Catalytic Studies Research Articles

Introduction of Methyl Group in Substituted Isoselenazolones: Catalytic and Mechanistic Study.

Copper-catalyzed direct selenation of substituted 2-bromo-N-phenylbenzamide substrates with elemental selenium powder provided a series of methoxy-substituted isoselenazolones via the C-Se and Se-N bond formations. Phenolic substituted isoselenazolones have been obtained by O-demethylation of the corresponding methoxy-substituted analogues using boron tribromide. Some isoselenazolones have been structurally characterized by X-ray single-crystal analysis. The glutathione peroxidase (GPx)-like antioxidant activity of isoselenazolones has been evaluated both in thiophenol and coupled-reductase assays. All isoselenazolones showed good GPx-like activities in the coupled-reductase assay. The ferric-reducing antioxidant power of phenolic antioxidants has also been evaluated. The best phenolic antioxidants were found to be good ferric-reducing antioxidant power agents. The single electron transfer, hydrogen atom transfer, and proton-coupled electron transfer mechanisms for the antioxidant properties of all catalysts have been supported by density functional theory calculations. The catalytic cycle was proposed for one of the phenolic isoselenazolones involving diselenide, selenenyl sulfide, selenol, and selenenic acid as intermediates using 77Se{1H} NMR spectroscopy.

Nitric acid free cyclohexane to adipic acid production using nickel and vanadium incorporated AlPO-5 molecular sieve

Rationally designing a stable and sustainable metal oxide supported over the molecular sieve catalysts for oxidizing cyclohexane (CYH) to adipic acid (AA) is vital in industrial applications. The in-situ hydrothermal synthesis method successfully incorporated vanadium and nickel into the aluminium phosphate-5 (AlPO-5) molecular sieves (MFI structure). The XPS and NH3 TPD analysis disclosed that the addition of Ni into V-AlPO-5 stabilizes the ratio of V4+/V5+, creating strong acidic sites and the formation of NiOOH, which are a vital role for the selective CYH oxidation to AA. An in-situ DRIFT study reveals that nickel takes part in the formation of dicarboxylate ions as an intermediate to form AA. Our catalytic studies profoundly suggested that the Ni0.1V0.2AlPO-5 catalyst used for CYH oxidation gives better selectivity towards AA (53%) in the presence of oxygen at an appropriate amount of solvent without an initiator or promoter within a short time (3h).

A Molybdenum(VI) Complex of 5-(2-pyridyl-1-oxide)tetrazole: Synthesis, Structure, and Transformation into a MoO3-Based Hybrid Catalyst for the Epoxidation of Bio-Olefins

The discovery of heterogeneous catalysts synthesized in easy, sustainable ways for the valorization of olefins derived from renewable biomass is attractive from environmental, sustainability, and economic viewpoints. Here, an organic–inorganic hybrid catalyst formulated as [MoO3(Hpto)]·H2O (2), where Hpto = 5-(2-pyridyl-1-oxide)tetrazole, was prepared by a hydrolysis–condensation reaction of the complex [MoO2Cl2(Hpto)]∙THF (1). The characterization of 1 and 2 by FT-IR and Raman spectroscopies, as well as 13C solid-state NMR, suggests that the bidentate N,O-coordination of Hpto in 1 (forming a six-membered chelate ring, confirmed by X-ray crystallography) is maintained in 2, with the ligand coordinated to a molybdenum oxide substructure. Catalytic studies suggested that 2 is a rare case of a molybdenum oxide/organic hybrid that acts as a stable solid catalyst for olefin epoxidation with tert-butyl hydroperoxide. The catalyst was effective for converting biobased olefins, namely fatty acid methyl esters (methyl oleate, methyl linoleate, methyl linolenate, and methyl ricinoleate) and the terpene limonene, leading predominantly to the corresponding epoxide products with yields in the range of 85–100% after 24 h at 70 °C. The versatility of catalyst 2 was shown by its effectiveness for the oxidation of sulfides into sulfoxides and sulfones, at 35 °C (quantitative yield of sulfoxide plus sulfone, at 24 h; sulfone yields in the range of 77–86%). To the best of our knowledge, 2 is the first molybdenum catalyst reported for methyl linolenate epoxidation, and the first of the family [MoO3(L)x] studied for methyl ricinoleate epoxidation.

