Catalytic Activity For Hydrogenation Research Articles

Recent Developments on CO2 Hydrogenation Performance over Structured Zeolites: A Review on Properties, Synthesis, and Characterization

This review focuses on an extensive synopsis of the recent improvements in CO2 hydrogenation over structured zeolites, including their properties, synthesis methods, and characterization. Key features such as bimodal mesoporous structures, surface oxygen vacancies, and the Si/Al ratio are explored for their roles in enhancing catalytic activity. Additionally, the impact of porosity, thermal stability, and structural integrity on the performance of zeolites, as well as their interactions with electrical and plasma environments, are discussed in detail. The synthesis of structured zeolites is analyzed by comparing the advantages and limitations of bottom-up methods, including hard templating, soft templating, and non-templating approaches, to top-down methods, such as dealumination, desilication, and recrystallization. The review addresses the challenges associated with these synthesis techniques, such as pore-induced diffusion limitations, morphological constraints, and maintaining crystal integrity, highlighting the need for innovative solutions and optimization strategies. Advanced characterization techniques are emphasized as essential for understanding the catalytic mechanisms and dynamic behaviors of zeolites, thereby facilitating further research into their efficient and effective use. The study concludes by underscoring the importance of continued research to refine synthesis and characterization methods, which is crucial for optimizing catalytic activity in CO2 hydrogenation. This effort is important for achieving selective catalysis and is paramount to the global initiative to reduce carbon emissions and address climate change.

Enhanced Catalytic Hydrogenation of Olefins in Sulfur-Rich Naphtha Using Molybdenum Carbide Supported on γ-Al2O3 Spheres under Steam Conditions: Simulating the Hot Separator Stream Process.

Spheres comprising 10 wt.% Mo2C/γ-Al2O3, synthesized through the sucrose route, exhibited unprecedented catalytic activity for olefin hydrogenation within an industrial naphtha feedstock that contained 23 wt.% olefins, as determined by supercritical fluid chromatography (SFC). The catalyst demonstrated resilience to sulfur, exhibiting no discernible deactivation signs over a tested 96 h operational period. The resultant hydrogenated naphtha from the catalytic process contained only 2.5 wt.% olefins when the reaction was conducted at 280 °C and 3.44 × 106 Pa H2, subsequently blended with Athabasca bitumen to meet pipeline specifications for oil transportation. Additionally, the carbide catalyst spheres effectively hydrogenated olefins under steam conditions without experiencing any notable hydrogenation in the aromatics. We propose the supported carbide catalyst as a viable alternative to noble metals, serving as a selective agent for olefin elimination from light petroleum distillates in the presence of steam and sulfur, mitigating the formation of gums and deposits during the transportation of diluted bitumen (dilbit) through pipelines.

Coupling of modulating d-band center and optimizing interface electronic structure via MXene and Bi-metal doping in CoP achieving efficient bifunctional catalytic activity for water splitting

Bifunctional electrocatalysts that exhibit excellent catalytic activity for both hydrogen (HER) and oxygen evolution reactions (OER) are ideal for alkaline overall water splitting. The unique structure and diverse composition of cobalt phosphide catalysts are highly favorable for enhancing catalytic reaction kinetics. However, cobalt phosphide electrocatalysts typically exhibit insufficient OER activity. To overcome this text, we synthesized a Ru and V co-doped CoP-coupled highly conductive MXene catalyst with nano-arrays by in-situ growth on the surface of carbon cloth. The HER and OER overpotentials of the catalyst at 10 mA cm−2 current density were 30 and 206 mV, respectively. Furthermore, a series of physicochemical characterizations and first-principles calculations demonstrated that the increased HER and OER activities resulted from the synergistic effect established by the double doping and heterostructure. This effect produced an effective modulation of the d-band center of the catalysts, promoting adsorption effects on the intermediates. In conclusion, this work presents a novel approach to improving the electrocatalytic activity of phosphides and provides a faster and more environmentally friendly method for separating hydrogen from water.

Tuning Catalytic Activity of CO2 Hydrogenation to C1 Product via Metal Support Interaction Over Metal/Metal Oxide Supported Catalysts.

