Catalyst For Synthesis Research Articles

Humin-sulfuric acid as a novel recoverable biocatalyst for pyrrole synthesis in water

Humin-sulfuric acid (Humin-SO3H) as a novel efficient biobased sulfonic acid was easily prepared by adding chlorosulfuric acid (ClSO3H) to Humin and characterized by potentiometric titration and FT-IR spectrum. Humin-SO3H is an eco-friendly, heterogeneous biobased, and efficient catalyst for Paal-Knorr and Clauson-Kaas pyrrole synthesis. The catalyst is easily recovered by simple filtration and has excellent turnover efficiency even after 4 cycles. Besides, due to the clearance of the biocatalyst away from the reaction media, the desired highly pure products can be achieved in high to excellent yields. Due to high water dispersibility, Humin-SO3H can be utilized as a highly efficient green catalyst for pyrrole synthesis.

Properties of palladium-phosphorus catalysts supported on HZSM-5 zeolite in the direct synthesis of hydrogen peroxide

The properties of Pd/HZSM-5 and Pd–nP/HZSM-5 catalysts in direct synthesis and side processes of decomposition and hydrogenation of H2O2 under mild conditions in ethanol and aqueous-ethanol medium in the presence of an acid inhibitor were studied. Using HR-TEM, XRD and ICP MS methods, it was shown that as a result of modification with phosphorus, X-ray amorphous highly dispersed systems are formed, which represent structurally disordered solid solutions of phosphorus in palladium. The main reasons for the promoting effect of phosphorus on the yield of H2O2 are considered. It has been established that, along with phosphorus and acid modifiers, the use of a zeolite support in the H-form favors the inhibition of the side process of H2O2 decomposition.

Simulated sunlight-driven photocatalytic activation of peroxydisulfate by core–shell Ag@SiO2/TiO2 nanocomposite for efficient methyl orange degradation

Herein, core–shell Ag@SiO2/TiO2 nanocomposites were synthesized and applied to activate peroxydisulfate (PDS) for wastewater purification. The Ag core and Ag-doped TiO2 shell were obtained by stober method and calcination method. The dispersion degree and size of Ag in TiO2 would influence the oxygen vacancy. Ag enhanced the visible absorption of TiO2 and activated PDS. Improved degradation performance was attributed to enhanced PDS activation by photogenerated e−, which separated h+and thus promoted methyl orange(MO) degradation. Reactive oxidative species were verified under dark and light conditions via quenching experiments and electron paramagnetic resonance tests, demonstrating SO4•–, h+, O2•–, and1O2were formed in light,whereasSO4•–, •OH, O2•–, and 1O2were responsible for MO degradation under dark conditions. The Ag@SiO2/TiO2/PDS/light system showed selectivity for removal of cationic dyes (e.g., methylene blue and malachite green) through adsorption and photocatalysis, whereas anionic dyes (e.g., MO) were degraded by photocatalysis alone. Besides, we found excess adsorption of micropollutant onto catalyst may be adverse to the activation of PDS. Therefore, the adsorption of oxidant (such as PDS) onto the catalyst surface would be beneficial for catalytic activation and micropollutant degradation, especially onto active sites. This work aims to provide a new avenue for core-shell structure catalyst synthesis in wastewater purification.

Advances in Chiral Pincer Complexes: Insights and Applications in Catalytic Asymmetric Reactions.

Chiral pincer complexes, characterized by their rigid tridentate coordination framework, have emerged as powerful catalysts in asymmetric synthesis. This review provides a comprehensive overview of recent advancements in the development of chiral pincer-type ligands and their corresponding transition metal complexes. We highlight the latest progress in their application across a range of catalytic asymmetric reactions, including the (transfer) hydrogenation of polar and non-polar bonds, hydrophosphination, alkynylation, Friedel-Crafts reactions, enantioselective reductive cyclization of alkynyl-tethered cyclohexadienones, enantioselective hydrosilylation, as well as Aza-Morita-Baylis-Hillman reactions. The structural rigidity and tunability of chiral pincer complexes enable precise control over stereoselectivity, resulting in high enantioselectivity and efficiency in complex molecular transformations. As the field advances, innovations in ligand design and the exploration of new metal centers are expected to expand the scope and utility of these catalysts, bearing significant implications for the synthesis of enantioenriched compounds in pharmaceuticals, materials science, and beyond.

