Reactive Facets Research Articles

The catalytic effect of chromium-doped ceria-praseodymium on soot oxidation activity and its kinetics.

Soot generated from the partial combustion of diesel significantly contributes to air pollution, and catalytic oxidation is currently an effective method for removing diesel soot particles. The chromium-doped ceria-praseodymium (Cr-CP) catalyst system is synthesized via solution combustion synthesis and evaluated for soot oxidation activity, with a subsequent kinetics study conducted. The XRD analysis of the catalysts indicated a decrease in crystallite size and increased lattice strain and reactive facet ratios for all Cr-doped CP samples. Raman analysis verified the existence of oxygen vacancy peaks in all chromium-doped CP catalysts. X-ray photoelectron spectroscopy (XPS) revealed the presence of adsorbed H2O or molecular water peaks in the O1s spectra for the 5 Cr-CP catalyst, which also exhibited a high concentration of surface Cr3+ ions. Thermogravimetric analysis (TGA) of soot oxidation indicated that 5 Cr-CP exhibited a superior T50 of 393 ± 2°C, mostly attributed to the presence of reducible surface Cr3+ ion species. Kinetic analysis was performed on all Cr-doped CP catalysts to assess the kinetic triplets: activation energy, pre-exponential factor, and reaction model. The activation energy was low (87kJmol-1, Ozawa method) for 15 Cr-CP, while the pre-exponential factor was higher for 5 Cr-CP (7.39 × 1010min-1). The Cr-CP catalyst system adhered to a power law, indicating a phase boundary-controlled reaction characterized by nucleation and growth mechanisms. The consistency between experimental and calculated curves confirmed that the developed catalysts adhered to the Avrami-Erofeev equation (Am) or the nucleation and growth model.

Synergistic Electronic Interaction in PdCu Alloy/TiO2-NSs for Ambient Efficient Dehydrogenation of Formic Acid.

Palladium-based catalysts are remarkable in endorsing hydrogen (H2) generation through formic acid (HCOOH, FA) dehydrogenation under near-ambient conditions. Hydrogen energy efficiency depends on high-performance catalyst design. In this study, Pd-Cu nanoalloy catalysts with mutable atomic ratios are successfully fabricated on TiO2 nanosheets (TiO2-NSs).The synergistic electronic interactions between Palladium (Pd) and copper (Cu) are revealed through a density of states (DOS) analysis of alloy supported over a mixed valence state of Ti linked to oxygen vacancies (Vo) in TiO2-NSs, Enhanced adsorption of target molecules reveals novel active sites for Formic acid dehydrogenation (FAD), with O─H bond cleavage via HCOO formate intermediate preceding C─H and C─O bond cleavage. Experimental and theoretical research demonstrates that the Pd-Cu/TiO2-NSs (3:7) catalyst d electron redistribution and d-band center shift lower the activation energy for O─H bond cleavage, exhibit superior H2 production than pure Pd and Cu, increasing Pd electron density due to synergistic effects from reactive crystal facets, defects, and strong metal support interactions (SMSI), lowering the activation energy for HCOOH dissociation step, generating carbon dioxide (CO2) and H2 with a unprecedented high turnover frequency (TOF) of 6268 molH2.h-1.molPd-1 at 303K with activation energy (Ea) of 15 KJ mol-1. This attempt models an efficient HCOOH-to-hydrogen catalyst.

A Facile Microwave-Promoted Formation of Highly Photoresponsive Au-Decorated TiO2 Nanorods for the Enhanced Photo-Degradation of Methylene Blue.

The integration of noble metal nanoparticles (NPs) effectively modifies the electronic properties of semiconductor photocatalysts, leading to improved charge separation and enhanced photocatalytic performance. TiO2 nanorods decorated with Au NPs were successfully synthesized using a cost-effective, rapid microwave-assisted method in H2O2 and HF media for methylene blue (MB) degradation under visible light illumination. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 physisorption, and UV-vis spectroscopy were employed to characterize the structures, morphologies, compositions, and photoelectronic properties of the as-synthesized materials. The fusing of Au NPs effectively alters the electronic structure of TiO2, enhancing the charge separation efficiency and improved electrical conductivity. The HF treatment promotes the exposure of the highly reactive (001) and (101) crystalline facets. The improved photocatalytic activity of Au/TiO2, achieving 97% efficiency, is attributed to the surface plasmon resonance (SPR) effect of the Au NPs and the presence of oxygen vacancies. The photodegradation of MB using the TiO2/Au photocatalysts follows pseudo-first-order kinetics, highlighting the enhanced catalytic efficiency of the synthesized nanostructures. The exceptional properties of the binary Au/TiO2 photocatalysts, including the SPR effect, exposed crystallographic faces, and efficient charge carrier separation through a decrease in the recombination of electrons and holes, contribute to the photocatalytic degradation of MB.

