Selective Catalytic Oxidation Research Articles

A Comprehensive Study about Functionalization and De-functionalization of MOF-808 as a Defect-Engineered Zr-MOFs for Selective Catalytic Oxidation

In metal–organic frameworks (MOFs), confined space as a chemical nanoreactor is as essential as coordinatively unsaturated metal site catalysis. The properties of MOFs can be adjusted through the incorporation of functional groups and open metal sites in frameworks that can modify the catalytic performance. In this regard, a set of defect-engineered MOFs, Ex-MOF-808(NH2, NO2, H) and Mix-MOF-808(NH2, NO2, H), were synthesized by ultrasonic-assisted linker exchange approach (Ex-MOFs) and solvothermal mixing ligand method (Mix-MOFs), respectively. Further, the relationship between the preparation method, structural properties, and catalytic efficiency of the prepared materials in the selective oxidation of methyl phenyl sulfide (MPS) has been investigated. By analyzing zeta potential, it was found that in the exchange method, the amount of defect and functional groups on the surface of MOFs are more than in the mixing method, which also affects the catalytic activity. In our contribution, mix-MOF-808(NO2) carrying nitro groups at their organic linkers, which has a well-dispersion of nitro groups at the framework exhibits selective conversion of MPS to sulfone (91%). Furthermore, the performance of stable heterogeneous catalysts was investigated for three cycles, which demonstrated their great potential for advanced catalytic oxidation.

Application of Mesoporous/Hierarchical Zeolites as Catalysts for the Conversion of Nitrogen Pollutants: A Review

Mesoporous/hierarchical zeolites (HZs) are a relatively new group of materials, and interest in their application in catalysis is continuously growing. This paper presents recent achievements in the application of mesoporous zeolites in catalytic reactions of nitrogen pollutant conversion. The analysis presented includes processes such as selective catalytic reduction of NOx with ammonia (NH3-SCR, DeNOx), selective catalytic oxidation of ammonia (NH3-SCO, AMOx), and catalytic decomposition of N2O. Different zeolite topologies and methods of their modification focused on mesoporosity generation (e.g., desilication, dealumination, steaming, self-assembly techniques, and application of hard and soft templates) are reviewed and compared with respect to catalytic processes. Special attention is paid to the role of porous structure and acidity, as well as the form of deposited transition metals, in the catalytic activation of modified zeolites in the elimination of nitrogen pollutants from flue gases.

Temperature-driven dynamic evolution process of Ag species on silver-loaded Zr0.2Sn0.8O2 catalyst for selective catalytic oxidation of ammonia

Silver-based catalysts are extensively utilized in the selective catalytic oxidation of ammonia (NH3-SCO). However, enhancing low-temperature activity often causes a decline in N2 selectivity, presenting a substantial challenge in balancing activity and N2 selectivity. In this work, we introduced zirconium into the SnO2 support, resulting in a significant enhancement of low-temperature activity by 200 °C for the Ag/Zr0.2Sn0.8O2 catalyst; yet, this also led to the formation of N2O at low temperatures and NOx at high temperatures. Characterizations such as XPS and in situ DRIFTS revealed that the dynamic changes of silver species driven by temperature had a profound impact on the reaction mechanism and guided the formation of different products. Below 200 °C, the predominance of Ag+ directed the imide mechanism, with the –HNO species being the key intermediate leading to the production of N2O. Above 300 °C, Ag0 became dominant, favoring the internal selective catalytic reduction (i-SCR) mechanism and the production of NOx. This work provides novel insights into improving N2 selectivity of Ag-based catalysts and contributes to a deeper understanding of the reaction mechanisms.

Insights into the Construction of Robust Pt Clusters with Satisfactory Stability on CeO2 for the Catalytic Oxidation of CO.

