggin-structured polyoxometalates, phosphotungstic acid, and silicotungstic acid with the small biomolecule guanosine monophosphate (GMP) in an aqueous medium. The polyoxometalate-GMP hydrogels that contained highly entangled nanofibers were mechanically robust and showed thixotropic properties. The gelation of the polyoxometalates with GMP not only rendered manifold enhancement in biocompatibility but also the fibril network in the hydrogel provided high water wettability and the polyoxometalates acted as an efficient haloperoxidase mimic to trigger oxidative iodination, as demonstrated by a haloperoxidase assay. The antifouling activity of the phosphotungstic acid-GMP hydrogel was demonstrated against both Gram-positive and Gram-negative bacteria, which showed enhanced antibacterial performance of the hydrogel as compared to the polyoxometalate alone. We envision that the polyoxometalate-GMP hydrogels may facilitate mechanically robust coatings in a simple pathway that can be useful for antifouling applications.

Durability assessment of hydrogel mountings for contrast-enhanced micro-CT.

Micro-computed tomography (micro-CT) provides valuable data for studying soft tissue, though it is often affected by sample movement during scans and low contrast in X-ray absorption. This can result in lower image quality and geometric inaccuracies, collectively known as 'artefacts'. To mitigate these issues, samples can be embedded in hydrogels and enriched with heavy metals for contrast enhancement. However, the long-term durability of these enhancements remains largely unexplored. In this study, we examine the effects of two contrast enhancement agents - iodine and phosphotungstic acid (PTA) - and two hydrogels - agarose and Poloxamer 407 - over a 14-day period. We used Drosophila melanogaster as a test model for our investigation. Our findings reveal that PTA and agarose are highly durable, while iodine and poloxamer hydrogel exhibits higher leakage rates. These observations lay the foundation for estimating contrast stabilities in contrast-enhanced micro-CT with hydrogel embedding and serve to inform future research in this field.

Catalytic Conversion of Carbohydrates into 5-Hydroxymethylfurfural by Phosphotungstic Acid Encapsulated in MIL-101 (Cr, Sn) Catalyst in Deep Eutectic Solvents.

Herein, we report the synthesis of bimetal-organic frameworks (BMOFs) with both Brønsted and Lewis acidities, in which phosphotungstic acid (PTA) was encapsulated in BMOFs. It is efficient in converting starch to 5-hydroxymethyl-furfural (HMF) in deep eutectic solvents (DESs) such as choline chloride and formic acid. The highest yield of HMF (37.94%) was obtained using P0.5/BMOFs1.0 to catalyze starch in a mixed solvent system comprising DESs and ethyl acetate (EAC) (v/v; 2:3) at 180 °C and a reaction time of 10 min. Employing a DES as a cocatalyst and solvent reduced the use of organic solvents. The catalyst showed adequate reusability, and the HMF yield only decreased by 2.88% after six cycles of reuse compared with that of the initial catalyst. This study demonstrates the application potential of BMOFs in the conversion of biomass to useful molecules with commercial and/or research value.

Ultrasensitive photoelectrochemical detection of glutathione based on the multifunctional catalytic properties of phosphotungstic acid.

A novel photoelectrochemical (PEC) sensor was constructed for the highly sensitive detection of reduced glutathione (GSH) based on the multiple catalytic properties of phosphotungstic acid (PTA). In this work, the catalytic properties of PTA were applied to PEC sensing for the first time and interpreted in detail. First, PTA as an electron acceptor can inhibit the complexation of photogenerated electron-hole pairs in p-Cu2O, thus significantly increasing the photogenerated current of p-type semiconductor material Cu2O. Secondly, when GSH is oxidized to oxidized glutathione (GSSG) by photogenerated holes on the photocathode, PTA is able to reduce GSSG to GSH by transferring protons, forming a redox cycle regeneration process of GSH. Finally, the relatively large amount of PTA in the background solution was able to pre-oxidize interfering substances such as L-cysteine and ascorbic acid, which improved the selectivity of the method. Under the optimal experimental conditions, the linear range of the PEC sensor response to GSH was 0.050-100 nmol L-1, with a detection limit as low as 0.017 nmol L-1 (S/N = 3), which can be applied to the detection of GSH content in cell lysate samples.

Keggin type phosphotungstic acid intercalated copper-chromium-layered double hydroxide reinforced porous hollow fiber as a sorbent for hollow fiber solid phase microextraction of selected chlorophenols besides their quantification via high performance liquid chromatography.

