Catalytic Oxidation Research Articles

Dynamically Confined Active Silver Nanoclusters with Ultrawide Operating Temperature Window in CO oxidation

Supported metal nanoclusters are often highly active in many catalytic reactions but less stable particularly under harsh reaction conditions. Here, we demonstrate that this activity‐stability trade‐off can be efficiently broken through rational design of surrounding microenvironment of the supported nanocatalyst including gas adsorbate overlayer and underneath support surface chemistry. Our studies reveal that chemisorbed oxygen species on Ag surface and surface hydroxyl groups on oxide support, which are dynamically consumed during reaction but sustained by reaction environment (O2 and H2O vapor), drive spontaneous redispersion of Ag particles and stabilization of highly active Ag nanoclusters. Such a dynamic confinement effect from gas‐catalyst‐support interaction enables the Ag nanoclusters to exhibit complete catalytic oxidation of CO over a wide temperature window of 25 ‐ 500 °C under dry conditions and 200 ‐ 800 °C under wet conditions as well as remarkable stability at 300 °C over 1000 h.

A Biomimetic Chip with Dendrimer-Encapsulated Platinum Nanoparticles for Enhanced Electrochemiluminescence Detection of Cardiac Troponin I

The measurement of cardiac troponin I (cTnI) is of vital importance for the early diagnosis of acute myocardial infarction. In this study, an enhanced electrochemiluminescent immunoassay for the highly sensitive and precise determination of cTnI was reported. A biomimetic chip with nepenthes peristome surface microstructures to achieve single-layer microbead arrays and integrated microelectrode arrays (MEAs) for ECL detection was microfabricated. Ru@SiO2 nanoparticles were prepared as signal amplificators labeling immunomagnetic beads. Dendrimer-encapsulated platinum nanoparticles (Pt DENs) were electrochemically modified on ITO MEAs. The resulting Pt DEN-modified ITO MEAs preserved good optical transparency and exhibited an approximately 20-fold ECL signal amplification compared to that obtained from bare ITO. The method made full use of the biomimetic chip with Pt DENs to develop single-layer immunomagnetic bead arrays with increasingly catalyzed electrochemical oxidation of the [Ru(bpy)3]2+–TPA system. Consequently, a limit of detection calculated as 0.38 pg/mL (S/N = 3) was obtained with excellent selectivity, demonstrating significant potential for the detection of cTnI in clinical diagnostics.

Cu12-Methylsilsesquioxane Cage Decorated with Cu(dppe)2 Moieties for Mild Oxidative Functionalization of Alkanes.

We report a high nuclear (Cu14) complex synthesized via the self-assembly of copper-methylsilsesquioxane induced by the complexation with 1,2-bis(diphenylphosphino)ethane (dppe). The structure includes two cationic CuI(dppe)2 moieties and an anionic silsesquioxane cage of an unprecedented CuII12 structural type. The Cu12 cage fragment exhibits a unique (i) combination of Si4-cyclic/Si2-acyclic silsesquioxane ligands and (ii) encapsulation of two different chloride and carbonate species. This complex acts as a promising precatalyst in the mild oxidation and carboxylation of light alkanes to produce alkyl hydroperoxides, alcohols, ketones, or carboxylic acids. The present study widens the family of copper-methylsilsesquioxane clusters with prospective use in oxidation catalysis.

Catalytic oxidation of Mn(II) in the co-presence of Fe(II) by free chlorine: significance of in situ formed Mn(II)-doped Fe(III) oxides

