Heterogeneous Catalyst Research Articles

Nanoconfined heterogeneous catalysis triggered by copper oxide supported metal–organic framework UiO-66-NH2/peroxymonosulfate for rapidly removing bisphenol A in water

Nanoconfined heterogeneous catalysis triggered by copper oxide supported metal–organic framework UiO-66-NH2/peroxymonosulfate for rapidly removing bisphenol A in water

Stereocatalytic Effect of CeO2 for the Synthesis of trans‐3‐Penten‐2‐ol

AbstractThe transformation of biobased alkanediols over heterogeneous catalysts is a major object. Here, a series of catalysts were prepared for 2,4‐pentanediol dehydration to 3‐penten‐2‐ol. Ceria‐based catalysts had a unique property of showing high efficiency. More importantly, a stereocatalytic effect was observed for CeO2, yielding trans‐3‐penten‐2‐ol with a high selectivity. Raman, XPS, TPD, and TPR were carried out to clarify the catalyst structure, and the relationship between the catalyst structure and catalytic performance were studied. The amount of Lewis acid sites can hardly be correlated with the total concentrations of the oxygen vacancies. It was suggested that the geometry structure of the active sites played a crucial role in trans‐3‐penten‐2‐ol production. The oxygen vacancies originating from CeO2 consisted of active sites with a geometrical structure, which were different from those created by Pr doping CeO2. In addition, the Pr doping enhanced the oxygen migration, which resulted in side reactions, consequently, giving a lower selectivity to trans‐3‐penten‐2‐ol.

Nature‐Inspired N, O Co‐Coordinated Manganese Single‐Atom Catalyst for Efficient Hydrogen Peroxide Electrosynthesis

AbstractThe two‐electron oxygen reduction reaction (2e− ORR) is a pivotal pathway for the distributed production of hydrogen peroxide (H2O2). In nature, enzymes containing manganese (Mn) centers can convert reactive oxygen species into H2O2. However, Mn‐based heterogeneous catalysts for 2e− ORR are scarcely reported. Herein, we developed a nature‐inspired single‐atom electrocatalyst comprising N, O co‐coordinated Mn sites, utilizing carbon dots as the modulation platform (Mn CD/C). As‐synthesized Mn CD/C exhibited exceptional 2e− ORR activity with an onset potential of 0.786 V and a maximum H2O2 selectivity of 95.8 %. Impressively, Mn CD/C continuously produced 0.1 M H2O2 solution at 200 mA/cm2 for 50 h in the flow cell, with negligible loss in activity and H2O2 faradaic efficiency, demonstrating practical application potential. The enhanced activity was attributed to the incorporation of Mn atomic sites into the carbon dots. Theoretical calculations revealed that the N, O co‐coordinated structure, combined with abundant oxygen‐containing functional groups on the carbon dots, optimized the binding strength of intermediate *OOH at the Mn sites to the apex of the catalytic activity volcano. This work illustrates that carbon dots can serve as a versatile platform for modulating the microenvironment of single‐atom catalysts and for the rational design of nature‐inspired catalysts.

Nature-Inspired N, O Co-Coordinated Manganese Single-Atom Catalyst for Efficient Hydrogen Peroxide Electrosynthesis.

The two-electron oxygen reduction reaction (2e- ORR) is a pivotal pathway for the distributed production of hydrogen peroxide (H2O2). In nature, enzymes containing manganese (Mn) centers can convert reactive oxygen species into H2O2. However, Mn-based heterogeneous catalysts for 2e- ORR are scarcely reported. Herein, we developed a nature-inspired single-atom electrocatalyst comprising N, O co-coordinated Mn sites, utilizing carbon dots as the modulation platform (Mn CD/C). As-synthesized Mn CD/C exhibited exceptional 2e- ORR activity with an onset potential of 0.786 V and a maximum H2O2 selectivity of 95.8 %. Impressively, Mn CD/C continuously produced 0.1 M H2O2 solution at 200 mA/cm2 for 50 h in the flow cell, with negligible loss in activity and H2O2 faradaic efficiency, demonstrating practical application potential. The enhanced activity was attributed to the incorporation of Mn atomic sites into the carbon dots. Theoretical calculations revealed that the N, O co-coordinated structure, combined with abundant oxygen-containing functional groups on the carbon dots, optimized the binding strength of intermediate *OOH at the Mn sites to the apex of the catalytic activity volcano. This work illustrates that carbon dots can serve as a versatile platform for modulating the microenvironment of single-atom catalysts and for the rational design of nature-inspired catalysts.