Kinetic Protection of a Water‐Soluble Olefin Metathesis Catalyst for Potential Use under Biological Conditions

AbstractOlefin metathesis catalysts like AquaMet are vulnerable to different decomposition pathways under biologically relevant conditions. Currently, stabilizing strategies are focused on approaches with limited relevance for application under biologically relevant conditions. Initial attempts to stabilise AquaMet by encapsulation within a supramolecular metallocage showed that the nitrate counterions of the cage improve the activity of the catalyst. We show that the chloride ligands of AquaMet can be replaced with nitrates by simple anion‐exchange. Catalytic studies into metathesis of a diallyl substrate showed that the presence of nitrate generates higher yields of the ring‐closed product compared to AquaMet alone, under aqueous and biological conditions. Kinetic studies support that the nitrate‐containing catalyst both initiates faster and performs catalysis at a much faster rate than AquaMet, while the rate of catalyst deactivation was similar. This new strategy of kinetic protection of a transition metal catalyst may have future applications for other catalytic reactions applied in vivo.

Kinetic and Spectroscopic Studies of Methyl Ester Promoted Methanol Dehydration to Dimethyl Ether on ZSM-5 Zeolite

Methyl carboxylate esters have been shown to be potent promoters of low-temperature methanol dehydration to dimethyl ether (DME) using various zeolite catalysts. In the present work, catalytic kinetic studies, in-situ Fourier-transform infrared spectroscopy (FT-IR) and solid-state nuclear magnetic resonance spectroscopy (NMR) techniques were used to elucidate the promotional mechanism of methyl carboxylate esters on methanol dehydration to DME, using the medium pore zeolite H-ZSM-5 (MFI) as the catalyst. Kinetic studies were performed using the very potent methyl n-hexanoate promoter. The DME yield was dependent on both the methanol and methyl n-hexanoate partial pressures across the temperature ranges used in this study (110 to 130 °C). This is consistent with the promoted reaction being a bimolecular reaction between methanol and ester species adsorbed at the catalyst active sites, via an SN2 type reaction, as previously postulated. The in-situ FT-IR studies reveal that the Brønsted acid (BA) sites on H-ZSM-5 were very rapidly titrated by ester carbonyl group adsorption and bonded more strongly with esters than with methanol. Upon methanol addition, an even lower DME formation temperature (30 °C) was observed with methyl n-hexanoate pretreated H-ZSM-5 samples in the in-situ NMR studies, further confirming the strong promotion of this methyl ester on methanol dehydration to DME. The adsorption and reactivity of different methyl esters on H-ZSM-5 indicates that while methyl formate more easily dissociates into a surface methoxy species, [Si(OMe)Al], and carboxylic acid, it is a less potent promoter than alkyl-chain-containing methyl esters in methanol dehydration to DME, which in turn did not show this dissociative behavior in the low-temperature NMR studies. This indicates that methyl alkyl carboxylates do not need to be dissociated to a surface methoxy species to promote the methanol dehydration reaction and that a bimolecular associative mechanism plays an important role in promoting DME formation.

Applications of X-Ray Photoelectron Spectroscopy to Catalytic Studies: From Routine Analysis to Cutting Edge Surface Characterization

Applications of X-Ray Photoelectron Spectroscopy to Catalytic Studies: From Routine Analysis to Cutting Edge Surface Characterization

Thermocatalytic Decomposition of Dimethyl Methylphosphonate Based on CeO2 Catalysts with Different Morphologies

The catalytic performances of the catalysts and decomposition mechanisms of dimethyl methylphosphonate (DMMP), a commonly used nerve agent simulant, are well understood based on previous studies. However, the effects of the morphology of the catalyst on DMMP decomposition performance and mechanisms remain unexplored. Thus, in this work, experimental studies were conducted on the thermocatalytic decomposition of DMMP on CeO2 nanomaterials with different morphologies, e.g., irregular nanoparticles, nanorods, and nanocubes. From the performance evaluation, CeO2 nanorods exhibited higher DMMP thermocatalytic decomposition performance as compared to irregular nanoparticles and nanocubes. The primary reaction pathways were the same on all three morphologies of materials, according to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) study, whereas side reaction paths showed variable behaviors. According to the catalytic reaction mechanism study, the surface lattice oxygen played a vital role in the thermocatalytic decomposition of DMMP and the accumulation of phosphates, carbonates, and formates were the main factors for deactivation of the catalyst. The behavior of CeO2 catalyst with different morphologies in the thermocatalytic decomposition of DMMP was revealed in this work, and this will be useful for the future design of high-performing catalysts for the efficient degradation of chemical toxicant.