Fe(II) and Mn(II) are abundant in groundwater and require operationally simple and efficient method to remove in drinking water treatment. The rapid oxidation of Mn(II) is essential in water treatment. This study investigates the efficiency of Mn(II) oxidation by free chlorine in the presence of Fe(II). The results demonstrate that the presence of Fe(II) significantly accelerates the oxidation rate of Mn(II) by free chlorine under neutral and alkaline conditions. The rapid oxidation of Fe(II) by free chlorine and the presence of Mn(II) promote the formation of in situ Mn(II)-doped ferrihydrite. Kinetic modeling and characterization of Fe(III) oxides confirm that the heterogeneous catalytic effect of the Mn(II)-doped ferrihydrite, rather than manganese oxides or their coupled catalytic effect, is responsible for the enhanced oxidation rates. The doped Mn(II) substitutes the tetrahedral Fe(III) ions in the ferrihydrite, introducing additional negative charges at the doped sites. The increased charge enhances Mn(II) adsorption and lowers its redox potential, thereby accelerating Mn(II) oxidation rate through direct electron transfer with adjacent free chlorine. Additionally, the lepidocrocite formed by the reaction between Fe(II) and dissolved oxygen significantly impedes the catalytic performance. These findings provide new insights into the catalytic co-oxidation mechanism of Fe(II) and Mn(II), and help the optimization of water treatment engineering practices.

Photooxidation of Toluene Derivatives under HAT and ROS Synergy.

The valorization of toluene offers a dual solution by addressing its environmental impact while also facilitating the synthesis of a diverse array of valuable fine chemicals and pharmaceutical intermediates, thus ensuring both ecological sustainability and economic viability. We report herein a synergistic approach that harmonizes hydrogen atom transfer (HAT) process with the generation of reactive oxygen species (ROS) under mild condition and low catalyst loading, which enables the efficient synthesis of a broad spectrum of esteemed benzoic acid derivatives and aryl ketones through the photocatalytic oxidation of toluene derivatives. Mechanistic elucidation reveals that the HAT reagent anthraquinone has both the capabilities to abstract hydrogen atoms and the ability to generate singlet oxygen 1O2 during energy transfer with triplet oxygen 3O2, and the combination of these two potencies significantly improves the catalytic efficiency of the reaction. This study not only introduces the amalgamation of HAT with ROS generation but also delineates a systematic approach for the selection of HAT reagents with energy transfer proficiency for ROS generation in catalytic oxidation reactions.

Biocatalytic degradation of environmental endocrine disruptor chlorobenzene via surfactant-optimized laccase-mediator system.

The emergence of environmental endocrine disruptor chlorobenzene (CB) in surface water and its potential environmental impacts have attracted serious global attention. It is still very difficult to achieve effective degradation of it by catalytic oxidation process under mild conditions. Here, an optimized method for degrading CB in aqueous solution using Trametes versicolor laccase and surfactant-assisted laccase-mediator (SALM) system was investigated. The use of a Tween 80 surfactant enhanced the solubility of CB and promoted its efficient degradation. Under favorable conditions, the SALM system yielded a degradation efficiency of 43.5% and a dechlorination efficiency of 41.55% for CB (25mg/L) within 24h. The possible degradation pathway of CB by this system was speculated by detecting the intermediates produced during the reaction. The outcome of the proliferation assays on MCF-7 human breast cancer cells demonstrated a reduction in the estrogenic activity of the CB solution following treatment with the SALM system. Furthermore, the influence of the quantity and positional variation of chlorine substituents on the degradation process was methodically investigated. Moreover, molecular analyses were employed to study the detailed interaction mechanism between laccase and CB, which revealed that the hydrophobic interaction contributed dominantly to binding process. These findings provide an efficient and environmentally friendly degradation system for the development of purification strategies for halogenated pollutants.

Enhanced formaldehyde oxidation of plywood using MnO2 nanoflowers supported on porous hydrothermal carbon at ambient temperature