Tailoring of Novel Ru (III) and Cr (III) Salen Complexes as Catalysts for a Sustainable and Green Synthesis of Dihydro‐tetrazolo [1,5‐a] thiazolo [4,5‐d] pyrimidin‐6‐yl morpholine: Experimental and Theoretical Approaches

ABSTRACTTwo novel Cr (III) and Ru (III) salen complexes based on {3,4‐Bis‐[(5‐chloro‐2‐hydroxy‐benzylidene)‐amino]‐phenyl}‐phenyl‐methanone ligand (CSAB) were synthesized. The complexes were characterized using various spectral and analytical methods. The catalytic performance of the CSAB complexes was investigated via a four‐component condensation reaction involving aromatic aldehydes, rhodamine, morpholine, and 5‐aminotetrazole under mild, environmentally friendly conditions. Different Lewis acids, bases, ionic liquid catalysts, solvents, and catalyst amounts were assessed to optimize the reaction parameters. Both catalyst systems demonstrated robust catalytic activity under strictly managed conditions, with the heterogeneous catalyst CSAB‐Ru showing superior efficacy compared to the homogeneous CSAB‐Cr catalyst. The study confirmed the catalytic capabilities of both complexes and evaluated their recyclability and reusability. The heterogeneous catalyst (CSAB‐Ru) could be reused seven times, whereas the homogeneous catalyst (CSAB‐Cr) could be recycled four times. Both complexes demonstrated strong catalytic activity and selectivity, resulting in high product yields. The study provides insights into the synthetic applications of novel CSAB complexes, highlighting their potential in organic transformations. It emphasizes their ease of use, safety, stability, component availability, quick reaction times, and high yields, making them promising for future industrial applications.

Cu-Supported ZnO under Conditions of CO2 Reduction to Methanol: Why 0.2 ML Coverage?

By hydrogenating carbon dioxide to value-added products such as methanol, heterogeneous catalysts can lower greenhouse gas emissions and generate alternative liquid fuels. The most common commercial catalyst for the reduction of CO2 to methanol is Cu/ZnO/Al2O3, where ZnO improves conversion and selectivity toward methanol. The structure of this catalyst is thought to be Zn oxy(hydroxyl) overlayers on the nanometer scale on Cu. In the presence of CO2 and H2 under reaction conditions, the Cu substrate itself can be restructured and/or partially oxidized at its interface with ZnO, or the Zn might be reduced, possibly completely to a CuZn alloy, making the exact structure and stoichiometry of the active site a topic of active debate. In this study, we examine Zn3 clusters on Cu(100) and Cu(111), as a subnano model of the catalyst. We use a grand canonical genetic algorithm to sample the system structure and stoichiometry under catalytic conditions: T of 550 K, initial partial pressures of H2 of 4.5 atm and CO2 of 0.5 atm, and 1% conversion. We uncover a strong dependence of the catalyst stoichiometry on the surface coverage. At the optimal 0.2 ML surface coverage, chains of Zn(OH) form on both Cu surfaces. On Cu(100), the catalyst has many thermally accessible metastable minima, whereas on Cu(111), it does not. No oxidation or reconstruction of the Cu is found. However, at a lower coverage of Zn, Zn3 clusters take on a metallic form on Cu(100), and slightly oxidized Zn3O on Cu(111), while the surface uptakes H to form a variety of low hydrides of Cu. We thus hypothesize that the 0.2 ML Zn coverage is optimal, as found experimentally, because of the stronger yet incomplete oxidation afforded by Zn at this coverage.

Valorization of marble sludge waste in biodiesel production using a central composite design.

This work addresses the scarcity of energy resources and environmental issues by concentrating on the synthesis of biodiesel by the transesterification of waste cooking oil with methanol. Marble sludge (MS), a novel heterogeneous catalyst, was used to speed up the rate of reaction. The catalyst's physical and chemical characteristics were thoroughly examined using a variety of methods, including X-ray diffraction, X-ray Fluorescence, SEM, particle size distribution, and BET analysis. Using the MS catalyst, the study investigated the impact of important parameters on the yield of biodiesel from waste cooking oil with the aid of response surface methodology using Design-Expert version 13 software. These parameters included temperature (50-70℃), reaction time (1-4h), catalyst concentration (1-5 wt%), and methanol-to-oil molar ratio (5-20mol/mol). Optimization of the parameters was performed for economic targets to lower the production cost of biodiesel. The results showed that a methanol-to-oil molar ratio of 20:1, a catalyst of 5 wt%, and a reaction time of 1h at 57℃ were the ideal parameters for obtaining a biodiesel yield of 93.5%. The resultant biodiesel revealed promising characteristics, such as a flash point of 160℃, a kinematic viscosity of 4 mm2/s, and a density of 0.871g/cm3. The study demonstrates the significant consequences and real-world advantages of using rational engineering methods to use MS as a very effective, stable, and easily recoverable catalyst for the long-term, sustainable generation of biodiesel from waste cooking oil.