Green Synthesis of Magnetic Fe2O3 Nanoparticle with Chenopodium glaucum L. as Recyclable Heterogeneous Catalyst for One-Pot Reactions and Heavy Metal Adsorption.

The growth of the environment depends upon developing greener and ecological methods for managing pollutants and contamination from industrial wastewater, which causes significant effects on human health. The removal of these pollutants from wastewater using nanomaterials covers an ecological method that is free from expensive and secondary pollution. In this report, we developed magnetic iron nanoparticles from Chenopodium glaucum (CG), which showed excellent adsorption capacity at pH 5 for selective Hg2+ and Pb2+ metal ions among various heavy metal ions, with maximum adsorption capacities of 96.9 and 94.1%, respectively. These metals' adsorption process conforms to the Langmuir model, which suggests that monolayer adsorption transpires on CG-Fe2O3 nanoparticles. CG-Fe2O3 nanoparticles also act as an efficient and recyclable heterogeneous catalyst for one-pot synthesis of xanthene derivatives, yielding products with high yields (up to 97%) and excellent purity (crystalline form) within a short timeframe (6 min) using microwave irradiations (at 120 W).

The Synthesis of Green Palladium Catalysts Stabilized by Chitosan for Hydrogenation

The proposed paper describes a simple and environmentally friendly method for the synthesis of three-component polymer–inorganic composites, which includes the modification of zinc oxide or montmorillonite (MMT) with chitosan (CS), followed by the immobilization of palladium on the resulting two-component composites. The structures and properties of the obtained composites were characterized by physicochemical methods (IRS, TEM, XPS, SEM, EDX, XRD, BET). Pd–CS species covered the surface of inorganic materials through two different mechanisms. The interaction of chitosan polyelectrolyte with zinc oxide led to the deprotonation of its amino groups and deposition on the surface of ZnO. The immobilization of Pd on CS/ZnO occurred by the hydrolysis of [PdCl4]2−, followed by forming PdO particles by interacting with amino groups of chitosan. In the case of CS/MMT, protonated amino groups of CS interacted with negative sites of MMT, forming a positively charged CS/MMT composite. Furthermore, [PdCl4]2− interacted with the –NH3+ sites of CS/MMT through electrostatic force. According to TEM studies of 1%Pd–CS/ZnO, the presence of Pd nanoclusters composed of smaller Pd nanoparticles of 3–4 nm in size were observed on different sites of CS/ZnO. For 1%Pd–CS/MMT, Pd nanoparticles with sizes of 2 nm were evenly distributed on the support surface. The prepared three-component CS–inorganic composites were tested through the hydrogenation of 2-propen-1-ol and acetylene compounds (phenylacetylene, 2-hexyn-1-ol) under mild conditions (T—40 °C, PH2—1 atm). It was shown that the efficiency of 1%Pd–CS/MMT is higher than that of 1%Pd–CS/ZnO, which can be explained by the formation of smaller Pd particles that are evenly distributed on the support surface. The mechanism of 2-hexyn-1-ol hydrogenation over an optimal 1%Pd–CS/MMT catalyst was proposed.

Rectifying Heterointerface Facilitated C-N Coupling Dynamics Enables Efficient Urea Electrosynthesis Under Ultralow Potentials.