Elimination of representative antibiotic-resistant bacteria, antibiotic resistance genes and ciprofloxacin from water via photoactivation of periodate using FeS2

The propagation of antibiotic-resistant bacteria (ARB) and antibiotic resistance genes (ARGs) induced by the release of antibiotics poses great threats to ecological safety and human health. In this study, periodate (PI)/FeS2/simulated sunlight (SSL) system was employed to remove representative ARB, ARGs and antibiotics in water. 1 × 107 CFU mL–1 of gentamycin-resistant Escherichia coli was effectively disinfected below limit of detection in PI/FeS2/SSL system under different water matrix and in real water samples. Sulfadiazine-resistant Pseudomonas and Gram-positive Bacillus subtilis could also be efficiently sterilized. Theoretical calculation showed that (110) facet was the most reactive facet on FeS2 to activate PI for the generation of reactive species (·OH, ·O2–, h+ and Fe(IV)=O) to damage cell membrane and intracellular enzyme defense system. Both intracellular and extracellular ARGs could be degraded and the expression levels of multidrug resistance-related genes were downregulated during the disinfection process. Thus, horizontal gene transfer (HGT) of ARB was inhibited. Moreover, PI/FeS2/SSL system could disinfect ARB in a continuous flow reactor and in an enlarged reactor under natural sunlight irradiation. PI/FeS2/SSL system could also effectively degrade the HGT-promoting antibiotic (ciprofloxacin) via hydroxylation and ring cleavage process. Overall, PI/FeS2/SSL exhibited great promise for the elimination of antibiotic resistance from water.

Palladium catalyzed C(sp3)–H trifluoroethoxylation

Palladium(II) complexes of the TPA family (TPA − tris(2-pyridylmethyl)amine) have recently emerged as efficient catalysts of highly 3°-regioselective hydroxylation and chemoselective 2°-ketonization of aliphatic C–H groups with peroxycarboxylic acids. Herewith, we present a novel facet of the catalytic reactivity of such complexes that have been shown to mediate highly efficient (at as low as 0.6 mol. % catalyst loadings) and selective trifluoroethoxylation of organic substrates at benzylic C–H groups, affording the corresponding trifluoroethoxy ethers in up to 73 % isolated yield. The developed synthetic protocol allows for diastereoselective trifluoroethoxylation of complex molecules of natural origin (steroids, terpenoids).

Silver Nanoparticles: Multifunctional Tool in Environmental Water Remediation.

Water pollution is a worldwide environmental and health problem that requires the development of sustainable, efficient, and accessible technologies. Nanotechnology is a very attractive alternative in environmental remediation processes due to the multiple properties that are conferred on a material when it is at the nanometric scale. This present review focuses on the understanding of the structure-physicochemical properties-performance relationships of silver nanoparticles, with the objective of guiding the selection of physicochemical properties that promote greater performance and are key factors in their use as antibacterial agents, surface modifiers, colorimetric sensors, signal amplifiers, and plasmonic photocatalysts. Silver nanoparticles with a size of less than 10 nm, morphology with a high percentage of reactive facets {111}, and positive surface charge improve the interaction of the nanoparticles with bacterial cells and induce a greater antibacterial effect. Adsorbent materials functionalized with an optimal concentration of silver nanoparticles increase their contact area and enhance adsorbent capacity. The use of stabilizing agents in silver nanoparticles promotes selective adsorption of contaminants by modifying the surface charge and type of active sites in an adsorbent material, in addition to inducing selective complexation and providing stability in their use as colorimetric sensors. Silver nanoparticles with complex morphologies allow the formation of hot spots or chemical or electromagnetic bonds between substrate and analyte, promoting a greater amplification factor. Controlled doping with nanoparticles in photocatalytic materials produces improvements in their electronic structural properties, promotes changes in charge transfer and bandgap, and improves and expands their photocatalytic properties. Silver nanoparticles have potential use as a tool in water remediation, where by selecting appropriate physicochemical properties for each application, their performance and efficiency are improved.