Herein, a copper-chromium-layered double hydroxide (Cu/Cr-LDH) was synthesized by the co-precipitation method. The Cu/Cr-LDH was intercalated to the Keggin-type polyoxometalate (H3PW12O40). The modified LDH accommodated in the pores of hollow fiber (HF), to prepare the extracting device for the HF-solid phase microextraction method (HF-SPME). The method was used for the extraction of 4-chlorophenol, 2,4-dichlorophenol, and 2,4,6- trichlorophenol from tap water, river water, and tea sample. The extracted target analytes were quantified via high-performance liquid chromatography-UV detection. The figures of merit of the method such as, linear dynamic ranges (LDRs), limit of detections (LODs) and, limit of quantifications (LOQs), were determined based on the obtained optimum condition. Based on the results, the LDR was between 1 and 500 µg L - 1 and r2 higher than 0.9960. The LODs and LOQs were obtained in the ranges of 0.28-0.36 µg L - 1 and 0.92-1.1 µg L - 1, respectively. The relative standard deviations ((RSDs% for inter-and intra-day) of the method for the extraction of target analytes were calculated in two different concentrations of (2 and 10 µg L - 1) and (5 and 10 µg L - 1) between 3.70% - 5.30% and 3.50% - 5.70%-respectively. The enrichment factors were obtained between 57 and 61. In order to investigate the accuracy of the method, also the relative recovery was obtained, between 93 and 105%. Finally, the proposed method was used for the extraction of the selected analytes in different water and tea samples.

Simultaneous microwave-assisted phosphotungstic acid catalysis for rapid improvements on the accessibility and reactivity of Kraft-based dissolving pulp.

Improving the cellulose accessibility and reactivity in an efficient and convenient way has become the focused issue in the field of dissolving pulp manufacturing. We herein demonstrate a simple yet efficient strategy, namely a simultaneous microwave (MW)-assisted phosphotungstic acid (PTA) catalysis (MW-PTAsim). The MW-PTAsim treatment was efficient to improve Fock reactivity from 49.1 % to 85.8 % and decrease viscosity from 561 to 360 mL/g within 10 min, which was superior to the single MW treatment and the sequential MW-PTAseq treatment. Besides, the MW-PTAsim treated fiber had rougher and more fibrillated surfaces with an enhanced fiber accessibility, showing increased specific surface area (SSA) from 1.43 to 6.31 m2/g, mean pore diameter (MPD) from 6.92 to 11.20 nm and water retention value (WRV) from 101 % to 172 %. These positive enhancements are mainly due to a synergy that MW-enhanced rotation of PTA mediums was served as "spinning cutters" to attack the fibers, plus MW-accelerated PTA transfer and catalytic hydrolysis further improved the fiber accessibility. Moreover, PTA also demonstrates a high reusability and chemical stability. This process offers an effective and sustainable alternative for manufacturing a premium dissolving pulp.

Synthesis and comparison of three photocatalysts for degrading tramadol as an analgesic and widely used drug in water samples.

Tramadol is an analgesic drug that is mainly excreted in the urine. The entry of Tramadol into water samples causes their biological contamination. Therefore, three catalysts such as bismuth ferrite, cobalt-doped bismuth ferrite, and a magnetized Keggin type of polyoxometalate (α-Fe2O3@phosphotungstic acid), were synthesized as photocatalysts to degrade Tramadol in water samples. The morphology and properties of the prepared photocatalysts were evaluated using several techniques. Effects of several factors, including tramadol concentration, pH, hydrogen peroxide concentration, and photocatalyst amount, were studied and optimized by a design experiment procedure based on Box-Behnken design for reducing the number of experiments and cost and investigating the interactions between factors in the photocatalytic degradation process of Tramadol. These factors were optimized for each prepared photocatalyst individually. Under the optimum conditions, the percentages of tramadol degradation and kinetics of the degradation process were evaluated in the presence of each photocatalyst. The tramadol degradation percentages using bismuth ferrite, cobalt-doped bismuth ferrite, and α-Fe2O3 @phosphotungstic acid were 81.10% for 120 min, 90.63% for 80 min, and 91.32% for 80 min, respectively. The rate constants of tramadol degradation were 0.0145, 0.0329, and 0.0312 min-1 for bismuth ferrite, cobalt-doped bismuth ferrite, and α-Fe2O3 @phosphotungstic acid, respectively. The results indicated the highest percentage of tramadol degradation and rate of the degradation process were obtained using α-Fe2O3 @phosphotungstic acid and cobalt-doped bismuth ferrite, respectively.