Chemical Upcycling of Waste Plastics to High Value-Added Products via Pyrolysis: Current Trends, Future Perspectives, and Techno-Feasibility Analysis.

Chemical upcycling of waste plastics into high-value-added products is one of the most effective, cost-efficient, and environmentally beneficial solutions. Many studies have been published over the past few years on the topic of recycling plastics into usable materials through a process called catalytic pyrolysis. There is a significant research gap that must be bridged in order to use catalytic pyrolysis of waste plastics to produce high-value products. This review focuses on the enhanced catalytic pyrolysis of waste plastics to produce jet fuel, diesel oil, lubricants, aromatic compounds, syngas, and other gases. Moreover, the reaction mechanism, a brief and critical comparison of different catalytic pyrolysis studies, as well as the techno-feasibility analysis of waste plastic pyrolysis and the proposed catalytic plastic pyrolysis setup for commercialization is also covered.

Steam reforming of methanol over combustion synthesized CuZnOx-based catalysts for fuel cell applications

Steam reforming of methanol is considered an effective way of producing hydrogen-rich reformate for fuel cell applications, with the CuZnOx catalysts to be the most widely used materials for this process. In this study, the incorporation of various promoters in the CuZnOx structure, via a solution-combustion method, was investigated in order to promote the performance of the catalysts in the steam reforming of methanol. The physicochemical results indicated that the Ga promotion can alter the environment of ZnO phase, creating ZnGa2O4 spinels, oxygen vacancies and thus, influencing the interaction with the active phase (strong metal-support interactions). The catalytic studies illustrated that an optimum amount in Ga2O3 (15 wt%) is beneficial in terms of activity and especially, selectivity, while the formation of a CuZnGaAlOx system enhances further the performance. The functionality of the most active material was successfully demonstrated in an integrated internal reforming methanol fuel cell operating at 220 °C.

Synthesis, Characterisation and Catalytic Studies of Ru (II) Carbonyl Complexes with Substituted Quinazoline Derivatives.

Several ruthenium(II) carbonyl complexes, of the type [RuCl2(CO)2L]∙nH2O {n = 1, L = L1, L2, L4, [RuCl2(CO)2(L)(H2O)]∙nH2O {n = 1, L = L3, L5, were prepared where L is 6-R-5,6-dihydrobenzoimidazo[1,2-c]quinazoline (R-Diq; R = ethyl: L1/ n or i-propyl: L2, L3/ n or i-butyl: L4, L5. The techniques used to identify them included elemental analysis, conductivity tests, TGA, infrared, electronic, NMR, and mass spectrometry. For all of the complexes, an octahedral geometry around the Ruthenium ion with monomeric and dimeric stereochemistry was proposed. Investigation of the catalytic activity of the complexes towards the oxidation of hydroquinone, cyclohexanol, and benzyl alcohol was carried out.

Photocatalytic degradation of aromatic pollutants using plasmonic Cu–Ag nanocomposites

Commercially viable solutions are required for the environmental pollution challenges that are plaguing the global community. Development of cost-effective and visible light active photocatalysts for degrading persistent organic pollutants was attempted herein. Copper (Cu) and silver (Ag) nanoparticles and their nanocomposites at various ratios were explored for pollutant degradation in presence of visible light. Para-nitrophenol (p-NP) was used as a model pollutant to compare the catalytic activities of the nanomaterials. The silver rich nanocomposite (CuAg2) was found to be the most active photocatalyst because of its stronger ability to harvest light and synergistic charge transfer between Cu and Ag. CuAg2 could photocatalytically mineralize pharmaceutical compounds such as sulfamethoxazole (SMX) and norfloxacin (NOR) in presence of a small amount of H2O2. Photogenerated hydroxyl radicals were found to be responsible for the degradation of the pollutants. Moreover, the CuAg2 could be used as a surface enhanced Raman spectroscopy (SERS) substrate for detecting the pollutants. Operando catalytic activity studies also could be conducted using the CuAg2. Finally, liquid chromatography-mass spectrometry (LC-MS) was used to understand the possible degradation pathways for SMX and NOR.