Effect of Facet on Local Electron Density of Oxygen Vacancy in Catalysts for Nitrogen Electro-Reduction.

Oxygen-vacancy (Ov) engineering is an effective strategy to manipulate the electronic configuration of catalysts for electrochemical nitrogen reduction reaction (eNRR). The influence of the stable facet on the electronic configuration of Ov is widely studied, however, the effect of the reactive facet on the local electron density of Ov is unveiled. In this work, an eNRR electrode R(111)-TiO2/HGO is provided with a high proportion exposed reactive facet (111) of rutile-TiO2 (denoted as R(111)-TiO2) nanocrystals with Ov anchored in hierarchically porous graphite oxide (HGO) nanofilms. The R(111)-TiO2/HGO exhibits excellent eNRR performance with an NH3 yield rate of 20.68 µg h-1 cm-2, which is ≈20 times the control electrode with the most stable facet (110) exposed (R(110)-TiO2/HGO). The experimental data and theoretical simulations reveal that the crystal facet (111) has a positive effect on regulating the local electron density around the oxygen vacancy and the two adjacent Ti-sites, promoting the π-back-donation, minimizing the eNRR barrier, and transforming the rate determination step to *NNH→*NNHH. This work illuminates the effect of crystal facet on the performance of eNRR, and offers a novel strategy to design efficient eNRR catalysts.

Fun With Unusual Functional Groups: Sulfamates, Phosphoramidates, and Di-tert-butyl Silanols.

Compared to ubiquitous functional groups such as alcohols, carboxylic acids, amines, and amides, which serve as central "actors" in most organic reactions, sulfamates, phosphoramidates, and di-tert-butyl silanols have historically been viewed as "extras". Largely considered functional group curiosities rather than launch-points of vital reactivity, the chemistry of these moieties is under-developed. Our research program has uncovered new facets of reactivity of each of these functional groups, and we are optimistic that the chemistry of these fascinating molecules can be developed into truly general transformations, useful for chemists across multiple disciplines. In the ensuing sections, I will describe our efforts to develop new reactions with these "unusual" functional groups, namely sulfamates, phosphoramidates, and di-tert-butyl silanols.

A novel iron sulfide phase with remarkable hydroxyl radical generation capability for contaminants degradation

The hydroxyl radical (·OH) stands as one of the most potent oxidizing agents, capable of engaging in non-selective and instantaneous reactions with contaminants in water. Herein, we present a novel iron sulfide phase (S-FeS) characterized by an unprecedented structure, accompanied by its remarkable hydroxyl radical generation capability and contaminant degradation efficiency surpassing that of the conventional metastable iron sulfide phase, namely, the Mackinawite (FeS). In comparison to FeS, S-FeS exhibits enhanced degradation kinetics and higher efficacy in the removal of methylene blue, ciprofloxacin, and trivalent arsenic. Utilizing density functional theory (DFT) calculations, we postulate the mechanism for the exceptional contaminant degradation performance of S-FeS to be attributed to the increased exposure of the highly reactive (110) crystal facets. This research uncovers a new metastable phase that expands the polymorphisms within the iron sulfide family and showcases its capability for driving the oxygen reduction reaction.

Well-defined tricobalt tetraoxide's critical morphology effect on the structure-reactivity relationship.