Electrocatalytic C-N coupling for urea synthesis from carbon dioxide (CO2) and nitrate (NO3-) offers a sustainable alternative to the traditional Bosch-Meiser method. However, the complexity of intermediates in co-reduction hampers simultaneous improvement in urea yield and Faradaic efficiency (FE). Herein, we developed a Cu/Cu2O Mott-Schottky catalyst with nanoscale rectifying heterointerfaces through precise controllable in-situ electroreduction of Cu2O nanowires, achieving notable FE (32.6-47.0%) and substantial yields (6.08-30.4 μmol h-1 cm-2) across a broad range of ultralow applied potentials (0 to -0.3 V vs. RHE). Operando synchrotron radiation-Fourier transform infrared spectroscopy (SR-FTIR) confirmed the formation of *CO intermediates and C-N bonds, subsequently density functional theory (DFT) calculations deciphered that the Cu/Cu2O rectifying heterointerface modulated *CO adsorption, significantly enhancing subsequent C-N coupling dynamics between *CO and *NOH intermediates. This work not only provides a groundbreaking and advanced pathway for C-N coupling, but also offers deep insights into copper-based heterointerface catalysts for urea synthesis.

Rectifying Heterointerface Facilitated C‐N Coupling Dynamics Enables Efficient Urea Electrosynthesis Under Ultralow Potentials

Electrocatalytic C‐N coupling for urea synthesis from carbon dioxide (CO2) and nitrate (NO3‐) offers a sustainable alternative to the traditional Bosch‐Meiser method. However, the complexity of intermediates in co‐reduction hampers simultaneous improvement in urea yield and Faradaic efficiency (FE). Herein, we developed a Cu/Cu2O Mott‐Schottky catalyst with nanoscale rectifying heterointerfaces through precise controllable in‐situ electroreduction of Cu2O nanowires, achieving notable FE (32.6‐47.0%) and substantial yields (6.08‐30.4 μmol h‐1 cm‐2) across a broad range of ultralow applied potentials (0 to ‐0.3 V vs. RHE). Operando synchrotron radiation‐Fourier transform infrared spectroscopy (SR‐FTIR) confirmed the formation of *CO intermediates and C‐N bonds, subsequently density functional theory (DFT) calculations deciphered that the Cu/Cu2O rectifying heterointerface modulated *CO adsorption, significantly enhancing subsequent C‐N coupling dynamics between *CO and *NOH intermediates. This work not only provides a groundbreaking and advanced pathway for C‐N coupling, but also offers deep insights into copper‐based heterointerface catalysts for urea synthesis.

1,5-Diaza-3,7-diphosphacyclooctanes (P2N2): An Underappreciated Ligand Class for Nickel- and Palladium-Catalyzed Heck-Type Cross-Couplings

Abstract1,5-Diaza-3,7-diphosphacyclooctane (P2N2) scaffolds represent a readily accessible, tunable ligand class for transition metals. However, despite their prevalence in areas such as electrocatalysis and coordination chemistry, P2N2 ligands have been rarely used to make catalysts for organic synthesis. Research into Mizoroki–Heck-type aldehyde, alcohol, and alkene arylation reactions has revealed that the P2N2 family outperforms many commonly used phosphines. This Synpacts article summarizes our work and provides a broad overview on the preparation and application of P2N2 ligands in organic synthesis. It also serves to highlight how a simple, modular class of ligands can solve contemporary challenges with transition-metal catalysis, including novel reactivity and exceptional regioselectivity.

Halloysite Nanotube Modified (CuO@HNTs-SO3H) Novel Heterogeneous Catalyst for One-Pot Synthesis of Tetrahydrobenzo[ɑ]Xanthen-11-One

In this study, CuO@HNTs-SO3H was investigated as a novel eco-friendly heterogeneous solid acid catalyst prepared by straightforward co-precipitation method. Thus, the cost-effective CuO NPs was used to modify halloysite nanotubes initially, which were subsequently further functionalized with sulfonic acid. The prepared catalyst was analyzed by means of FT-IR, XRD, EDX, SEM and TGA methods. Its catalytic activity is investigated in the solvent-free one-pot condensation of various aromatic aldehydes, dimedone, and β-naphthol to produce tetrahydrobenzo[a]xanthen-11-one derivatives. A few benefits of the discovered method are its simple process, quick reaction time, high yields (96%), affordable cost, and the catalyst ability to be reused without losing its activity.