Manganese(III) complexes with tetradentate O^C^C^O ligands: Synthesis, characterization and catalytic studies on the CO2 cycloaddition with epoxides

A novel class of manganese(III) complexes bearing bis(NHC)-bis(phenolate) (O^C^C^O) type ligands was successfully synthesized. Three differently substituted imidazolium salts (with 2-hydroxyphenyl, (H4L1)Br2, 5‑tert‑butyl‑2-hydroxyphenyl, (H4L2)Br2, and 3,5-di‑tert‑butyl‑2-hydroxyphenyl, (H4L3)Br2, groups) were prepared as precursors of the (O^C^C^O) ligands and a convenient high-yield complexation reaction using manganese(III) acetate was developed. Electrospray ionization mass spectrometry (ESI-MS) and single-crystal X-ray diffraction (SC-XRD) data confirm the formation of the complexes of general formula [MnBrL1–3] and clarify their coordination geometry. The complexes were studied as homogeneous catalysts in the cycloaddition of CO2 to benzyl glycidyl ether (BGE) to form the corresponding cyclic carbonate, using tetrabutylammonium bromide (TBAB) or bis(triphenylphosphine)iminium bromide (PPNBr) as co-catalysts. The complex [MnBrL3] shows the highest activity, and kinetic investigations revealed a pseudo-first order dependence with respect to BGE under neat conditions. The temperature effect was also investigated using the Eyring and Arrhenius equations and the activation parameters for the neat reaction using [MnBrL3] and TBAB were experimentally determined (ΔH‡ = 11.2 kcal·mol-1 and ΔS‡ = -50 cal·mol-1·K-1). On the basis of the performed mechanistic studies and DFT investigations, a catalytic cycle which involves the CO2 1,2-insertion as the rate determining step is proposed.

Schiff base modified starch: A promising biosupport for palladium in Suzuki cross-coupling reactions

Starch can be used in diverse fields because it is a readily available, non-toxic polysaccharide with adaptable functionality and biodegradability. In this study, taking the aforementioned characteristics into consideration, we designed a modified starch (Starch-SB), which serves as supporting material for palladium stabilization. This new air and moisture-stable robust palladium composite [Starch-SB-Pd(II)] was characterized by FT-IR, XRD, TGA, XPS, SEM, EDX, TEM, CP/MAS 13C NMR, and ICP-MS analytical techniques. The catalytic studies exhibit high activity (up to 99 %) and stability in Suzuki cross-coupling reactions for this starch supported catalytic system under mild conditions (lower reaction temperature and green solvents) because of the cooperative interactions of multifunctional capturing sites on starch (Schiff base, hydroxy and amine groups) with palladium species. The experiments on reusability demonstrate that Starch-SB-Pd(II), which was prepared from functionalized starch, could be readily recycled several cycles through centrifugation. Moreover, we proposed a possibly multifunctional complex structure. This work presents an appealing and intriguing pathway for the utilization of polysaccharide as crucial support in green chemical transformations.

Synthesis and Catalytic Studies of Thermoresponsive Copper (I) Complex towards Click Reactions

AbstractClick reaction or copper‐assisted azide–alkyne cycloaddition (CuAAC) reaction can conveniently synthesize desired organic molecules or functionalize biological macromolecules. In many cases, trace amounts of residual copper from the reaction mixture are not trivial to remove when the exhaustive purification step is avoided to fulfill the essential criteria of a click reaction. It is often detrimental, particularly for biochemical applications or when it involves biological macromolecules. Herein, we have reported the synthesis of a new type of copper (I) complex as a smart catalyst for click reaction, which can be separated from the reaction mixture very easily by the slight elevation of temperature, thanks to its thermoresponsive behavior. The click reactions using a thermoresponsive catalyst were first studied in an aqueous medium using various organic molecules containing alkyne and azide functional groups. Later, the strategy was extended to biological macromolecules like collagen.