Phosphotungstic Acid-treated Picrosirius Red Staining Improves Whole-slide Quantitative Analysis of Collagen in Histological Specimens.

We tried to prevent nonspecific nuclear staining (NS-NS) of picrosirius red (PSR) staining by treating the specimens with one of the heteropoly acids phosphotungstic acid (PTA). We analyzed a total of 35 cases of non-cancerous liver tissue for fibrosis and NS-NS under PSR-alone, phosphomolybdic acid (PMA)-pretreated PSR (PMA + PSR), or PTA-pretreated PSR (PTA + PSR) condition. In addition, we analyzed the photosensitivity of PMA or PTA single stain specimens. PTA + PSR significantly suppressed NS-NS compared with PSR. The color of the specimens did not change into blue by 30 times the exposure to whole slide scanner (WSS) light. The PTA + PSR condition showed the highest correlation with the Ishak score (pathological evaluation of liver fibrosis) compared with other conditions. Furthermore, Sirius Red-positive percentage (SRP%) in PSR was increased in the NS-NS observed cases. SRP% in PMA + PSR was significantly affected by WSS light exposure time. Moreover, the deposition of non-polarized PSR-stained substances (NP-PSR+S) clinging to the collagen fibers potentially explains why SRP% seemed bigger under PSR than PTA + PSR. Our protocol enabled us to analyze the whole slide image of PSR staining by high magnification, which would contribute to the accurate analysis of collagen amount in the tissue sections.

Multifunctional Materials from Aerobic Degradation of Epoxy Thermoset via Phosphotungstic Acid-Involved Activation and Bonding.

The growing scale of production of wind turbines represents a big challenge for chemical recycling of amine-cured epoxy resin (EP) to achieve high-efficiency degradation and high-value utilization of degradation products. Here, H2 O2 /phosphotungstic acid (HPW) catalytic oxidation system is demonstrated to completely degrade EP thermoset with the solid recovery rate of 96% at a reaction temperature of 80 °C for 4 h. Owing to protonation and bonding effect of HPW to the amine groups, the degradation products had a weight-average molecular weight of 4285 with narrow molecular weight distribution. They were used as dye adsorption blend films and supramolecular adhesives based on hydrogen bonding and coordination bonding respectively. The work demonstrates a feasible and promising method to recover the EP thermoset into high-performance materials.

Computational and experimental elucidation of the boosted stability and antibacterial activity of ZIF-67 upon optimized encapsulation with polyoxometalates.

Water microbial purification is one of the hottest topics that threats human morbidity and mortality. It is indispensable to purify water using antimicrobial agents combined with several technologies and systems. Herein, we introduce a class of nanosized metal organic framework; Zeolitic imidazolate framework (ZIF-67) cages encapsulated with polyoxometalates synthesized via facile one-step co-precipitation method. We employed two types of polyoxometalates bioactive agents; phosphotungstic acid (PTA) and phosphomolybdic acid (PMA) that act as novel antibacterial purification agents. Several characterization techniques were utilized to investigate the morphological, structural, chemical, and physical properties such as FESEM, EDS, FTIR, XRD, and N2 adsorption/desorption isotherms techniques. The antibacterial assessment was evaluated using colony forming unit (CFU) against both Escherichia coli and Staphylococcus aureus as models of Gram-negative and Gram-positive bacteria, respectively. The PTA@ZIF-67 showed higher microbial inhibition against both Gram-positive and Gram-negative bacteria by 98.8% and 84.6%, respectively. Furthermore, computational modeling using density functional theory was conducted to evaluate the antibacterial efficacy of PTA when compared to PMA. The computational and experimental findings demonstrate that the fabricated POM@ZIF-67 materials exhibited outstanding bactericidal effect against both Gram-negative and Gram-positive bacteria and effectively purify contaminated water.

Comparing Cs+ binding affinity of Keggin type polyoxometalate and sodium Tetrakis(4-florophenyl)borate in solution and from Cs-doped pure phase vermiculite.