The metal supported catalysts are emerging catalysts that are receiving a lot of attention in CO2 hydrogenation to C1 products. Numerous experiments have demonstrated that the support (usually an oxide) is crucial for the catalytic performance. The support metal oxides are used to aid in the homogeneous dispersion of metal particles, prevent agglomeration, and control morphology owing to the metal support interaction (MSI). MSI can efficiently optimize the structural and electronic properties of catalysts and tune the conversion of key reaction intermediates involved in CO2 hydrogenation, thereby enhancing the catalytic performance. There is an increasing attention is being paid to the promotion effects in the catalytic CO2 hydrogenation process. However, a systematically understanding about the effects of MSI on CO2 hydrogenation to C1 products catalytic performance has not been fully studied yet due to the diversities in catalysts and reaction conditions. Hence, the characteristics and modes of MSI in CO2 hydrogenation to C1 products are elaborated in detail in our work.

Enhanced conversion of CO2 into C2H4 on single atom Cu-anchored graphitic carbon nitride: Synergistic diatomic active sites interaction

Single atom metal–nitrogen–carbon materials have emerged as remarkably potent catalysts, demonstrating unprecedented potential for the photo-driven reduction of CO2. Herein, a unique Cu@g-C3N5 catalyst obtained by cooperation of single atom Cu and nitrogen-rich g-C3N5 is proposed. The particular CuN diatomic active sites (DAS) in Cu@g-C3N5 contribute to the formation of highly stable CuOCN adsorption, a key configuration for CO2 activation and CC coupling. The synergistic diatomic active sites interaction is found responsible for the efficient photoreduction of CO2 to C2H4 which has been demonstrated in our Gibbs free energy calculation and COHP analysis. The CO2 activation mechanism was studied, the charge density difference and DOS analysis show that the low oxidation state Cu atom significantly affects the electronic structure of g-C3N5 and then enhance the catalytic activity of CO2 hydrogenation.

Nitrogen species from Spirulina platensis derived bio-oil enhance catalytic activity of cobalt catalysts for hydrogenation

High nitrogen content in Spirulina platensis-derived bio-oil is a highly undesirable feature in upgrading of bio-oil to biofuel via hydrodeoxygenation. However, the nitrogen species could be potentially used as dopant for tailoring the catalytic behaviors of metallic sites in heterogeneous catalysts. In this study, the nitrogen species in the bio-oil from hydrothermal carbonization (HTC) of Spirulina platensis was used to modify Co-based catalyst for enhancing their catalytic activity for hydrogenation of o-chloronitrobenzene (o-CNB). The results showed that the introduction of N species not only promoted dispersion of Co particles via formation of Co–N sites, but also generated extra pores and significantly increased H2 uptake. The abundant Co–N sites, high dispersion of Co and higher surface area of N-doped catalyst (CoFeAl–N) jointly contributed to the enhanced catalytic activity for hydrogenation of o-CNB, achieving the yield of 90.3% for o-chloroaniline (o-CA) and lowering the activation energy from 63.0 kJ mol−1 (with N-free CoFeAl catalyst) to 55.1 kJ mol−1. The effectiveness of introducing nitrogen for enhancing catalytic activity for hydrogenation of o-CNB was also confirmed in the experiments for doping Co/Al2O3 (prepared via impregnation) and CoAl (prepared via co-precipitation) catalysts with the Spirulina platensis derived bio-oil.

Facile synthesis of Cu@Ag/SiO2 catalysts for the selective hydrogenation of dimethyl oxalate to methyl glycolate

A promising route for producing biodegradable polyglycolic acid material from syngas has garnered increasing attentions. In this route, one of the pivotal issues is developing favorable catalysts for semi-hydrogenation of dimethyl oxalate (DMO) to methyl glycolate (MG). Silver catalysts were reported to be effective but suffered from the high cost. Herein, we prepared small-sized Cu@Ag/SiO2 catalysts with appropriate Ag/Cu ratios by a facile wet impregnation method. This core–shell structure facilitated the intermetallic electronic transference from Cu to Ag. The surface exposure of electron-rich silver species could promote the catalytic activity and MG desorption in the DMO hydrogenation, which achieved high efficiency without compromising the MG selectivity. The optimal catalyst with Ag/Cu mass ratio of 3/2 displayed excellent space time yield towards MG of 47.3 g·gAg−1·h−1. These insights could offer a potential strategy to reduce the silver-based catalyst cost for the semi-hydrogenation of DMO to MG.