Fabrication of heterogeneous catalyst for production of biodiesel form municipal sludge

Sewage sludge, a semi-solid byproducts of municipal wastewater treatment processes, offers a sustainable and cost-effective feedstock for biodiesel production through the synthesis of catalytic heterogeneous catalysts. In this study, we developed a novel heterogeneous catalyst by impregnating aluminum nitrate and calcite, obtained from carbon dioxide-sequestering bacteria, onto DigSBiochar (Biochar derived from digested sewage sludge). The produced catalyst was subsequently immobilized with the lipase enzyme isolated from Bacillus sp., creating a bioactive material for the transesterification of lipids in sewage sludge. Comprehensive characterization of the biocatalysts was conducted using Energy Dispersive Spectroscopy (EDS), Fourier Transform Infrared Spectroscopy (FTIR), and Field Emission Scanning Electron Microscopy (FE-SEM). Gas Chromatography-Mass Spectrometry (GC-MS) analysis of the resulting fatty acid methyl esters (FAMEs) demonstrated that the highest yield was achieved with the enzyme immobilized on the activated heterogeneous catalyst using methanol (99 %), followed by the activated heterogeneous catalyst with methanol (96 %), and methanol with Sulfuric acid (82 %). This study underscores the potential of utilizing municipal sewage sludge as a valuable resource for producing efficient heterogeneous catalysts, thereby advancing sustainable waste management practices and promoting renewable energy production.

Direct Synthesis of Dimethyl Carbonate from Methanol and CO2 over ZrO2 Catalysts Combined with a Dehydrating Agent and a Cocatalyst

Zirconia nanocrystals as catalysts for the direct synthesis of dimethyl carbonate (DMC) from methanol and carbon dioxide have received significant interest recently. In this paper, three zirconia-based catalysts presenting different monoclinic and tetragonal phase contents are prepared and characterized by X-ray diffraction (XRD), N2 adsorption–desorption, transmission electron microscopy (TEM), and temperature-programmed desorption of NH3 and CO2 (NH3-TPD and CO2-TPD). The catalytic performances of these solids are evaluated in terms of DMC production. This production is low when using the bare zirconias, but it is significantly increased in the presence of 1,1,1-trimethoxymethane (TMM) playing the role of a dehydrating agent, which shifts the thermodynamic equilibrium. Moreover, the production of DMC is further improved by adding a second solid catalyst (cocatalyst), the molecular sieve 13X, to accelerate the hydration of TMM. Hence, the molecular sieve 13X plays a dual role by trapping water molecules formed by the reaction of DMC synthesis and providing strong acidic sites catalyzing TMM hydrolysis. To the best of our knowledge, the combination of two solid catalysts in the reaction medium to accelerate the water elimination to obtain higher DMC production from CO2 and methanol has never been reported.

Recent advances in the synthesis of highly substituted imidazolidines.

Imidazolidine is a saturated heterocycle with a cyclic aminal core that can be found in natural products and biologically active molecules. Additionally, these heterocyclic compounds have been utilized as chiral ligands, N-heterocyclic carbene precursors, and catalysts in organic synthesis. This review is an attempt to compile the literature of various synthetic procedures of highly substituted imidazolidines, chiral imidazolidines with high diastereoselectivities and enantioselectivities, bis-imidazolidines, and spiro-imidazolidines, as well as their pharmacological properties during the period from 1949 to 2023.