MnO2 nanoflowers were supported on porous hydrothermal carbon via in situ loading and used for the catalytic oxidation of formaldehyde from plywood manufactured with UF adhesive. The prepared MnO2 had a δ-type structure. The use of hydrothermal carbon (Hcs) improved the dispersion of active components in the materials and provided space for the catalytic reactions. Hcs/MnO2 exhibited catalytic activity and stability during formaldehyde oxidation at room temperature. The formaldehyde removal efficiency reached 90.43 % in 30 min. The Hcs/MnO2 had more oxygen vacancies than the MnO2 catalyst, providing more abundant active substances such as -OH, O2-, O- and other active substances to promote the catalytic reaction. The effects of Hcs/MnO2 on the formaldehyde emission and the mechanical properties of plywood were investigated. The MOR, MOE and bonding strength of the Hcs/MnO2-loaded plywood with 9 % Hcs were 51.1 MPa, 2994 MPa, and 0.8 MPa, respectively. After 28 d of exposure, the formaldehyde emitted from the plywood treated with Hcs/MnO2 decreased to 0.023 mg/m3, which fulfilled the requirement for ENF grading. The controlled release of free formaldehyde from plywood by Hcs/MnO2 was reflected by changes in mass transfer and catalytic oxidation. The manganese oxides in the micropores of the wood reduced the diffusion coefficient of free formaldehyde and hindered migration through the substrate. Once the concentration of formaldehyde decreased to a certain level, it was degraded by Hcs/MnO2, thus removing formaldehyde from the source.

Metal ions-mediated concerted electron-proton transfer enables catalytic oxidation of phenolic contaminants by permanganate

Permanganate has been extensively applied in water treatment due to its ease of handling and high stability. However, the impact of common water constituents, especially metal ions, on permanganate oxidation is poorly understood. Here, we report that many redox-inactive metal ions, such as Ca2+, Mg2+, Zn2+, Cu2+, and Al3+, can enhance the reactivity of permanganate with phenolic compounds. Moreover, the enhancing effects of metal ions are highly pH-dependent with the largest promotion effect obtained at the pH close to phenols’ pKa. Experimental and computational analysis revealed that the oxidation of protonated phenols by permanganate underwent proton-coupled electron transfer (PCET) pathways, regardless of the presence of metal ions. Nonetheless, metal ions could catalyze the concerted electron-proton transfer (CEPT) but exhibited negligible effect on ETPT (electron transfer followed by proton transfer) and PTET (proton transfer followed by electron transfer) reactions, accounting for the pH-dependent effects of metal ions. Correlation between CEPT rate constants and the complexing capability of metal ions with phenols suggested that the co-existing metal ions may coordinate to phenolic O–H group and thus facilitate the CEPT reaction of phenols. This study could shed light on the application of permanganate in real practice and the modulation of CEPT reactions.

Revealing OH species in situ generated on low-valence Cu sites for selective carbonyl oxidation

Catalytic oxidation through the transfer of lattice oxygen from metal oxides to reactants, namely the Mars-van Krevelen mechanism, has been widely reported. In this study, we evidence the overlooked oxidation route that features the in situ formation of surface OH species on Cu catalysts and its selective addition to the reactant carbonyl group. We observed that glucose oxidation to gluconic acid in air (21% O2) was favored on low-valence Cu sites according to X-ray spectroscopic analyses. Molecular O2 was activated in situ on Cu0/Cu+ forming localized, adsorbed hydroxyl radicals (*OH) which played the primary reactive oxygen species as confirmed by the kinetic isotope effect (KIE) study in D2O and in situ Raman experiments. Combined with DFT calculations, we proposed a mechanism of O2-to-*OH activation through the *OOH intermediate. The localized *OH exhibited higher selectivity toward glucose oxidation at C1HO to form gluconic acid (up to 91% selectivity), in comparison with free radicals in bulk environment that emerged from thermal, noncatalytic hydrogen peroxide decomposition (40% selectivity). The KIE measurements revealed a lower glucose oxidation rate in D2O than in H2O, highlighting the role of water (H2O/D2O) or its derivatives (e.g., *OH/*OD) in the rate-determining step. After proving the C1-H activation step kinetically irrelevant, we proposed the oxidation mechanism that was characterized by the rate-limiting addition of *OH to C1=O in glucose. Our findings advocate that by maneuvering the coverage and activity of surface *OH, high-performance oxidation of carbonyl compounds beyond biomass molecules can be achieved in water and air using nonprecious metal catalysts.