Cu-Doped CoZn@NC promotes catalytic activity of furfural hydrogenation at low temperature: Regulation of copper

The low-cost Cu-based catalysts have excellent selectivity in biomass hydrogenation, but it is challenging to improve their catalytic activity at low temperature. Herein, the trimetallic CuxCoZn@NC (where x = 0.1, 0.3, 0.5 mmol is the molar mass of Cu) were prepared by in suit pyrolysis using trimesic acid with stronger coordination ability. When it was applied to the furfural (FF) selective hydrogenation process, the catalytic yield of the optimal Cu0.3CoZn@NC reached >99 % under mild condition of 90 °C, which was 29 times superior to that of the CoZn@NC without Cu doping. The results demonstrate that the doping of Cu reduces the activation energy of CuxCoZn@NC and increases the catalytic activity at low temperature relative to CoZn@NC. The characterizations and density functional theory (DFT) calculations show that the incorporation of suitable Cu content enhances the interaction between Cu and Co. The amount of surface-active Co0 and the electron density are significantly enhanced, which effectively stimulates the dissociation of hydrogen. Moreover, the Lewis acid content is significantly increased to facilitate the adsorption and activation of FF. Meanwhile, the impact of Cu content variation on the performance of the multi-metal catalyst is discussed. This work is promising to establish a foundation for the accurate design of polymetallic catalysts through adjusting the Cu content to regulate the reaction activity and selectivity.

Effects of ZrO2 crystalline phase on oxygen vacancy of GaZr oxides and their properties for CO2 hydrogenation to light olefins

A bifunctional catalyst, comprising GaZr oxide and SAPO-34 zeolite, manifests enhanced catalytic activity in CO2 hydrogenation to light olefins; nonetheless, the comprehensive analysis of the pivotal role played by the underlying structure of ZrO2 in Ga-Zr oxide has not been investigated. Herein, different crystalline structures of ZrO2 were prepared by the co-precipitation method and adopted as a support to deposit Ga to obtain ZrO2 with different ratios of monoclinic ZrO2 (m-ZrO2) to tetragonal ZrO2 (t-ZrO2) in GaZr oxides for CO2 hydrogenation to light olefins. Various characterizations demonstrated that the interface between Ga and the mixed phase of (m-t) ZrO2 produces more oxygen vacancies which favors the adsorption and activation of CO2, and the larger specific surface area and stronger H2 adsorption and dissociation capacity promote CO2 conversion. Interestingly, the GaZr oxide with high m-ZrO2 content exhibits superior catalytic activity than the GaZr oxide with high content of t-ZrO2. The highest light olefins yield (9.0%) and selectivity (77.9%) (CO free) with 27.9% CO2 conversion was achieved. In-situ DRIFT spectra further elaborated that the GaZr oxides with different ZrO2 crystalline phases follow the same reaction pathway to hydrogenate CO2 first to HCOO* and then to CH3O* on GaZr oxide surface. While compared with sole ZrO2, the introduction of Ga significantly promotes the hydrogenation of HCOO* to CH3O*, acting as a crucial reaction intermediate that subsequently diffuses into SAPO-34 pores to enhance the desired light olefins selectivity.

Reduced Siderite Ore Combined with Magnesium Oxide as Support Material for Ni-Based Catalysts; An Experimental Study on CO2 Methanation

Ni-based catalysts play a fundamental role in catalytic CO2 methanation. In this study, the possibility of using siderite ore as a catalyst or catalytic support material for nickel-based catalysts was investigated, aiming at the exploitation of an abundant natural resource. The catalytic performance of Ni-based catalysts with reduced siderite ore as a support was evaluated and compared to MgO as a support material. MgO is known as an effective support material, as it provides access to bifunctional catalysts because of its basicity and high CO2 adsorption capacity. It was shown that undoped and Ni-doped reduced siderite ore have comparable catalytic activity for CO2 hydrogenation (20−23%) at 648 K, but show limited selectivity toward methane (<20% for sideritereduced and 60.2% for Ni/sideritereduced). When MgO was added to the support material (Ni/sideritereduced/MgO), both the CO2 conversion and the selectivity toward methane increased significantly. CO2 conversions were close to the thermodynamic equilibrium, and methane selectivities of ≥99% were achieved.

Mechanism of NCNTs Growth on Foamed Nickel and Thus-Prepared PS Hydrogenation High-Performance Carrier NCNTs@FN.