Enhanced hydrothermal stability by a semi-embedded structure: An efficient Ru catalyst for levulinic acid conversion in the aqueous phase

Catalyst stability is believed to be one of the greatest challenges faced for the supported metal catalysts in the catalytic conversion of biomass and its derivatives because many biomass transformations are conducted in the aqueous phase. In this work, we report a simple yet efficient coating-impregnation-pyrolysis (CIP) strategy to fabricate Al2O3 supported Ru catalyst (Ru-Al2O3@CN) with Ru NPs (nanoparticles) semi-embedded into N-doped carbon (CN) layer for the efficient hydrogenation of levulinic acid (LA) to γ-valerolactone in the aqueous phase. Benefit from the special structure of Ru-Al2O3@CN catalyst, it possesses both high catalytic activity and stability, giving a TOF of 28,099 h-1 for LA hydrogenation at 120 °C and 2 MPa H2, which is superior to the most of reported Ru-based catalysts. More importantly, compared with conventional impregnated Ru/Al2O3 catalyst, the Ru-Al2O3@CN catalyst exhibits a remarkably improved hydrothermal stability. Based on series of catalyst characterizations and control experiments, it was found that the presence of CN can weak the interaction between Ru and Al2O3, as well as protect the Al2O3 and Ru NPs from hydrolysis and aggregation, respectively. We anticipate that such a novel strategy may provide some valuable insights into the synthesis of oxides-supported metal catalyst with high hydrothermal stability.

Synthesis of novel zeolite-supported zinc-cobalt bimetallic catalyst by co-precipitation-calcination method for efficient activation of persulfate to degrade tetracycline hydrochloride

Synthesis of novel zeolite-supported zinc-cobalt bimetallic catalyst by co-precipitation-calcination method for efficient activation of persulfate to degrade tetracycline hydrochloride

Transition metal atoms embedded into B/N co-doped graphene as electrocatalysts toward nitrogen reduction reaction: Search for the optimal combination

The catalytic performance of a series of single transition metal (TM = 3d, 4d, and 5d series) atoms anchored on B/N co-doped graphene (BxNy@Gra) toward electrocatalytic nitrogen reduction reaction (eNRR) was systematically investigated by first-principles calculations. Among 180 possible materials, four catalysts (Tc-B1N3@Gra, Os-B2N2α@Gra, Re-B2N2γ@Gra, Nb-B3N1@Gra) feature the highest activity with UL no higher than 0.31 V. Interestingly, a volcano curve between UL and ΔEads(*NNH) can be established, so ΔEads(*NNH) can be applied as a descriptor to unveil the structure-activity relationship and characterize the activity of catalysts. The properties, thermal stability, and selectivity for the four catalysts were analyzed. Os-B2N2α@Gra is identified as a promising catalyst in this work for catalyzing N2 electroreduction to NH3 owing to its potent catalytic activity (UL = −0.28 V), high stability and distinct selectivity. This work can give some meaningful guidance for rapid screening and the rational design of efficient single-atom catalysts for electrocatalytic ammonia synthesis and other related electrochemical reaction. We expect that the present study will inspire and promote the efforts from both experimental and theoretical in this direction.

Synthesis of Novel Planar-Chiral Charge-Compensated nido-Carborane-Based Amino Acid.

Amino acids with unusual types of chirality and their derivatives have recently attracted attention as precursors in the synthesis of chiral catalysts and peptide analogues with unique properties. In this study, we have synthesized a new nido-carborane-based planar-chiral amino acid, in the molecule of which the amino group is directly bonded to the B(3) atom, and the carboxyl group is attached to the B(9) atom through the CH2S+(Me) fragment. 3-Amino-9-dimethylsulfonio-nido-carborane, prepared in three steps from 3-amino-closo-carborane in a high yield, was a key intermediate in the synthesis of the target planar-chiral amino acid. The carboxymethyl group at the sulfur atom was introduced by the demethylation reaction of the dimethylsulfonio derivative, followed by S-alkylation. The structure of new 3,9-disubstituted nido-carboranes was studied for the first time using NMR spectroscopy. The resonances of all boron atoms in the 11B NMR spectrum of 3-amino-9-dimethylsulfonio-nido-carborane were assigned based on the 2D NMR correlation experiments. The nido-carborane-based planar-chiral amino acid and related compounds are of interest as a basis for peptide-like compounds and chiral ligands.