Improving the efficiency of platinum group metals (Pt, Pd, Rh, etc.) in catalytic oxidation reactions remains an urgent topic. The conflict between the low-temperature activity and high-temperature stability of noble metals can hardly reach a consensus. For instance, Pt cluster catalysts supported on CeO2 with high low-temperature activity will suffer from deactivation due to the redispersion under high-temperature lean-burn reaction conditions. Herein, two Pt1/CeO2 prepared by the incipient wetness impregnation method using different Pt precursors possessed varied Pt-O and Pt-O-Ce coordination numbers (CNs). They showed various priorities in CO oxidation versus NH3 selective catalytic oxidation, materials with higher CNPt-O-Ce selectively catalyzing NH3 oxidation to N2 more superior, conversely materials with lower CNPt-O-Ce performing better in CO oxidation. After activation by H2 reduction, both formed massive Pt clusters on the CeO2 surface but showed drastically distinct stability in lean-burn CO oxidation reactions. By summarizing the experimental results of high-angle annular dark-field scanning transmission electron microscopy, X-ray absorption spectroscopy, Raman spectroscopy, in situ diffuse reflectance infrared Fourier transform spectroscopy, etc., it is beyond doubt that the difference in the initial states of Pt1 due to distinct precursors indeed determine the redispersion behavior of the reduced Pt clusters on CeO2. Materials with lower CNPt-O-Ce and higher CNPt-O are more likely to form robust Pt clusters, as they are not conducive to Pt anchoring, thus restricting the reversible structural evolution occurring under lean-burn CO oxidation and reductive conditions. This approach serves as a guide for the convenient and efficient construction and exploration of robust Pt cluster catalysts.

Density functional theory-based screening of Ti4C3O2-loaded single atoms for efficient selective catalytic oxidation of formaldehyde

Indoor formaldehyde (HCHO) pollution poses a major risk to human health. Low-temperature catalytic oxidation is an effective method for HCHO removal. The high activity and selectivity of single atomic catalysts provide a possibility for the development of efficient non-precious metal catalysts. In this study, the most stable single-atom catalyst Ti–Ti4C3O2 was screened by density functional theory among many single atomic catalysts with two-dimensional (2D) monolayer Ti4C3O2 as the support. The computational results show that Ti–Ti4C3O2 is highly selective to HCHO and O2 in complex environments. The HCHO oxidation reaction pathways are proposed based on the Eley-Rideal (E-R) and Langmuir-Hinshelwood (L-H) mechanisms. According to the reaction energy and energy span models, the E-R mechanism has a lower maximum energy barrier and higher catalytic efficiency than the L-H mechanism. In addition, the stability of the Ti–Ti4C3O2 structure and active center was verified by diffusion energy barrier and ab initio molecular dynamics simulations. The above results indicate that Ti–Ti4C3O2 is a promising non-precious metal catalyst. The present study provides detailed theoretical insights into the catalytic oxidation of HCHO by Ti–Ti4C3O2, as well as an idea for the development of efficient non-precious metal catalysts based on 2D materials.

The Development of the Regenerable Catalytic System in Selective Catalytic Oxidation of Ammonia with High N2 Selectivity.

Supported particulate noble-metal catalysts are widely used in industrial catalytic reactions. However, these metal species, whether in the form of nanoparticles or highly dispersed entities, tend to aggregate during reactions, leading to a reduced activity or selectivity. Addressing the frequent necessity for the replacement of industrial catalysts remains a significant challenge. Herein, we demonstrate the feasibility of the 'regenerable catalytic system' exemplified by selective catalytic oxidation of ammonia (NH3-SCO) employing Ag/Al2O3 catalysts. Results demonstrate that our highly dispersed Ag catalyst (Ag HD) maintains >90% N2 selectivity at 80% NH3 conversion and >80% N2 selectivity at 100% NH3 conversion after enduring 5 cycles of reducible aggregation and oxidative dispersion. Moreover, it consistently upholds over 98% N2 selectivity at 100% NH3 conversion after 10 cycles of Ar treatment. During the aggregation-dispersion process, the Ag HD catalyst intentionally aggregated into Ag nanoparticles (Ag NP) after H2 reduction and exhibited remarkable regenerable capabilities, returning to the Ag HD state after calcination in the air. This structural evolution was characterized through in situ transmission electron microscopy, atomically resolved high-angle annular dark-field scanning transmission electron microscopy, and X-ray absorption spectroscopy, revealing the on-site oxidative dispersion of Ag NP. Additionally, in situ diffuse reflectance infrared Fourier transform spectroscopy provided insights into the exceptional N2 selectivity on Ag HD catalysts, elucidating the critical role of NO+ intermediates. Our findings suggest a sustainable and cost-effective solution for various industry applications.