We assessed the aptitude of cesium (Cs+) binding by Keggin type polyoxometalates (POMs) and compared the results with the Cs+ binding by sodium tetrakis(4-fluorophenyl)-borate (Na-TFPB). In this work, we aimed to establish a system to treat radioactive Cs+ contaminated soil with POMs economically. We evaluated the effect of initial Cs+ concentration (0.1M) and precipitant (POMs and TFPB) concentrations (0.01M) on Cs+ precipitation. Our comparison of Cs+ precipitation by three different POMs and TFPB was obtained by Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES). We synthesized POMs molybdovanadophosphoric acid, H5PMo10V2O40 (MVPA), and silicotungstic acid, H4SiW12O40 (STA), and used commercially available phosphotungstic acid, H3PW12O40 (PTA), and TFPB. Cs-doped pure phase vermiculite was also used to demonstrate the extraction potential of Cs+ by TFPB, STA, and PTA. All the POMs and corresponding Cs-bound POMs were characterized by UV-visible spectroscopy, Fourier-transform infrared spectroscopy (FTIR), Raman spectroscopy, and X-ray powder diffraction (XRD). In this simulation study, we demonstrated that the Cs+ removal by POMs is much more effective than TFPB and could be a promising method for the treatment of radiocesium contaminated soil.

Micro-CT visualization of the CNS: Performance of different contrast-enhancing techniques for documenting the spider brain.

Spider brain and central nervous system (CNS) have remained unexplored, due in part to the difficulty of observing these organs, usually only possible through histological preparations. Recently, internal anatomy studies have been supplemented by the inclusion of X- ray micro-CT. Unmineralized tissue such as the body of invertebrates requires a staining process to enhance tissue X-ray absorption and improve contrast during observation. Many current protocols are based on iodine staining requiring critical point drying (CPD) of the sample for optimal contrast. This process induces shrinking of the soft tissue generating artifacts in the morphology, volume, and even position of internal structures. Phosphotungstic acid (PTA) is an alternative staining agent recently used in marine invertebrate and plant studies. Here, we used several specimens of the common spider Araneus diadematus to visualize the spider brain and compare both contrast-enhancing ethanol-based solutions. We assessed a gradient of staining times, observed and tested the repercussions of CPD, and examined the use of vacuum to accelerate PTA diffusion. We show that PTA provides the best contrast on micro-CT scans in ethanol eliminating the need for CPD, and offering more realistic in situ visualizations of the internal organs. In combination with different scanning settings, PTA allowed observation of internal organs like the CNS, digestive system, muscles, and finer structures like the retina, visual nerves, and optic neuropiles. This fast and less invasive method could facilitate the proper documentation of the internal anatomy in the context of evolutionary, developmental and functional studies.

Acid modification enhances selective catalytic reduction activity and sulfur dioxide resistance of manganese-cerium-cobalt catalysts: Insight into the role of phosphotungstic acid.

Improving the SO2 resistance of catalysts is crucial to driving commercial applications of Mn-based catalysts. In this work, the phosphotungstic acid (HPW) modification strategy was applied to improve the N2 selectivity, SO2 and H2O resistance of the Mn-Ce-Co catalyst, and further, the mechanism of HWP modification on enhanced catalytic performance was explored. The results showed that HPW-Mn-Ce-Co catalyst exhibits higher NOx conversion (~100% at 100-250 °C) and N2 selectivity (exceed 80% at 50-350 °C) due to more oxygen vacancies, greater surface acidity, and lower redox capacity. In situ diffused reflectance infrared Fourier transform spectroscopy (in situ DRIFTS) reveal that HPW changed the reaction path of Mn-Ce-Co catalysts, promoted the adsorption and activation of NH3, and reduced the effect of SO2 on the active bidentate nitrate species, and thereby exhibiting good SO2 resistance. X-ray photoelectron spectrometer (XPS) and NH3 temperature-programmed desorption of (NH3-TPD) results show that HPW can inhibit the formation of metal sulfate, and SO2 can be combined with Ce species more easily. The generated Ce2(SO3)3 can not only protect Mn species but also increase the acid sites and weaken the poisoning effect of metal sulfate. This study provides a simple design strategy for the catalyst to improve the low-temperature catalytic performance and toxicity resistance.

Micro-computed tomography with contrast enhancement: An excellent technique for soft tissue examination in humans.