Ring-opening polymerization of lactides and ε-caprolactone catalyzed by Zn(II) aryl carboxylate complexes supported by 4-pyridinyl schiff base ligands

Synthesis and catalytic studies of aryl carboxylate Zn (II) complexes is reported. Reaction of substituted (E)-N-phenyl-1-(pyridin-4-yl)methanimine with a methanolic solution of Zn(CH3COO)2 and substituted aryl carboxylate co-ligands gave heteroleptic Zn(II) complexes; [Zn(C6H5COO)2(L1)]2 (1), [Zn(C7H7COO)2(L1)]2 (2), [Zn (4-F-C6H4COO)2(L1)]2 (3), [Zn(C6H5COO)2(L2)]2 (4), [Zn(C7H7COO)2(L2)]2 (5), [Zn (4-F-C6H4COO)2(L2)]2 (6), [Zn(C6H5COO)2(L3)]2 (7), [Zn(C7H7COO)2(L3)]2 (8), [Zn (4-F-C6H4COO)2(L3)]2 (9). The molecular structures of complexes 1 and 4 are dinuclear with the zinc atom in complex 1 adopting a distorted trigonal bipyramidal geometry in a bi-metallacycle while complex 4 is square pyramidal where all four benzoate ligands bridge the zinc metals in a paddle wheel arrangement. All complexes successfully initiated mass/bulk ring-opening polymerization (ROP) of ϵ-caprolactone (ϵ-CL) and lactides (LAs) monomers with or without alcohol co-initiators at elevated temperatures. Complexes 1, 4 and 6 containing the unsubstituted benzoate co-ligands were the most active in their triad; with complex 4 being the most active (kapp) of 0.3450 h−1. The physicochemical properties of the polymerization products of l-lactide and rac-lactide in toluene revealed melting temperatures (Tm) between 116.58 °C and 188.03 °C, and decomposition temperatures between 278.78 °C and 331.32 °C suggestive of an isotactic PLA with a metal capped end.

Design and synthesis of thermosensitive target segment resin with precisely controlled distance between immobilization sites for immobilization of penicillin G acylase

PurposeTo save the economic cost and improve the performance of enterprises, this study aims to synthesize high performance immobilized penicillin G acylase (PGA) carriers with fast reaction speed, high recovery rate of enzyme activity and good reusability through corresponding theoretical guidance and experimental exploration.Design methodology approachA diblock resin was synthesized by reversible addition-fragmentation chain transfer polymerization method using N, N-diethylacrylamide (DEA) and β-hydroxyethyl methacrylate (HEMA) as functional monomers poly(N, N-diethylacrylamide)-b-poly(β-hydroxyethyl methacrylate) (PDEA-b-PHEMA) was obtained, and the effect of the ratio of DEA and HEMA on the activity of PGA was investigated, and the appropriate block ratio of DEA and HEMA was obtained. After that, the competitive rate of HEMA and glycidyl methacrylate (GMA) under the carrier preparation conditions was investigated. Based on the above work, a thermosensitive resin carrier PDEA-b-PHEMA-b-P(HEMA-co-GMA) with different target distances was synthesized, and the chemical structures and molecular weight of copolymers were investigated by hydrogen NMR (1H NMR).FindingsThe lower critical solution temperature of the resin support decreases with the increase of the monomer HEMA in the random copolymerization; the catalytic performance study indicated that the response rate of the immobilized PGA is fast, and the recovery rate of the enzyme activity of the immobilized PGA varies with the distance between the targets. When the molar ratio of HEMA to GMA in the resin block is 8.15:1 [i.e. resin PDEA100-b-PHEMA10-b-P(HEMA65-co-GMA8)], the activity recovery rate of immobilized PGA can reach 50.51%, which was 15.49% higher than that of pure GMA immobilized PGA.Originality valueThis contribution provides a novel carrier for immobilizing PGA. Under the optimal molar ratio, the enzyme activity recovery could be up to 50.51%, which was 15.49% higher than that of PGA immobilized on the carrier with nonregulated distance between two immobilization sites.

Comprehensive catalytic and biological studies on new designed oxo- and dioxo-metal (IV/VI) organic arylhydrazone frameworks