Rational Design of Cobalt Phthalocyanine (CoPc)‐Anchored TiO2 Nanorods for High‐Efficiency Selective Catalytic Oxidation

AbstractQuinclorac is important precursor for pharmaceutical, agricultural, and synthetic chemistry. The state‐of‐art synthesis of quinclorac via condensation, chlorination and oxidative hydrolysis often uses homogeneous catalysts and strong acid oxidant agents to promote the catalytic oxidation, which requires huge manpower input for the late‐stage purification process and is usually environmentally unfriendly. In this work, we successfully fabricated a stable cobalt phthalocyanine (CoPc) Co‐based composite (CoPc/TiO2) by anchoring CoPc on the surface of TiO2 nanorods for the selective oxidation of 3,7‐dichloro‐8‐dichloro methyl quinoline (3,7‐D‐8‐DMQ) into quinclorac. More impressively, CoPc/TiO2‐2.5 %‐Mn‐Br exhibits a high selectivity of 91.9 % for the catalytic oxidation of 3,7‐D‐8‐DMQ to quinclorac in acetic acid, with a quinclorac yield of 86.4 %, which is approximately 2.43 times higher than that of pristine CoPc‐Mn‐Br. The obtained heterogeneous catalytic system shows good reusability. Detailed mechanistic investigations reveal that the system works through a free radical mechanism via the formation of Co2+/Co3+ redox cycles. This work provides a new understanding for the stabilization of reaction intermediates and facilitates the designs of catalysts for selective catalytic oxidation.

Regulating the valence and size of the active center of Co/Al2O3 catalyst improved the performance and selectivity of NH3-SCO

To improve the activity of Co/Al2O3 catalysts in selective catalytic oxidation of ammonia (NH3-SCO), valence state and size of active centers of Al2O3-supported Co catalysts were adjusted by conducting H2 reduction pretreatment. The NH3-SCO activity of the adjusted 2Co/Al2O3 catalyst was substantially improved, outperforming other catalysts with higher Co-loading. Fresh Co/Al2O3 catalysts exhibited multitemperature reduction processes, enabling the control of the valence state of the Co-active centers by adjusting the reduction temperature. Changes in the state of the Co-active centers also led to differences in redox capacity of the catalysts, resulting in different reaction mechanisms for NH3-SCO. However, in situ diffuse reflectance infrared Fourier transform spectra revealed that an excessive O2 activation capacity caused overoxidation of NH3 to NO and NO2. The NH3-SCO activity of the 2Co/Al2O3 catalyst with low redox capacity was successfully increased while controlling and optimizing the N2 selectivity by modulating the active centers via H2 pretreatment, which is a universal method used for enhancing the redox properties of catalysts. Thus, this method has great potential for application in the design of inexpensive and highly active catalysts.

Engineering a PtCu Alloy to Improve N2 Selectivity of NH3-SCO over the Pt/SSZ-13 Catalyst.

Improving the N2 selectivity is always a great challenge for the selective catalytic oxidation of ammonia (NH3-SCO) over noble-metal-based (especially Pt) catalysts. In this work, Cu as an efficient promoter was introduced into the Pt/SSZ-13 catalyst to significantly improve the N2 selectivity of the NH3-SCO reaction. A PtCu alloy was formed in the PtCu/SSZ-13 catalyst, as confirmed by X-ray diffraction, transmission electron microscopy, energy dispersive spectrometry mapping, and X-ray absorption spectroscopy results. As indicated by the X-ray photoelectron spectroscopy analysis, the Pt species in the alloyed PtCu nanoparticle was mainly present in the electron-rich state on PtCu/SSZ-13, while the electron-deficient Cu and isolated Cu2+ species were both present on the surface of PtCu/SSZ-13. Due to such a unique alloyed structure with an altered oxidation state, the N2 selectivity of NH3-SCO on the PtCu/SSZ-13 catalyst was remarkably improved, while the NH3-SCO activity was kept comparable to that on Pt/SSZ-13. The reaction path was changed from the NH mechanism on Pt/SSZ-13 to both NH and internal selective catalytic reduction mechanisms on the PtCu/SSZ-13 catalyst, which was considered the main reason for the enhanced N2 selectivity. This work provides a new route to synthesize efficient alloy catalysts for optimizing the N2 selectivity of NH3-SCO for NH3 slip control in diesel exhaust purification.