Nano-MnOx prepared by redox method for toluene oxidation removal from air

Catalytic oxidation is an efficient VOCs removal technology with great potential and development advantages. The key to the oxidative elimination of VOCs lies in the development and application of the catalyst with high efficiency. In this work, the nano-MnOx catalysts were prepared by redox method and the catalytic oxidation performance of toluene was studied. The calcination temperature could effectively change the surface chemical composition and the nano-MnOx catalyst structures, which could effectively regulate the number of active centers on the catalyst surface to improve the adsorption, activation, and oxidation ability of the nano-MnOx catalysts for toluene molecules. The nano-MnOx catalyst dominated by the MnO2 phase, which was prepared at the calcination temperature of 400 °C, had a high specific surface area, developed porosity, abundant reactive oxygen species, and oxygen vacancies. The structural characteristics are conducive to the adsorption, activation, and oxidation of toluene molecules, and thus exhibited excellent toluene catalytic oxidation activity. At the reaction temperature of 140 °C, the toluene oxidation conversion was as high as 99.4 %, and the toluene conversion remained above 96.6 % after experiencing a 690 min stability test.

Improved catalytic NO oxidation over Pt supported on sulfuric acid treated TiO2

Promoting the formation of metallic Pt over the catalysts is the key to improving the NO reactivity. In general, TiO2 suppresses the oxidation of Pt by surface acidity and induces the formation of the metallic phase of Pt by Pt-Ti interaction. However, the limited number of acidic sites (–OH) contributes to the formation of large Pt particles, which may lead to the formation of Pt2+ or Pt4+, resulting in performance degradation. In this study, we further formulated the acidic sites of the TiO2 with sulfuric acid treatment (SA-TiO2) to improve catalytic NO oxidation. During the SA treatment, the TiO2 surface is positively charged by the low pH, providing an environment for well-distributed sulfate. In the subsequent introduction of Pt, the increase in acidic sites for Pt adsorption greatly enhanced the dispersion of Pt. During this process, Pt formed bonds with sulfate as [Pt(NH3)4]-SO4. The surface species combined with SO4 and NH3 were decomposed during the calcination process, thereby inhibiting the oxidation of Pt, which promotes the formation of metallic Pt. As a result, highly reactive Pt0 and Pt2+ were further formulated by increasing the acidic sites of SA-TiO2, where the low-temperature NO oxidation performance was improved, regardless of the Pt loading (0.3 to 3 wt.%).

Preparation and performance of catalyst for organic peroxide wastewater treatment

To improve the oxidation pretreatment efficiency of wastewater from organic peroxides, a catalyst (CeO2-C catalyst) was developed using the calcination method with ceramic particles as the support. The crystalline structure and elemental composition of the CeO2-C catalyst were characterized by Scanning Electron Microscope (SEM), Energy Dispersive Spectrometer (EDS), and X-ray diffraction (XRD). This study explored the effects of CeO2 mass ratio, calcination temperature, and calcination time on the performance of the catalyst. The optimal preparation conditions were established through orthogonal experiments. Additionally, the synergistic effect of the catalyst on the ozone oxidation treatment of peroxide wastewater was investigated. The results indicated that the optimal preparation parameters were a CeO2 mass ratio of 4 %, a calcination temperature of 500 °C, and a duration of 5 h, respectively. After five cycles of reuse, the catalytic activity slightly decreased but remained relatively stable. With an ozone flow rate of 6 L/min, the CeO2-C/ozone catalytic oxidation process achieved a Chemical Oxygen Demand (COD) removal rate of 28.11 % in wastewater, and the B/C (the ratio of BOD concentration to COD concentration) of wastewater improved from 0.093 to 0.152. The calcination method proved effective for preparing the CeO2-C catalyst, which demonstrated significant catalytic performance and held promising application prospects in the oxidation pretreatment of organic peroxide wastewater.