Aeration‐Free Photo‐Fenton‐Like Reaction Mediated by Heterojunction Photocatalyst toward Efficient Degradation of Organic Pollutants

The regulation of peroxymonosulfate (PMS) activation by photo‐assisted heterogeneous catalysis is under in‐depth investigation with potential as a replaceable advanced oxidation process in water purification, yet it remains a significant challenge. Herein, we demonstrate a strategy to construct polyethylene glycol (PEG) well‐coupled dual‐defect VO‐M‐Co3O4@CNx S‐scheme heterojunction to degrade organic pollutants without aeration, which dramatically provides abundant active sites, excellent photo‐thermal property, and distinct charge transport pathway for PMS activation. The degradation rate of VO‐M‐Co3O4@CNx in anaerobic conditions shows a higher efficient rate (4.58 min‐1 g‐2) than in aerobic conditions (1.67 min‐1 g‐2). Experimental evidence reveals that VO‐M‐Co3O4@CNx promotes more rapid redox conversion of photoexcited electrons induced by defects with PMS under anaerobic conditions compared to aerobic conditions. Additionally, in situ experiments and DFT provide mechanistic insights into the regulation pathway of PMS activation via synergistic defect‐induced electron, revealing the competitive effect between O2 and PMS over VO‐M‐Co3O4@CNx during the reaction process. The continuous flow reactor and flow cytometry results demonstrated that the VO‐M‐Co3O4@CNx/PMS/Vis system has remarkably enhanced stability and purification capability for removing organic pollutants. This work provides valuable insights into regulating the heterologous catalysis oxidation process without aeration through the photoexcitation synergistic PMS activation.

Fundamentals and Challenges of Ligand Modification in Heterogeneous Electrocatalysis

AbstractThe development of efficient catalytic materials in the energy field could promote the structural transformation from traditional fossil fuels to sustainable energy. In heterogeneous catalytic reactions, ligand modification is an effective way to regulate both electronic and steric structures of catalytic sites, thus paving a prospective avenue to design the interfacial structures of heterogeneous catalysts for energy conversion. Although great achievements have been obtained for the study and applications of heterogeneous ligand‐modified catalysts, the systematical refinements of ligand modification strategies are still lacking. Here, we reviewed the ligand modification strategy from both the mechanistic and applicable scenarios by focusing on heterogeneous electrocatalysis. We elucidated the ligand‐modified catalysts in detail from the perspectives of basic concepts, preparation, regulation of physicochemical properties of catalytic sites, and applications in different electrocatalysis. Notably, we bridged the electrocatalytic performance with the electronic/steric effects induced by ligand modification to gain intrinsic structure‐performance relations. We also discussed the challenges and future perspectives of ligand modification strategies in heterogeneous catalysis.

Aeration-Free Photo-Fenton-Like Reaction Mediated by Heterojunction Photocatalyst toward Efficient Degradation of Organic Pollutants.

The regulation of peroxymonosulfate (PMS) activation by photo-assisted heterogeneous catalysis is under in-depth investigation with potential as a replaceable advanced oxidation process in water purification, yet it remains a significant challenge. Herein, we demonstrate a strategy to construct polyethylene glycol (PEG) well-coupled dual-defect VO-M-Co3O4@CNx S-scheme heterojunction to degrade organic pollutants without aeration, which dramatically provides abundant active sites, excellent photo-thermal property, and distinct charge transport pathway for PMS activation. The degradation rate of VO-M-Co3O4@CNx in anaerobic conditions shows a higher efficient rate (4.58 min-1 g-2) than in aerobic conditions (1.67 min-1 g-2). Experimental evidence reveals that VO-M-Co3O4@CNx promotes more rapid redox conversion of photoexcited electrons induced by defects with PMS under anaerobic conditions compared to aerobic conditions. Additionally, in situ experiments and DFT provide mechanistic insights into the regulation pathway of PMS activation via synergistic defect-induced electron, revealing the competitive effect between O2 and PMS over VO-M-Co3O4@CNx during the reaction process. The continuous flow reactor and flow cytometry results demonstrated that the VO-M-Co3O4@CNx/PMS/Vis system has remarkably enhanced stability and purification capability for removing organic pollutants. This work provides valuable insights into regulating the heterologous catalysis oxidation process without aeration through the photoexcitation synergistic PMS activation.

Solvent Free Ambient Pressure CO2 Cycloaddition Catalyzed by Cobalt-Impregnated 2D-Nanofibrous COFs.