This review focuses on exploring the intricate relationship between the catalyst particle size and shape on a nanoscale level and how it affects the performance of reactions. Drawing from decades of research, valuable insights have been gained. Intentionally shaping catalyst particles makes exposing a more significant percentage of reactive facets possible, enabling the control of overactive sites. In this study, the effectiveness of Co3O4 nanoparticles (NPs) with nanometric size as a catalyst is examined, with a particular emphasis on the coordination patterns between oxygen and cobalt atoms on the surface of these NPs. Investigating the correlation between the structure and reactivity of the exposed NPs reveals that the form of Co3O4 with nanometric size can be modified to tune its catalytic capabilities finely. Morphology-dependent nanocatalysis is often attributed to the advantageous exposure of reactive crystal facets accumulating numerous active sites. However, experimental evidences highlight the importance of considering the reorganization of NPs throughout their actions and the potential synergistic effects between nearby reactive and less-active aspects. Despite the significant role played by the atomic structure of Co3O4 NPs with nanometric size, limited attention has been given to this aspect due to challenges in high-resolution characterizations. To bridge this gap, this review strongly advocates for a comprehensive understanding of the relationship between the structure and reactivity through real-time observation of individual NPs during the operation. Proposed techniques enable the assessment of dimensions, configuration, and interfacial arrangement, along with the monitoring of structural alterations caused by fluctuating temperature and gaseous conditions. Integrating this live data with spectroscopic methods commonly employed in studying inactive catalysts holds the potential for an enhanced understanding of the fundamental active sites and the dynamic behavior exhibited in catalytic settings.

Selectively etching-off the highly reactive (002) Zn facet enables highly efficient aqueous zinc-metal batteries

By selectively etching-off the chemically unstable (002) Zn facet, vertically aligned Zn pillars of etched Zn greatly suppress the formation of dendritic Zn and water induced byproducts, thus enabling AZMBs with high coulombic efficiencies and long lifespans.

Anatase TiO2 film with dominant (001) facets prepared by radio frequency atmospheric pressure plasma

Anatase TiO2 nanosheets film with dominant (001) facets (TF-1) has attracted widespread research interest owing to wide-ranging industrial applications and fundamental importance. In this work, we prepared TF-1 with well adhesion on quartz substate in a short time (20 min) by radio frequency (RF) pulse-modulated plasma with hydrofluoric acid (HF) as the morphology controlling agent (MCA). Many intercrossed nanosheets were observed on the surface of TF-1 through SEM images, which provides more exposed reactive (001) facets. The degree of truncation (B/A) and the percentage of exposed (001) facets (S001/S) were estimated by XRD patterns and Raman spectra, which have been increased due to the presence of HF. XPS results indicate that F atoms are only adsorbed on anatase surface rather than doped into TiO2 lattice. The functions of HF on the growth of anatase TiO2 nanosheets were studied by density functional theory (DFT), revealing the stabilization effects associated with chemisorbed fluorine (F) atoms over (001) surface, and thus stimulating its preferred growth.

Enhanced photocatalytic performance of SnS2 under visible light irradiation: strategies and future perspectives.

Tin(II) sulfide (SnS2) has emerged as a promising candidate for visible light photocatalytic materials. As a member of the transition metal dichalcogenides (TMDs) family, SnS2 features a band gap of approximately 2.20 eV and a layered structure, rendering it suitable for visible light activation with a high specific surface area. However, the application of SnS2 as a visible light photocatalyst still requires improvement, particularly in addressing the high recombination of electrons and holes, as well as the poor selectivity inherent in its perfect crystal structure. Therefore, ongoing research focuses on strategies to enhance the photocatalytic performance of SnS2. In this comprehensive review, we analyze recent advances and promising strategies for improving the photocatalytic performance of SnS2. Various successful approaches have been reported, including controlling the reactive facets of SnS2, inducing defects in the crystal structure, manipulating morphologies, depositing noble metals, and forming heterostructures. We provide a detailed understanding of these phenomena and the preparation techniques involved, as well as future considerations for exploring new science in SnS2 photocatalysis and optimizing performance.

Facet-controlled growth and soft-chemical exfoliation of two-dimensional titanium dioxide nanosheets.

TiO2 remains one of the most popular materials used in catalysts, photovoltaics, coatings, and electronics due to its abundance, chemical stability, and excellent catalytic properties. The tailoring of the TiO2 structure into two-dimensional nanosheets prompted the successful isolation of graphene and MXenes. In this review, facet-controlled TiO2 and monolayer titanate are outlined, covering their synthesis route and formation mechanism. The reactive facet of TiO2 is usually controlled by a capping agent. In contrast, the monolayer titanate is achieved by ion-exchange and delamination of layered titanates. Each route leads to 2D structures with unique physical and chemical properties, which expands its utilisation into several niche applications. We elaborate the detailed outlook for the future use and research studies of facet-controlled TiO2 and monolayer titanates. Advantages and disadvantages of both structures are provided, along with suggested applications for each type of 2D TiO2 nanosheets.