Activation of periodate by CNT for selective catalytic oxidation: The overlooked significant role of residual metal species as catalytic sites

Carbon nanotubes (CNTs) catalyzed activation of peroxides has been extensively investigated, while the role of residual metal species in CNT in the catalysis is largely overlooked. In the study, calcination treatment of pristine CNT at high temperatures was employed as an approach to gain an insight into the role of residual metal species as catalytic sites in promoted catalytic activation of periodate (PI). Firstly, the calcination treatment at 500–1100 °C significantly promoted PI activation by calcined CNT. By constructing the quantitative structure–activity relationships (QSARs) between several surface and bulk properties of CNT (such as total surface oxygen content, surface carbonyl group, bulk defect and residual metal species) and PI activation performance, the residual metal species were identified as the catalytic sites. Moreover, the purification method of pristine CNT in the concentrated HNO3 was confirmed to be not efficient to remove these residual metals. The calcination treatment can tune the electronic structure of residual metal species, and promote their exposure and electron donation capacity for PI activation, thus significantly improving PI activation performance. Moreover, IO3• was identified as the dominant reactive species in CNT/PI system via a line of approaches including quenching experiments, PI decomposition in the presence/absence of organic pollutants, electrochemical testes, high selectivity in degradation of organic pollutants, QSARs of substituted phenols, and analysis of degradation products of 4-bromophenol. Furthermore, the CNT/PI system exhibited a wide pH application range of 3–11, high anti-interference to bicarbonate, chloride and phosphate in water. The study advances the understanding on the residual metal species in CNT and its overlooked catalytic role in PI activation, and also provides a high-performance oxidation process for wastewater purification.

Oxidation of Toluene over the Pt-Embedded Mesoporous CeO2 Hollow Nanospheres with Advanced Catalytic Performances.

In this study, the novel Pt-embedded mesoporous CeO2 hollow nanospheres (Pt-MS-CeO2-H) with varying Pt contents (0.5-3.0 wt %) were facilely prepared. The Pt nanoparticles were one-pot embedded within the mesoporous shell of Pt-MS-CeO2-H and assisted with the reduction Ostwald ripening process. The traditional preparation methods often face challenges, such as the uneven distribution or aggregation of nanoparticles, as well as difficulty in maintaining high catalytic activity at low Pt content. Compared with the traditional supported Pt/MS-CeO2 catalyst, the embedding strategy facilitated precise control over the position, distribution, and uniformity of Pt nanoparticles within the CeO2 mesoporous shell. Additionally, the encapsulation process of Pt nanoparticles played a pivotal role in generating oxygen vacancies and activating surface chemical adsorption of oxygen. Resultantly, the toluene oxidation performances of 1Pt-MS-CeO2-H catalyst showed much lower T90 (171 °C) than 1Pt/MS-CeO2 (311 °C). To elucidate the underlying reasons, in situ diffuse reflectance infrared Fourier transform spectroscopy of toluene oxidation was employed to identify the reaction intermediates and pathways over these catalysts. In summary, the Pt-embedded mesoporous CeO2 hollow nanosphere catalysts were considered as potential candidates when designing high-performance toluene catalytic oxidation catalysts.

Low-temperature oxidation of methane mediated by Al-doped ZnO cluster and nanowire: a first-principles investigation.

First-principles calculations are performed to investigate the catalytic oxidation of methane by using N2O as an oxidizing agent over aluminum (Al)-doped Zn12O12 cluster and (Zn12O12)2 nanowire. The impact of Al impurity on the geometry, electronic structure, and surface reactivity of Zn12O12 and (Zn12O12)2 is thoroughly studied. Our study demonstrates that Al-doped ZnO systems have a better adsorption ability than the corresponding pristine counterparts. It is found that N2O molecule is initially decomposed on the Al site to provide the N2 molecule, and an Al-O intermediate which is an active species for the CH4 oxidation. The conversion of CH4 into CH3OH over AlZn11O12 and (AlZn11O12)2 requires an activation energy of 0.45 and 0.29eV, respectively, indicating it can be easily performed at normal temperatures. Besides, the overoxidation of methanol into formaldehyde cannot take place over the AlZn11O12 and (AlZn11O12)2, due to the high energy barrier needed to dissociate C-H bond of the CH3O intermediate. Dispersion-corrected density functional theory calculations were performed through GGA-PBE exchange-correlation functional combined with a numerical double-ζ plus polarization (DNP) basis set as implemented in DMol3. To include the relativistic effects of core electrons of Zn atoms, DFT-semicore pseudopotentials were adopted. The DFT + D scheme proposed by Grimme was used to involve weak dispersion interactions within the DFT calculations. The reaction energy paths were generated by the minimum energy path calculations using the NEB method.