Traditional heterogeneous catalysts are affected in the catalytic hydrogenation of PS by the scale effect, viscosity effect, adhesion effect, and conformational effect, resulting in poor activity and stability. Monolithic Pd-CNTs@FN catalysts could eliminate or weaken the impact of these negative effects. We grew nitrogen-doped carbon nanotubes (NCNTs) on monolithic-foamed nickel (FN) and investigate their growth mechanism. Meanwhile, the feasibility of using the NCNTs@FN carrier for PS hydrogenation reaction was also verified. The growth of NCNTs on FN can be divided into 3 stages: initial growth stage, stable growth stage, and supersaturation stage. Finally, a three-layer structure of NCNT layer, dense carbon layer, and FN skeleton is formed. Two types of structures, nickel-doped carbon nanotubes (NiCNTs) and C-Ni alloy, are formed by combining C and Ni, while four nitrogen-doped structures, NPD, NPR, NG, and NO, are formed by C and N. The prepared carrier exhibited an extremely outstanding specific surface area (2.829 × 106 cm2/g) and strength (no NCNTs falling off after 24 h 500 rpm agitation), as well as high catalytic activity for PS hydrogenation after loaded with Pd (2.13 ± 0.95 nm), with a TOF of up to 27.6 gPS/(gPd•h). After 8 repetitions of the catalyst, there was no significant decrease in activity. This proves the excellent performance of Pd-NCNTs@FN in polymer hydrogenation reactions, laying a solid foundation for further research on the mechanism of NCNTs promoting PS hydrogenation and regulating the growth of NCNTs.

Pd nanoflakes epitaxially grown on defect MoS2 nanosheets for enhanced nitroarenes hydrogenation to anilines

Hydrogenation of nitroarenes to anilines under mild conditions is attractive from both theoretical and practical viewpoints. Here, high-performance catalyst with layered Pd nanoparticles epitaxially growing on ultrathin MoS2 nanosheets (Pd/MoS2) were prepared. It shows surprisingly high catalytic activity, selectivity and stability for hydrogenation of various nitroarenes to corresponding anilines; the turnover frequency is one or two magnitudes higher than conventional Pd-based catalysts. Surface sulfur vacancies are formed on MoS2 nanosheets with low formation energy barrier. These S vacancies provide efficient positions for adsorbing Pd atoms, which enables facile cleavage of N–O bond as result of strong interfacial electron interaction that decreases activation energy by 0.41 eV in comparison with conventional Pd catalysts. In situ spectroscopy and DFT calculation results reveal a dual-site mechanism, in which surface Pd sites adsorb and dissociate H2 into active H*, and then readily reacts with nearby activated nitroarene to form aniline on interfacial Pd-MoS2 sites.

Seafood waste derived Pt/Chitin nanocatalyst for efficient hydrogenation of nitroaromatic compounds

The fabrication of reliable, reusable and efficient catalyst is crucial for the conversion of nitroaromatic compounds into more chemically valuable amine-based molecules. In this study, a series of chitin supported platinum (Pt) catalysts with high catalytic activity, stability, and reusability were developed by using chitin derived from seafood waste as raw materials. The catalytic performance differences among these catalysts activated by different methods were investigated by hydrogenation of nitroaromatic compounds. The results showed that the multilayer hierarchical pore structure and abundance of hydroxyl and acetamido groups in chitin provided ample anchoring sites for Pt nanoparticles (NPs), ensuring the high dispersion of Pt NPs. Moreover, the interconnected channels between chitin nanofibrous microspheres facilitated rapid transport of reaction substrates. The best Pt/Chitin catalyst exhibited excellent catalytic activity and broad substrate applicability in hydrogenation of nitroaromatic compounds. Significantly, even after 20 runs, no discernible deactivation of activity was observed, demonstrating exceptional catalytic reusability. The application of seafood waste-based catalysts is conducive to the development of a green/sustainable society.

Performance of Cu-Mn-Zn/ZrO2 catalysts for methanol synthesis from CO2 hydrogenation: The effect of Zn content

A series of Cu-Mn-Zn/ZrO2 catalysts with different Zn contents were prepared by sol-gel method and characterized by XRD, BET, TPR, N2O-adsorption, XPS, TPD and in-situ DRIFTS. It was found that by increasing a certain amount of Zn, the catalytic activity for CO2 hydrogenation increased. Among all samples, Cu3MnZn0.5Zr0.5 (CMZZ-0.5) possessed the best CO2 conversion (6.5%) and methanol selectivity (73.7%) at 250 °C and 5 MPa. Characterization results showed that Zn entered the Cu1.5Mn1.5O4 spinel structure, forming ZnOx and thus more surface OH groups. This increased the content of Cu0 and Cuα, which improved the activation of H2 and CO2. The pathway of CO2 to methanol was also clarified through in-situ DRIFTS.