Oxygen vacancy–enriched Y2O3 nanoparticles having reactive facets for selective sensing of methyl ethyl ketone peroxide explosive

Methyl ethyl ketone peroxide (MEKP) is a highly-reactive and exothermically unstable compound that has caused many explosion accidents. Therefore, a simple, rapid and sensitive method for online monitoring of MEKP is urgently required to address such problems. Herein, yttrium oxide (Y2O3) nanoparticles with different levels of oxygen vacancies (OV) and exposed reactive facets were synthesised at different calcination temperatures. Gas-sensing studies revealed that a cataluminescence (CTL) sensor based on Y2O3 nanoparticles annealed at 600 °C achieved the highest response to MEKP with a limit of detection of 1 ppb at a working temperature of 80 °C. Density functional theory calculations indicated the {222} and {440} facets in Y2O3 as the most reactive sites towards MEKP. Moreover, the introduction of OV into the exposed reactive facets can considerably enhance the adsorption of O2 and MEKP on Y2O3 nanoparticles. Further sensing mechanism studies unveiled the singlet and triplet excited states of acetaldehyde produced by the catalytic oxidation of MEKP as the possible luminophores for CTL emission. This study not only offers a promising method for online monitoring of MEKP but also offers deep insights into the improved sensing mechanism caused by OV and exposed reactive facets, thus providing guidance for designing high-performance CTL sensors.

Highly efficient sequestration of aqueous lead on nanostructured calcite substrates

Following defocused ion beam sputtering, large area highly corrugated and faceted nanoripples are formed on calcite (10.4) faces in a self-organized fashion. High resolution atomic force microscopy (AFM) imaging reveals that calcite ripples are defined by facets with highly kinked (11.0) and (2.12) terminations. In situ AFM imaging during the exposure of such modified calcite surfaces to PbCl2 aqueous solution reveals that the nanostructured calcite surface promotes the uptake of Pb. In addition, we observed the progressive smoothing of the highly reactive calcite facet terminations and the formation of Pb-bearing precipitates elongated in registry with the underlying nanopattern. By SEM–EDS analysis we quantified a remarkable 500% increase of the Pb uptake rate, up to 0.5 atomic weight % per hour, on the nanorippled calcite in comparison to its freshly cleaved (10.4) surfaces. These results suggest that nanostructurated calcite surfaces can be used for developing future systems for lead sequestration from polluted waters.

Facet-Controlled Synthesis of Mn3O4 Nanorods for Photothermal Synergistic Catalytic Oxidation of Carcinogenic Airborne Formaldehyde

Crystal facet engineering, the selective exposure of reactive crystal facets, has emerged as an important technique for the design of efficient catalysts. However, in the facet-controlled synthesis of nanocrystals by either traditional top-down or bottom-up routes, the selection of capping agents is crucial and challenging. Herein, a phase transition strategy that does not require the assistance of capping/etching agents was developed to achieve the selective exposure of {103}, {101}, and {112} facets in Mn3O4. Facet-dependent activity in the photothermal decomposition of the carcinogen formaldehyde was investigated. The resulting Mn3O4 with exposed {103} facets showed the best photothermal catalytic activity, achieving the complete mineralization of formaldehyde at ambient temperature. The synergistic mechanism of the photothermal catalysis of Mn3O4 was discovered to be a thermal-assisted photocatalytic process rather than solar-light-driven thermal catalysis. In addition, the photothermal synergistic decomposition process of HCHO was also revealed. The photothermal decomposition of HCHO undergoes the processes of HCHO → DOM (dioxymethylene) → formates → carbonates → CO2. The findings proposed in this work not only broaden the study of crystal facet engineering but also provide suggestions for the purification of volatile organic compounds (VOCs) in indoor air.