Manual dissection and histologic examination are commonly used to investigate human structures, but there are limitations in the damage caused to delicate structures or the provision of limited information. Micro-computed tomography (microCT) enables a three-dimensional volume-rendered observation of the sample without destruction and deformation, but it can only visualize hard tissues in general. Therefore, contrast-enhancing agents are needed to help in visualizing soft tissue. This study aimed to introduce microCT with phosphotungstic acid preparation (PTA-microCT) by applying the method to different types of human tissue. Specimens from human cadavers were used to examine the orbicularis retaining ligament (ORL), nasolabial fold (NLF), and the calcaneal tunnel of the sole. Using PTA-microCT, relevant information of human structures was identified. In the ORL study, tiny and delicate ligamentous fibers were visualized in detail with multidirectional continuity. In the NLF study, complex structural formation consisting of various types of soft tissue were investigated comprehensively. In the calcaneal tunnel study, the space surrounded by diverse features and its inner vulnerable structures were examined without damage. Consequently, we successfully applied the PTA-microCT technique to the analysis of specific human soft tissue structures that are challenging to analyze by conventional methods.

Integrating phosphotungstic acid-assisted prerefining with cellulase treatment for enhancing the reactivity of kraft-based dissolving pulp.

Viscosity control and reactivity enhancement are of practical importance for high-quality dissolving pulp manufacturing. In this work, we demonstrate a two-step activating process consisting of a phosphotungstic acid (PTA)-assisted prerefining (PTA/R pretreatment), followed by cellulase treatment for this purpose. The cellulase adsorption can increase from 29.1% to 49.7% as a result of PTA/R pretreatment (8000 r at 90 °C). The viscosity of the resultant pulp decreases from 665 to 430 mL/g, while its Fock reactivity increases from 31.5% to 74.4% under a low-loading cellulase treatment (0.5 mg cellulase /g odp), which mainly due to the fact that the PTA/R pretreatment can increase fiber accessibility and viscosity control, thus facilitating cellulase adsorption and reaction efficiency. Moreover, PTA also shows a high recyclability/ reusability (more than 86%) during the PTA/R pretreatment. Therefore, the new proposed two-step activating process provides a green, and efficient pathway for large-scale manufacturing of high-quality dissolving pulp.

Solvent-Free Desulfurization System to Produce Low-Sulfur Diesel Using Hybrid Monovacant Keggin-Type Catalyst.

Two quaternary ammonium catalysts based on the monovacant polyoxotungstate ([PW11O39]7-, abbreviated as PW11) were prepared and characterized. The desulfurization performances of the PW11-based hybrids (of tetrabutylammonium and trimethyloctadecylammonium, abbreviated as TBA[PW11] and ODA[PW11], respectively), the corresponding potassium salt (K7PW11O39, abbreviated as KPW11) and the peroxo-compound (TBA-PO4[WO(O2)2], abbreviated as TBA[PW4]) were compared as catalysts for the oxidative desulfurization of a multicomponent model diesel (2000 ppm S). The oxidative desulfurization studies (ODS) were performed using solvent-free systems and aqueous H2O2 as oxidant. The nature of the cation in the PW11 catalyst showed to have an important influence on the catalytic performance. In fact, the PW11-hybrid catalysts showed higher catalytic efficiency than the peroxo-compound TBA[PW4], known as Venturello compound. TBA[PW11] revealed a remarkable desulfurization performance with 96.5% of sulfur compounds removed in the first 130 min. The reusability and stability of the catalyst were also investigated for ten consecutive ODS cycles without loss of activity. A treated clean diesel could be recovered without sulfur compounds by performing a final liquid/liquid extraction diesel/EtOH:H2O mixture (1:1) after the catalytic oxidative step.

Redox Dyshomeostasis Strategy for Hypoxic Tumor Therapy Based on DNAzyme-Loaded Electrophilic ZIFs.

Redox homeostasis is one of the main reasons for reactive oxygen species (ROS) tolerance in hypoxic tumors, limiting ROS-mediated tumor therapy. Proposed herein is a redox dyshomeostasis (RDH) strategy based on a nanoplatform, FeCysPW@ZIF-82@CAT Dz, to disrupt redox homeostasis, and its application to improve ROS-mediated hypoxic tumor therapy. Once endocytosed by tumor cells, the catalase DNAzyme (CAT Dz) loaded zeolitic imidazole framework-82 (ZIF-82@CAT Dz) shell can be degraded into Zn2+ as cofactors for CAT Dz mediated CAT silencing and electrophilic ligands for glutathione (GSH) depletion under hypoxia, both of which lead to intracellular RDH and H2 O2 accumulation. These "disordered" cells show reduced resistance to ROS and are effectively killed by ferrous cysteine-phosphotungstate (FeCysPW) induced chemodynamic therapy (CDT). In vitro and in vivo data demonstrate that the pH/hypoxia/H2 O2 triple stimuli responsive nanocomposite can efficiently kill hypoxic tumors. Overall, the RDH strategy provides a new way of thinking about ROS-mediated treatment of hypoxic tumors.