Influence of Charge Delocalization on Manganese Catalyzed Transfer Hydrogenation

AbstractHydrogen transfer reactions promoted by Mn(I)‐based catalysts are a recently emerged field of research. Herein, we demonstrate the crucial effect of charge delocalization on the catalytic activity in transfer hydrogenation. Therefore, we synthesized pyridyl‐pyrazole ligands and a pyridyl‐pyridazinone ligand which exhibit resonance structures upon deprotonation with varying capability to transfer charge to the manganese center. The corresponding Mn(I) complexes were characterized and their activity as catalyst in transfer hydrogenation of acetophenone was determined using in‐situ IR techniques. Kinetic data and DFT calculations reveal that the ligands are deprotonated throughout the catalytic cycle and that the catalysts in which resonance structures point towards more negative charge at the metal center are also the more active ones. Thus, we deliver ample evidence that for effective hydrogen transfer the manganese catalyst requires a ligand with a deprotonable moiety allowing efficient delocalization to the metal while geometrical access of the acidic proton to the substrate is not essential. Our findings highlight the importance of an anionic hydrido intermediate, where mesomerism allows an effective charge transfer to the metal. This may support the ongoing development of new manganese‐based catalysts.

Probing the Reactive Intermediates in CO2 Hydrogenation on Ni/Al2O3 Catalysts with Modulation Excitation Spectroscopy

AbstractIn‐situ infrared spectroscopy is one of the most effective methods to study the surface species on solid catalysts. Still, it is sometimes difficult to identify the reactive intermediates because spectator species, the catalyst support, and experimental noise also contribute to the total spectra. In this study, we prepared three archetypical Ni/Al2O3 catalysts that showed significantly different catalytic activity and selectivity for CO2 hydrogenation, depending on the calcination and reduction temperature. After detailed characterization, we used a combination of Modulation Excitation‐Phase Sensitive Detection‐Diffuse Reflectance Infrared Fourier Transform Spectroscopy (ME‐PSD‐DRIFTS) and Steady State Isotopic Kinetic Analysis (SSITKA) to show that bicarbonates and formates are key reactive intermediates. Furthermore, we also observe carbonyls on the catalyst with the most metallic character and highest selectivity towards CH4. These results confirm that the hydrogenation of CO2 occurs in an associative and consecutive reaction pathway that is highly structure‐sensitive. In this way, we also demonstrate how the simultaneous collection of spectroscopic and kinetic data during modulated or transient experiments is a powerful tool for investigating solid catalysts under realistic operation conditions.

Air-Stable Coordinatively Unsaturated Ruthenium(II) Complex for Ligand Binding and Catalytic Transfer Hydrogenation of Ketones from Ethanol.

Coordinatively unsaturated complexes are interesting from a fundamental level for their formally empty coordination site and, in particular, from a catalytic perspective as they provide opportunities for substrate binding and transformation. Here, we describe the synthesis of a novel underligated ruthenium complex [Ru(cym)(N,N')]+, 3, featuring an amide-functionalized pyridylidene amide (PYA) as the N,N'-bidentate coordinating ligand. In contrast to previously investigated underligated complexes, complex 3 offers potential for dynamic modifications, thanks to the flexible donor properties of the PYA ligand. Specifically, they allow both for stabilizing the formally underligated metal center in complex 3 through nitrogen π-donation and for facilitating through π-acidic bonding properties the coordination of a further ligand L to the ruthenium center to yield the formal 18 e- complexes [Ru(cym)(N,N')(L)]+ (4: L = P(OMe)3; 5: L = PPh3; 6: L = N-methylimidazole; 7: L = pyridine) and neutral complex [RuCl(cym)(N,N')] 8. Analysis by 1H NMR and UV-vis spectroscopies reveals an increasing Ru-L bond strength along the sequence pyridine <1-methylimidazole < PPh3 < P(OMe)3 with binding constants varying over 3 orders of magnitude with log(Keq) values between 2.8 and 5.7. The flexibility of the Ru(PYA) unit and the ensuing accessibility of saturated and unsaturated species with one and the same ligand are attractive from a fundamental point of view and also for catalytic applications, as catalytic transformations rely on the availability of transiently vacant coordination sites. Thus, while complex 3 does not form stable adducts with O-donors such as ketones or alcohols, it transiently binds these species, as evidenced by the considerable catalytic activity in the transfer hydrogenation of ketones. Notably, and as one of only a few catalysts, complex 3 is compatible with EtOH as a hydrogen source. Complex 3 shows excellent performance in the transfer hydrogenation of pyridyl-containing substrates, in agreement with the poor coordination strength of this functional group to the ruthenium center in 3.