Tuning selectivity and activity of the electrochemical glycerol oxidation reaction by manipulating morphology and exposed facet of spinel cobalt oxides

To further explore the electrooxidation mechanism of biomass-based compounds, it is highly desirable to regulate the proportion of reactive facets and identify facet-governing reactivity through crystal facet engineering. In this study, octahedral and cubic cobalt spinel oxide (Co3O4), each exclusively exposed by one specific type of facet, are selected as two representative microstructure models for tuning the selectivity and productivity of electrochemical glycerol oxidation reaction. The results indicate that the {111}-dominant octahedral Co3O4 plane with a higher population of Co2+ sites exhibits superior electrocatalytic activity for glycerol oxidation compared with the {001}-dominant cubic Co3O4, allowing nearly 65% of glycerol to be converted into a high-value-added dihydroxyacetone (DHA) compound. The average DHA production rate over octahedral Co3O4 (2.5 μmol cm−2h−1) are approximately 3.5 times greater than that over cubic Co3O4 (0.7 μmol cm−2h−1). Electrochemical studies and surface atomic configuration analysis reveal that {111}-dominant octahedral Co3O4 with a higher density of active cobalt ion yields unique reactant adsorption and charge transfer, leading to increased glycerol oxidation reactivity and productivity. The present study emphasizes the significance of controlling the highly active facet in developing efficient and selective electrocatalysts.

Linking glucocorticoid variations to monthly and daily behavior in a wild endangered neotropical primate.

Identifying the factors swaying physiological stress levels in wild animals can help depict how they cope with environmental and social stressors, shedding light on their feeding ecology, behavioral plasticity, and adaptability. Here, we used noninvasive methods to explore the link between glucocorticoid levels and behavior in an endangered neotropical primate facing habitat fragmentation pressure, the black lion tamarin (Leontopithecus chrysopygus). We investigated monthly and day-to-day glucocorticoid variations independently to attempt to disentangle the complex nature of the adrenocortical activity. Between May 2019 to March 2020, we followed two groups of black lion tamarins in two different areas, a continuous forest and a small fragment, and gathered behavioral data (over 95 days in total; 8.6 ± 3.9 days/month) and fecal samples (Nsamples = 468; 4.93 ± 3.5 samples/day) simultaneously. Preliminary analyses enabled us to identify circadian variations linked to the biological rhythm, which were taken into account in subsequent models. Monthly analyses revealed that black lion tamarin fecal glucocorticoid metabolite levels vary according to changes in activity budget associated with the fruit consumption, movement, and resting time of the groups. At a day-to-day level, while intergroup encounters led to increases in fecal glucocorticoid metabolite concentrations, we found that changes in food intake or activity level did not trigger physiological stress responses. These findings suggest that diet and ranging patterns, driven by food availability and distribution, influence physiological stress at a seasonal scale, while acute stressors such as interspecific competition trigger short-term stress responses. Exploring fecal glucocorticoid metabolite variations over different timescales can help uncover the predictive and reactive facets of physiological stress in wild species. Moreover, having a comprehensive understanding of the physiological state of species is a valuable conservation tool for evaluating how they cope in changing environments.

Electrolyte effects on the shape-controlled synthesis of Pt nanocrystals by electrochemical square-wave potential method

Surface structures or shapes of metal nanocrystals (NCs) greatly affect their catalytic performance. Electrochemical square-wave potential (SWP) method shows great advantages in the shape-controlled synthesis of Pt-group metal nanocrystals with high reactive high-index facets, due to the ease in controlling the growth and oxidation (or etching) by potentials. The potential conditions have been investigated substantially for the SWP method previously. However, the effects of electrolytes on the shapes of NCs are rarely explored. Herein, we investigated the effect of electrolyte (H2SO4 and Na2SO4) on the shape evolution of Pt NCs prepared by electrochemical SWP method. We found that high-index faceted Pt NCs, including {hk0}-faceted tetrahexahedral (THH) and {hkk}-faceted trapezohedral (TPH) Pt NCs can be obtained in 0.1 M H2SO4 in broad potential window, while mainly low-index {111}-faceted octahedral Pt NCs are formed in 0.1 M Na2SO4 electrolyte. Through evaluating the effects of cations, anions, and solution pH value, we observed that the pH value plays a key role in shape evolution. Low acidity in Na2SO4 electrolyte enhances the oxygen adsorption on Pt on the one hand, and promotes the hydrolysis of PtCl62− that decreases the growth rate of Pt NCs on the other hand. These two factors enhance the oxidative etching effect at upper potential limit of SWP, which can remove low-coordinated step atoms, and form flat low-index facets. This study shows insight into the electrolyte effects on electrochemical shape-controlled synthesis of Pt NCs, and helps to understand the growth mechanism.