Exploration of catalytic activities of Caesalpinia bonduc (L.) Roxb. ash on green-oxidation of small organic substrates: an effective way to reduce the use of harsh chemicals

In this modern era, large-scale industrial use of harsh chemicals is an alarming problem as it can cause serious environmental damage. Among industrial pollutants, harsh chemical oxidizing agents are one of the leading chemicals that can cause severe environmental threats. These harmful harsh chemicals are practically omnipresent in industries and are used to oxidize numerous small organic substrates. Replacement of these harsh chemicals with some plant-based products might be helpful to safeguard our environmental damage. In this study, Caesalpinia bonduc (L.) Roxb. ash is used as a catalyst to activate aerial oxygen for promoting the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) and o-aminophenol (OAPH) like small organic substrates. Detailed kinetic studies for these catalytic oxidation reactions have been performed spectrophotometrically, which confirms that catalytic reactions follow Michaelis–Menten kinetics. Several enzyme-kinetics plots such as the Michaelis–Menten plot, Lineweaver–Burk plot, Hanes–Woolf plot, and Eadie–Hofstee plot have been used to determine the maximum rate achieved by the reaction (Vmax) and Michaelis constant (KM) like kinetic parameters. The average values of Vmax and KM for catalytic oxidation of 3,5-DTBC are (8.6669 ± 0.6519) × 10–5 M S−1 and (21.4289 ± 0.4741) × 10–4 M, respectively. Similarly, the average values of Vmax and KM for catalytic oxidation of OAPH are (2.1781 ± 0.2071) × 10–5 M S−1 and (20.1062 ± 1.2690) × 10–3 M, respectively. The mineral composition of Caesalpinia bonduc (L.) Roxb. ash has also been evaluated by using inductively coupled plasma optical emission spectroscopy (ICP-OES).Graphical

EGCG mildly reduced single atom Co-MXene catalytic membrane: Catalytic and antioxidant properties

As a 2D nanomaterial with high hydrophilic and co-catalytic properties, MXene has been widely studied in the field of membrane separation and advanced oxidation. However, its susceptibility to oxidation in catalytic environments poses a significant challenge to its long-term stability and performance. Therefore, constructing an oxidation-resistant MXene catalytic membrane technology and ensuring its excellent flux and catalytic performance are important for the practical application of MXene membranes. Herein, we prepared a cobalt monoatomic intercalated M/E0.1-Co catalytic separation membrane by mild reduction of epigallocatechin-3-gallate (EGCG). EGCG not only connects the MXene lamellae during filtration through strong hydrogen bonding, but also protects the chemical stability of the MXene substrate through its antioxidant ability. Furthermore, the trace amount of EGCG in the confined domain space also promotes the rate-limiting step of the transition from the high-valent state to the low-valent state in Co single-atom catalysis. The stability of the catalytic separation layer was ensured along with a 100% degradation performance of sulfamethoxazole. This study establishes a bridge between the catalytic oxidation and chemical stability of a wide range of MXene-based materials nowadays and provides a viable proposal for the practical application of long-term utilized MXene materials in catalysis.

Enhancing catalytic oxidation of benzene with Cu-Doped MnO2: Insights into structural defects and electronic modifications

The present research focuses on the role of copper (Cu) doping in enhancing the catalytic efficacy of manganese dioxide (α-MnO2) for benzene oxidation, a representative volatile organic compound (VOC). Despite the abundance and low cost of MnO2, its pristine form requires improvement for industrial VOC oxidation processes. Utilizing a range of characterization methods, the study reveals that Cu doping generates oxygen vacancies and increases the Mn3+ content within the catalyst structure, which are crucial for enhancing the adsorption and activation of reactants. The findings indicate that Cu-doped α-MnO2 exhibits superior catalytic activity and lower activation energy for benzene oxidation compared to the undoped counterpart. The electronic interactions induced by the doping of Cu and the effect on the catalytic process are demonstrated and discussed in depth. This work emphasizes the strategic importance of dopant optimization and contributes to the advancement of MnO2-based catalysts for environmental remediation, aligning with goals of environmental protection and human health safety.