Oxygen reduction reaction on Ag nanocatalysts prepared by the microemulsion method

The microemulsion (water-in-oil) method is used to prepare novel silver catalysts onto three different carbon supports (multi-walled carbon nanotubes (MWCNT), mesoporous carbon (MC) and Vulcan carbon (C)). It allows to control the Ag particle growth and produces particles that range between 2 and 3 nm. The Ag-based catalysts are characterised by scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy (EDS). The electrocatalytic activity towards the oxygen reduction reaction (ORR) in 0.1 M KOH is studied using the rotating disc electrode method. High-angle annular dark-field (HAADF) STEM images reveal the Ag particle size range between 1.8 and 2.4 nm, and the EDS mapping shows uniform Ag distribution on the substrates used. Ag1/MC (two-step synthesis) and Ag2/MC (one-step synthesis) catalysts prepared onto the MC support show the highest mass activity of 30–37 A g−1. The two-step synthesis method is preferred to prepare Ag/MWCNT and Ag/C catalysts. The mass activity of the Ag1/MWCNT catalyst is more than two times higher than that of Ag2/MWCNT. Ag1/MWCNT shows the highest electrochemical stability after the accelerated durability test, with only a 6 mV shift in half-wave potential. The microemulsion method is very promising for the production of highly stable Ag-based catalysts with Ag particles smaller than 3 nm in size.

Exploring Cu(triNHC) as a Bifunctional Catalyst for Carbonate Synthesis From CO2 and Epoxy Amines/Sulfides/Ethers

ABSTRACTThis study highlights the synergistic interplay between a Lewis acidic copper ion and a dissociated ligand from Cu(triNHC) complexes in the synthesis of cyclic carbonates from CO2 and epoxy compounds. The reactions were found to proceed efficiently under Cu(triNHC)‐catalyzed conditions, yielding significant quantities of cyclic carbonates across various epoxy substrates encompassing amine, sulfide, and ether functionalities. Stereochemical analyses underscore a pronounced propensity for retaining the stereochemistry of epoxy compounds in the resultant carbonates. This suggests a mechanism involving double inversion of stereochemistry during the reaction, which comprises catalyst‐mediated epoxide ring opening, subsequent CO2 addition, and carbonate ring closing. These findings align with established mechanisms for CO2 fixation reactions, shedding light on the intricate pathways underlying this catalytic process.

Convergent Active Site Evolution in Platinum Single Atom Catalysts for Acetylene Hydrochlorination and Implications for Toxicity Minimization.

Platinum single atoms anchored onto activated carbon enable highly stable Hg-free synthesis of vinyl chloride (VCM) via acetylene hydrochlorination. Compared to gold-based alternatives, platinum catalysts are in initial phases of development. Most synthetic approaches rely on chloroplatinic acid, presenting opportunities to explore other precursors and their impact on catalyst structure, reactivity, and toxicity aspects. Here, we synthesize platinum single atom catalysts (Pt SACs, 0.2-0.8 wt % Pt) employing diverse Pt2+ and Pt4+ complexes with ammine, hydroxyl, nitrate, and chloride ligands, following a scalable impregnation protocol on activated carbon extrudates. X-ray absorption spectroscopy (XAS) reveals that Pt4+ species reduce to Pt2+ upon deposition onto the support. Despite similar oxidation states, the initial activity is precursor dependent, with tetraammine-derived Pt SACs displaying 2-fold higher VCM yield than chlorinated counterparts, linked to superior hydrogen chloride binding abilities by density functional theory (DFT) simulations. Their activity gradually converges due to dynamic active site restructuring, delivering remarkable precursor-independent stability over 150 h. Operando XAS and DFT studies uncover reaction-induced ligand exchange, generating common active and stable Pt-Cl x (x = 2-3) species. Convergent active site evolution enables flexibility in metal precursor selection and thus toxicity minimization through multiparameter assessment. This study advances safe-by-design catalysts for VCM synthesis, highlighting the importance of toxicity analyses in early-stage catalyst development programs.