Constructing fully exposed Pt atomically dispersed catalysts for enhanced multifunctional selective hydrogenation reactions

Constructing highly efficient and low-cost catalysts is essential for the selective hydrogenation reaction. Herein, we developed fully exposed Pt atomically dispersed catalysts (PtAD/C-Al2O3) by a simple carbon modified strategy. Importantly, the co-existence of Pt-O1C2 single atoms and Pt nanoclusters in the PtAD/C-Al2O3 system could exhibit excellent catalytic activity in the selective hydrogenation of quinoline and p-nitrophenol. Notably, the quinoline conversion and the corresponding selectivity of 1,2,3,4-tetrahydroquinoline is 99.6 % and 99.3 %, respectively. Meanwhile, the turnover frequency of PtAD/C-Al2O3 (1081 h−1) is 3.8 and 5.7 times higher than that of Pt single-atom catalysts (PtSA/C-Al2O3) and Pt nanoparticles (PtNPs/C-Al2O3), respectively, during quinoline hydrogenation. Besides, the rate constant of PtAD/C-Al2O3 could reach 192.5 min-1mgPt-1 for p-nitrophenol hydrogenation, which is much better than most of the reported catalysts. Mechanism studies revealed the synergistic effect between Pt-O1C2 single atoms and Pt nanoclusters acts as the main role in enhancing the hydrogenation activity. Specifically, Pt single atoms sites mainly adsorb and activate quinoline molecules, while Pt nanoclusters boost the dissociation of H2 molecules to H atoms. This work paves an origin carbon modified method to construct Pt atomically dispersed catalysts for efficient multifunctional hydrogenation.

BICAAC-Derived Covalent and Cationic Ir(I) Complexes: Application of Ir(BICAAC)Cl(COD) Complexes as Catalysts for Transfer Hydrogenation and Hydrosilylation Reactions.

The ambiphilic bicyclic (alkyl)(amino)carbenes (Me/iPrBICAAC) upon reaction with [IrCl(COD)]2 smoothly afford mononuclear Ir(I) complexes that have been spectroscopically and structurally characterized. These complexes exhibit good catalytic activity for transfer hydrogenation (TH) of 4-chlorobenzaldehyde using isopropyl alcohol (iPrOH), with turnover frequency values ranging between 6269 and 8093 h-1. Choosing the covalent complex Ir(MeBICAAC)Cl(COD) as a catalyst, a wide array of carbonyls and imines functionalized with electron-withdrawing and electron-donating substituents have been surveyed and afforded their reduced products in moderate-to-good yields. No detachment of the BICAAC unit from the Ir center was observed upon prolonged heating of Ir(MeBICAAC)Cl(COD) in toluene-d8 or isopropyl alcohol-d8, which evidenced good thermal stability of the catalyst. Complex Ir(MeBICAAC)Cl(COD) was also found to be catalytically active for the hydrosilylation of a variety of aldehydes using triethylsilane (Et3SiH).

Synthesis of Nitrogen- and Oxygen-Containing Heterocycles Catalysed by Metal Nanoparticles Reported in 2022

AbstractThe versatility of aza- and oxa-heterocyclic compounds has garnered significant attention in recent times. A large number of currently approved pharmaceutical products include nitrogen- and oxygen-containing heterocycles. Recent nanotechnological developments have propelled an upsurge in the applications of nanocatalysis for heterocyclic synthesis. Metal nanoparticles (MNPs) have emerged as promising catalysts for the synthesis of aza- and oxa-heterocycles owing to their unique physicochemical properties. Various MNPs including gold, silver, nickel and palladium have been evaluated for their catalytic activities in different reaction types, including cyclisation, coupling, hydrogenation and oxidative transformations. The MNPs have exhibited remarkable catalytic efficiency when utilised under optimal conditions. These catalysts have showcased high reusability and recyclability, yielding satisfactory amounts of the desired heterocyclic compound. The present work provides a detailed overview of recent advances in the area of MNP-assisted synthetic construction of aza- and oxa-heterocycles, published during the previous calendar year, 2022. The review serves as a valuable resource and also paves the way for future investigations in the development of novel catalytic strategies for heterocycle synthesis.1 Introduction2 Nanocatalysis3 Aza- and Oxa-Heterocycle Synthesis Catalysed by MNPs3.1 AuNPs3.2 CuNPs3.3 CoNPs3.4 FeNPs3.5 NiNPs3.6 PdNPs3.7 PtNPs3.8 SiNPs3.9 ZnNPs3.10 Bimetallic NPs3.11 Other MNPs4 Summary and Outlook