Electrochemical alcohol oxidation reaction on Precious‐Metal‐Free catalysts: Mechanism, activity, and selectivity

AbstractThe electrochemical alcohol oxidation reaction (AOR) is pivotal for the development of sustainable energy. The complete oxidation of alcohols has attracted extensive attention as a vital process in fuel cells. Moreover, as an alternative reaction to the oxygen evolution reaction, the selective oxidation of alcohols emerges as an effective means to lower the energy expenditure associated with electrolytic hydrogen production while yielding high‐value products. Nonprecious metal materials have been widely applied in the selective oxidation catalysis of alcohols due to their cost‐effectiveness and excellent durability. In recent years, leveraging the advantages of nonprecious metal materials in electrocatalytic AOR, researchers have delved into catalytic mechanisms and various efficient catalysts have been fabricated and evaluated. This review provides an overview of the current advancements in the electrocatalytic selective oxidation of diverse alcohols and the catalytic systems centered around nonprecious metal materials. It systematically summarizes the shared traits and distinctions in catalytic reaction characteristics across various systems, thereby laying the theoretical foundation for developing novel catalyst systems that are efficient, stable, and highly selective. This review will facilitate the utilization of nonprecious metal catalysts further toward the electrocatalytic oxidation of alcohols.

Recent Progresses and Challenges in Upcycling of Plastics through Selective Catalytic Oxidation.

Chemical upcycling of plastics provides an important direction for solving the challenging issues of plastic pollution and mitigating the wastage of carbon resources. Among them, catalytic oxidative cracking of plastics to produce high-value chemicals, such as catalytic oxidation of polyethylene (PE) to produce fatty dicarboxylic acids, catalytic oxidation of polystyrene (PS) to produce benzoic acid, and catalytic oxidation of polyethylene terephthalate (PET) to produce terephthalic acid under mild conditions has attracted increasing attention, and some exciting progress has been made recently. In this article, we will review recent progresses on the catalytic oxidation upcycling of plastics and provide our understanding on the current challenges in catalytic oxidation upcycling of plastics.

Unraveling the H2S Selective Oxidation in Cobalt Phosphate Cluster Loaded Polymeric Carbon Nitride

H2S selective catalytic oxidation via photocatalysis is a low-cost and efficient approach. Herein, we modeled a (CoP)4 cluster loaded melon-based carbon nitride to represent experimental cobalt phosphate cocatalyst adsorption on polymeric carbon nitride for revealing the mechanism of H2S selective catalytic oxidation to SO2 via the density functional theory (DFT) calculations. Due to the hydrogen bond effect, the calculated results show that H2S selective oxidation prefers to occur through the quasi Mars–van Krevelen (quasi-MvK) mechanism rather than Langmuir-Hinshelwood (LH) mechanism according to the thermodynamic perspective, in which quasi-MvK mechanism exhibits a favorable limiting potential of 0.26 V. Overall, this work offers a basic understanding for microscopic mechanism of H2S catalytic oxidation.

Efficient Cu-Co Dual-Site promotes selective catalytic oxidation of ammonia over cobalt based catalysts