Mild and rapid construction of Ti electrodes for efficient and corrosion-resistant oxidative catalysis at industrial-grade intensity

The development of cost-effective and corrosion-resistant catalytic electrodes for chlorine/oxygen evolution reaction (CER/OER) in large-scale industrial applications is a significant challenge. Herein, the sol–gel method is employed to achieve a uniform coating of ruthenium (Ru) doping copper (Cu) on titanium sheet (Ru + 20 %Cu@Ti), and the highly efficient industrial grade stable Ti dimensional stable anode can be quickly constructed at 723.15 K for 2 h. Cu doping reduces the vacancy formation energy of surface oxygen, promotes additional lattice oxygen vacancy assisted hydrolysis dissociation pathway, improves the selectivity and specific activity of CER at high concentration doping, and reduces the binding energy of OER intermediates (e.g., *OH, *O, and *OOH) at adjacent Ru active sites. The overpotentials require to reach the current density of 10 mA cm−2 for CER and OER were only 365 mV and 232 mV at the conditions of 5.0 M NaCl (pH = 7.0) and 1.0 M KOH + 0.5 M NaCl. More importantly, Ru + 20 %Cu@Ti demonstrates excellent stability, operates continuously for over 340h at industrial current density in neutral and alkaline electrolytes, and its strengthening life reaches 64 h, with ultra-low performance attenuation. Impressively, the designed applied electrode (8.0 cm ✕ 15.0 cm) achieves long-term CER at 0.2–0.3 A cm−2. Further industrial grade evaluation of CER shows that its chlorine extraction polarizability, enhances life and weight loss meet the requirements of industrial applications.

Uncertainty Quantification of Linear Scaling, Machine Learning, and Density Functional Theory Derived Thermodynamics for the Catalytic Partial Oxidation of Methane on Rhodium.

Accurate and complete microkinetic models (MKMs) are powerful for anticipating the behavior of complex chemical systems at different operating conditions. In heterogeneous catalysis, they can be further used for the rapid development and screening of new catalysts. Density functional theory (DFT) is often used to calculate the parameters used in MKMs with relatively high fidelity. However, given the high cost of DFT calculations for adsorbates in heterogeneous catalysis, linear scaling relations (LSRs) and machine learning (ML) models were developed to give rapid estimates of the parameters in MKM. Regardless of the method, few studies have attempted to quantify the uncertainty in catalytic MKMs, as the uncertainties are often orders of magnitude larger than those for gas phase models. This study explores uncertainty quantification and Bayesian Parameter Estimation for thermodynamic parameters calculated by DFT, LSRs, and GemNet-OC, a ML model developed under the Open Catalyst Project. A model for catalytic partial oxidation of methane (CPOX) on Rhodium was chosen as a case study, in which the model's thermodynamic parameters and their associated uncertainties were determined using DFT, LSR, and GemNet-OC. Markov Chain Monte Carlo coupled with Ensemble Slice Sampling was used to sample the highest probability density (HPD) region of the posterior and determine the maximum of the a posteriori (MAP) for each thermodynamic parameter included. The optimized microkinetic models for each of the three estimation methods had quite similar mechanisms and agreed well with the experimental data for gas phase mole fractions. Exploration of the HPD region of the posterior further revealed that adsorbed hydroxide and oxygen likely bind on facets other than Rhodium 111. The demonstrated workflow addresses the issue of inaccuracies arising from the integration of data from multiple sources by considering both experimental and computational uncertainties, and further reveals information about the active site that would not have been discovered without considering the posterior.