Ionotropic Gelation of Chitosan for Next-Generation Composite Proton Conducting Flat Structures.

(1) Background: Ionotropic gelation of cost-effective and eco-friendly biopolymer chitosan (Chit) is a novel and promising approach to the one-step synthesis of proton-conducting fuel cell bio-membranes.The method discovered by the author in 2011 and subsequently drowned among very few papers. This work aimed to relaunch this method through clear and effective communication of new unpublished results emphasizing the key aspects of this topic for successful dissemination of the results and significant future developments. (2) Methods and results: The mechanism of in-situ ionotropic gelation of Chit on an alumina substrate by phosphotungtate anions (PWA3-) was discussed and analyzed. The study sheds light on the effect of prolonged post-treatment in phosphotungstic acid (PWA) solution on the obtained chitosan/phosphotungstate (Chit-PWA) flat structures. Methods used included combined structural (XRD), thermal-gravimetric (DTG), electrochemical (in-situ EIS), compositional (EDX),morphological analysis (SEM), as well as the performances in a low temperature H2/O2 fuel cell(4) Conclusions: This contribution discloses novel possibilities aimed at increasing the impact of ionotropic gelation of chitosan on the scientific community working on the synthesis of novel proton conductive bio-composite membranes and structures.

Phosphotungstic acid-enhanced microCT: Optimized protocols for embryonic and early postnatal mice.

BACKGROUND: Given the need for descriptive and increasingly mechanistic morphological analyses, contrast-enhanced microcomputed tomography (microCT) represents perhaps the best method for visualizing 3D biological soft tissues in situ. Although staining protocols using phosphotungstic acid (PTA) have been published with beautiful visualizations of soft tissue structures, these protocols are often aimed at highly specific research questions and are applicable to a limited set of model organisms, specimen ages, or tissue types. We provide detailed protocols for micro-level visualization of soft tissue structures in mice at several embryonic and early postnatal ages using PTA-enhanced microCT. RESULTS: Our protocols produce microCT scans that enable visualization and quantitative analyses of whole organisms, individual tissues, and organ systems while preserving 3D morphology and relationships with surrounding structures, with minimal soft tissue shrinkage. Of particular note, both internal and external features of the murine heart, lungs, and liver, as well as embryonic cartilage, are captured at high resolution. CONCLUSION: These protocols have broad applicability to mouse models for a variety of diseases and conditions. Minor experimentation in the staining duration can expand this protocol to additional age groups, permitting ontogenetic studies of internal organs and soft tissue structures within their 3D in situ position.

Reduction of N2O by H2 Catalyzed by Keggin-Type Phosphotungstic Acid Supported Single-Atom Catalysts: An Insight from Density Functional Theory Calculations.

In the present paper, the mechanisms of N2O reduction by H2 were systemically examined over various polyoxometalate-supported single-atom catalysts (SACs) M1/PTA (M = Fe, Co, Mn, Ru, Rh, Os, Ir, and Pt; PTA = [PW12O40]3-) by means of density functional theory calculations. Among these M1/PTA SACs, Os1/PTA SAC possesses high activity for N2O reduction by H2 with a relatively low rate-determining barrier. The favorable catalytic pathway involves the first and second N2O decomposition over the Os1/PTA SAC and hydrogenation of the key species after the second N2O decomposition. Molecular geometry and electronic structure analyses along the favorable reaction pathway indicate that a strong charge-transfer cooperative effect of metal and support effectively improves the catalytic activity of Os1/PTA SAC. The isolated Os atom not only plays the role of adsorption and activation of the N2O molecule but also works as an electron transfer medium in the whole reaction process. Meanwhile, the PTA support with very high redox stability has also been proven to be capable of transporting the electron to promote the whole reaction. We expect that our computation results can provide ideas for designing new SACs for N2O reduction by using H2 selective catalytic reduction technology.