Selective catalytic oxidation of NH3 (NH3-SCO) into N2 and H2O is an efficient method to eliminate excessive NH3 emission from stock farming, agriculture, industrial sectors and NH3 slip in coal-fired power plants and diesel vehicles. However, it is a great challenge to develop the Co3O4 catalyst with high activity and high N2 selectivity at low temperature. Herein, a series of Cu doped Co3O4 catalysts is designed and synthesized, with discovering the role of Co-O bond strength by copper regulation in modulating oxygen vacancies and lattice oxygen to enhance the intrinsic activity and N2 selectivity of NH3-SCO. The Cu1Co2O4 catalyst (93 % NH3 conversion and 80 % N2 selectivity at 160 °C) achieves a higher catalytic performance compared with Co3O4 (78 % NH3 conversion and 50 % N2 selectivity at 160 °C). In addition, the N2 generation rate by normalizing over specific surface area for Cu1Co2O4 (13.1 μmol m-2h−1) is 1.7 times to that of Co3O4 (8.0 μmol m-2h−1), and the apparent activation energy of Cu1Co2O4 (36.7 kJ mol−1) is lower compared to that of Co3O4 (59.8 kJ mol−1). Reactive oxygen species and enhanced electron transfer promote the oxidation of NH3 to nitrate species, which can be further converted to N2 rather than N2O by remaining NH3 on the Cu site. The Cu-Co dual sites significantly contribute to the catalytic activity and N2 selectivity. This doping strategy is beneficial for the development of Co-O bond strength modulation in spinel catalyst and also provides a new idea for improving the NH3-SCO activity and N2 selectivity of Co-based spinel.

Prussian Blue Analogue-Derived Co3O4 as Catalysts for Enhanced Selective Oxidation of Cyclohexane Using Molecular Oxygen.

Selective conversion of inert C-H bonds in alkanes into high-value-added functional groups (alcohols, ketones, carboxylic acids, etc.) plays a vital role in establishing a green and sustainable chemical industry. Catalytic selective oxidation of cyclohexane to KA oil (cyclohexanol and cyclohexanone) is a typical representative of alkane functionalization. In this work, hollow cage-like Co3O4 (Co3O4-C) and particle Co3O4 (Co3O4-P) were synthesized by calcining two types of Prussian blue analogues (PBAs), which were used to catalyze the selective oxidation of cyclohexane. The Co3O4-C predominantly exposed (311) crystal plane is easier to adsorb cyclohexane than Co3O4-P, which is beneficial to shorten the induction period, accelerate the reaction rate, and improve the conversion. Consequently, Co3O4-C displayed a 10% conversion of cyclohexane within 1 h, and the KA oil selectivity reached 90%. The Co3O4-P exposed (220) crystal plane has a higher molar percentage of oxygen vacancies and more active oxygen species, as well as a strong cyclohexanone adsorption capacity, which is conducive to the deep oxidation of cyclohexanone to adipic acid and other diacid products. The mechanism analysis of cyclohexane oxidation catalyzed by PBA-based Co3O4 shows that it exemplifies the feasibility to tailor the surface of catalysts by modulating the PBAs, which ultimately influences their reaction performance for accelerating the reaction and maintaining high cyclohexane conversion and KA oil selectivity.

Selective Catalytic Oxidation of 5-Hydroxymethylfurfural to Produce 2,5-Diformylfuran Over Nitrogen Doped Porous Carbons

Selective Catalytic Oxidation of 5-Hydroxymethylfurfural to Produce 2,5-Diformylfuran Over Nitrogen Doped Porous Carbons

Recent Progress in the Application of Transition‐Metal Containing MFI topologies for NH3‐SCR‐DeNOx and NH3 oxidation

AbstractTransition metal‐containing MFI‐based catalysts are widely investigated in the selective catalytic reduction of NOx with ammonia (NH3‐SCR‐DeNOx), and the selective catalytic oxidation of ammonia (NH3‐SCO) into nitrogen and water vapor. While MFI‐based catalysts are less intensively studied than smaller pore zeolites (i. e., chabazite, CHA) they are still used commercially for these processes and are of great interest for future study in particular to better understand structure‐activity relationships. Hierarchically porous MFI catalysts (containing both micropores and mesopores) often show enhanced catalytic properties compared to conventional (microporous) materials in both NH3‐SCR‐DeNOx and NH3‐SCO. Thus, a critical overview of the current understanding of the salient physico‐chemical properties that influence the performance of these catalysts is examined. Furthermore, strategies for the development of ZSM‐5 based catalysts with enhanced catalytic lifetime, supported by the investigations of reaction mechanisms are reviewed and discussed.