Aryl Schiff base hydrazone have strong ability to form high stable complexes with transition metals with numerous applicability in catalysis and biology. For that, mononuclear pincer complexes of oxo/dioxo high valent metal ions (MoO22+, UO22+ and VO2+ ions, as MoO2Lhz, UO2Lhz and VOLhz, respectively) with aryl Schiff base hydrazone ligand (H2Lhz) were synthesized. H2Lhz and its MOxLhz complexes were characterized within alternative considerable tools. The complexes were formed in 1: 1 M ratios of MOx2+ (X = 1 or 2) ion to H2Lhz with octahedral geometries of cis-MoO2- and cis-UO2-complexes, and a square pyramidal geometry of VO-complex. The catalytic potential of MOxIILhz was estimated in the productive redox system of benzyl alcohol using H2O2 in an aerobic homogeneous phase. High productivity was progressed affording the corresponded aldehyde (benzaldehyde) with all catalysts. VOLhz displays the highest affectivity by 95 % of benzaldehyde (at 70 °C, after 2 h), MoO2Lhz represents an excellent action with 91 % (at 80 after 2 h). However, UO2Lhz shows the less efficacy with 80 % after 4 h of benzaldehyde. Hence, the catalytic performance depends upon the metal ion type (MOx2+ in the complex catalyst) in the proposed mechanism (oxygen transfer). For the bio-chemical assays, the anticancer and antimicrobial action of H2Lhz and its MOxLhz complexes were examined versus various microbes and human tumor cell lines. Their bio-interaction was also explored with ctDNA (calf thymus DNA) spectrophotometrically and the viscometric changes. All MOxLhz complexes exhibited higher inhibiting potential against the current microorganism growth (depending on the inhibiting zone in mm and MIC in μM values) and the human cancer cells over their free ligand H2Lhz. The ctDNA interaction was evaluated within Kb, the binding constants, and also the Gibbs’ free energy values for all studied compounds, exploring their role within the type and nature of MOx2+ ion for enhancement of their ctDNA interaction mode.

Synthesis of hybrid POSS based heterogeneous catalysts for N-alkylation of amines with alcohols

Herein, novel hybrid catalysts Cu@APPOSS-2 PC and Ni@APPOSS-2 PC have been synthesized by grafting the 2-pyridinecarboxaldehyde (2-PC) ligand on octa-aminopropyl polyhedral oligomeric silsesquioxanes (APPOSS) followed by immobilizing copper and nickel. The as-synthesized sustainable catalysts were characterized by FT-IR, SEM, and pXRD. Catalytic studies showed that both catalysts were excellent for CN coupling reactions to synthesize N-alkylated amines. Moreover, the facile synthesis, easy catalyst recovery, and good sustainability were the advantages from the catalytic point of view.

Synthesis and Catalytic Study of NiAg Bimetallic Core-Shell Nanoparticles.

This publication presents the synthesis of core-shell nanoparticles, where the core was Ni, and the shell was a Ag-Ni nano alloy. The synthesis was based on the reduction of Ni and Ag ions with sodium borohydride in the presence of trisodium citrate as a stabilizer. In order to determine the phase composition of the obtained nanoparticles, an XRD study was performed, and in order to identify the oxidation states of the nanoparticle components, an XPS spectroscopic study was performed. The composition and shape of the particles were determined using the HR-TEM EDS test. The obtained nanoparticles had a size of 11 nm. The research on catalytic properties was carried out in the model methylene blue reduction system. The investigation of the catalytic activity of colloids was carried out with the use of UV-Vis spectrophotometry. The Ag-Ni alloy was about ten times more active than were pure silver nanoparticles of a similar size.

Porous Magnesium Oxide by Twin Polymerization: From Hybrid Materials to Catalysis

AbstractTwin monomers [Mg(2‐OCH2‐cC6H4O)][L]0.8 (2, L=diglyme) and [Mg(2‐OCH2‐cC6H4O)][L]0.66 (3, L=tmeda) form by their thermal polymerization interpenetrating organic‐inorganic hybrid materials in a straightforward manner. Carbonization (Ar) followed by calcination gave porous MgO (2: surface area 200 m2 g−1, 3: 400 m2 g−1), which showed in catalytic studies towards Meerwein‐Ponndorf‐Verley reductions excellent yields and complete conversions for cyclohexanone and benzaldehyde. However, with crotonaldehyde a mixture of C4–C8 compounds was obtained. When MgO was exposed to air then primarily crotyl alcohol was formed. The range of applications could be easily extended by twin polymerization of 3 in presence of [Cu(O2CCH2O(CH2CH2O)2Me)2] (4) or [Ag(O2CCH2‐cC4H3S)(PPh3)] (5), resulting in the formation of nanoparticle‐decorated porous CuO@MgO or Ag@MgO materials, which showed high catalytic reactivity towards the reduction of methylene blue.