Mesoporous silica-supported Ni–Co composite metal oxide as a heterogeneous catalyst for air oxidation of benzyl alcohols

A mesoporous silica-supported Ni–Co composite metal oxide has been synthesized and applied as an effective heterogeneous catalyst for the selective catalytic oxidation of benzyl alcohols. Various characterization methods were employed to confirm the successful synthesis of the catalysts and their nanostructure. The catalytic performances of these catalysts in the selective oxidation of substituted benzyl alcohols to aromatic aldehydes were systematically investigated using molecular oxygen from the air as the oxidant under atmospheric pressure. The NiCo@SBA-15 catalyst exhibited remarkable performance, achieving nearly 98 % conversion and almost complete selectivity at a temperature of 120 °C for 10 h, operating at 1 atm of air pressure. This catalytic performance can be attributed to the synergistic effect between Ni and Co ions, resulting in the generation of new surface-active sites in the catalyst. The catalyst also demonstrated favorable applicability and universality. Moreover, A plausible catalytic mechanism has been proposed involving the synergistic effect between bimetal species and oxygen vacancy.

Enhanced the intrinsic oxidase-like activity of chiral carbon dots via manganese doping for selective catalytic oxidation

It is highly desirable to design and construct chemical catalysts with high activity and specificity as the alternatives of natural enzymes for industrial application. Chiral carbon dots (CDs), possessing both the intrinsic enzyme-like activity and specific recognition ability, are one of good candidates for enzyme-like catalysts. However, their catalytic activity is far from that of natural enzymes and needs to be enhanced. In this work, the modulation of the chiral structure and catalytic activity of chiral CDs with intrinsic oxidase-like activity was implemented by manganese (Mn) doping. Under the light condition, chiral CDs (l-Ser-CDs and d-Ser-CDs) derived from chiral serine (Ser) show weak catalytic activity and low selectivity toward the oxidation of L type of dopamine (l-DOPA), whereas the Mn functionalized chiral CDs (l-Mn-CDs or d-Mn-CDs) exhibit 6.9 times higher in catalytic activity and 2.9 times in selectivity ratio (SR) than Ser-CDs. Mn-CDs involve two-path catalytic process, in which the photogenerated electrons could reduce O2 to O2− as the active species and the holes would oxidize DOPA directly. Moreover, doping of Mn enables the CDs to generate more O2−. Besides, l-Mn-CDs have higher catalytic activity than that of d-Mn-CDs (+54.2 %), and the chiral Mn-CDs have stronger selective adsorption capacity towards chiral DOPA than Ser-CDs. Our work provides a new method for designing and preparing novel chiral artificial enzymes.

Insight into hydroxyl groups in anchoring Ir single–atoms on vacancy–deficient rutile TiO2 supports for selective catalytic oxidation of ammonia

High–performance catalysts are extremely required for controlling NH3 emission via selective catalytic oxidation (SCO), and the anchoring structural feature of active sites is a key prerequisite for developing them. This study confirms the importance of hydroxyl groups on vacancy–deficient reducible oxides as active groups. On the one hand, spontaneous atomic dispersion of active metal Ir is promoted by the abundant terminal hydroxyl groups. On the other hand, Ir cations anchor on the TiO2 surface through exchange with H+ in Ti–OH groups, and thus occupy the Brönsted acid sites. The adsorption strength of NH3 is another key factor affecting the reaction rate–determining step, namely NH3 dehydrogenation, which occurs at a faster rate in the coordinated L–NH3 rather than the ionic B–NH4+. Meanwhile, the coordinated L–NH3 significantly avoids the competitive adsorption of water vapor in the NH3–SCO reaction by reducing the number of hydrogen bonding. The TOF of preferred 0.8Ir/TiO2 sample is significantly higher than 0.2Ir/TiO2 sample, although Ir is almost always atomic dispersed. Finally, NH3 conversion is 85% in a wet circumstance (5% H2O) at 240 °C (GHSV = 85 000 h–1), with a N2 selectivity of up to 65% on 0.8Ir/TiO2 sample.

Cobalt phthalocyanine (CoPc) anchored on Ti3C2 MXene nanosheets for highly efficient selective catalytic oxidation

The first case of highly efficient selective catalytic oxidation for the production of quinclorac over CoPc anchored Ti3C2 MXene nanosheets.