Covalent organic frameworks (COFs) constitute an evolving class of permanently porous and ordered materials, and they have recently attracted increased interest due to their intriguing morphological features and numerous applications in gas storage, adsorption, and catalysis. However, their low aqueous stabilities and tedious syntheses generally hamper their use in heterogeneous catalysis. Nonetheless, a capable and water-stable heterogeneous catalytic system for coupling CO2/epoxides to generate industrially important cyclic carbonates is still of great interest. Herein, exceedingly water- and thermally stable 2D-cobalt-impregnated hydrazone-linked fibrous COFs are reported as a catalyst for CO2/epoxide coupling reactions at ambient pressure. The functionalized cobalt (Co)-doped COFs demonstrated excellent catalytic activities with the high TONs (80925) and TOFs (6466 h-1), outperforming reported heterogeneous catalysts for CO2/epoxide coupling at ambient pressure. We found that the Co2+ ions within the COF matrix catalyze CO2 cycloaddition through density functional theory calculations. We also confirmed the excellent structural stability and consistent activity of Co-doped COFs up to ten repeating cycles.

Nickel and Molybdenum-Containing Perovskites as Efficient Heterogeneous Catalysts for the Conversion of Biobased Furfural to a Fuel Additive Intermediate

AbstractIn this work, the catalytic conversion of furfural was found to follow both CTHs and etherification pathways in one-pot over multicationic inorganic perovskites (LaNi1-xMoxO3±δ) as heterogeneous catalysts. The conversion of furfural (FA) into alcohols and ether functionalities using the as-synthesized perovskite catalysts showed good conversions that are above 80% and excellent selectivity towards the desired product. The LaMoO3 catalyst was found to achieve the highest percentage conversion of 83%. Simple and multicationic inorganic perovskites were successfully employed in the transformation of furfural to produce β-methoxy-2-furanethanol. Furthermore, we postulate the hydrogenation of the keto-group to be the first step in the mechanism of the formation of β-methoxy-2-furanethanol and that its formation is characterized by rearrangement of the intermediate over the surface of the catalyst. Graphical abstract

Aromatics Alkylated with Olefins Utilizing Zeolites as Heterogeneous Catalysts: A Review

The alkylation reaction of aromatic compounds gains considerable attention because of its wide application in bulk and fine chemical production. Aromatics alkylated with olefins is a well-known process, particularly for linear alkylbenzene, phenyloctanes, and heptyltoluene production. As octane boosters and precursors for various petrochemical and bulk chemical products, a wide range of alkylated compounds are in high demand. Numerous unique structures have been proposed in addition to the usual zeolites (Y and beta) utilized in alkylation procedures. The inevitable deactivation of industrial catalysts over time on stream, which is followed by a decrease in catalytic activity and product selectivity, is one of their disadvantages. Therefore, careful consideration of catalyst deactivation regarding the setup and functioning of the process of catalysis is necessary. Although a lot of work has been carried out to date to prevent coke and increase catalyst lifespan, deactivation of the catalyst is still unavoidable. Coke deposition can lead to catalyst deactivation in industrial catalytic processes by obstructing pores and/or covering acid sites. It is very desirable to regenerate inactive catalysts in order to remove the coke and restore catalytic activity at the same time. Depending on the kind of catalyst, the deactivation processes, and the regeneration settings, each regeneration approach has pros and cons. In this comprehensive study, the focus was on discussing the reaction mechanism of 1-octene isomerization and toluene alkylation as an example of isomerization and alkylation reactions that occur simultaneously, shedding light in detail on the catalysts used for this type of complex reaction, taking into account the challenges facing the catalyst deactivation and reactivation procedures.

Heterogeneous Asymmetric Hydrogenation of C═C and C═O Double Bonds

AbstractNowadays, heterogeneous catalysts play a crucial role in the field of asymmetric catalysis to produce enantiopure compounds for various applications. The unique properties of heterogeneous systems, such as high stability, reusability, or ease of separation, allow effective catalysis of asymmetric transformations and their further implementation in industrial processes. In this mini‐review, we address the recent trend in the synthesis of chiral heterogeneous catalysts and their subsequent application in asymmetric hydrogenation reactions. We focus on current advances in asymmetric hydrogenation reactions of C═C and C═O bonds due to their high relevance in the fine chemicals industry. Our main aim is to provide a short overview of this expanding field, its current challenges, and future perspectives.

Tailoring rhodium-based metal-organic layers for parahydrogen-induced polarization: achieving 20% polarization of 1H in liquid phase

Abstract Heterogeneous catalysts for parahydrogen-induced polarization (HET-PHIP) would be useful for producing high sensitivity contrasting agents for magnetic resonance imaging (MRI) in liquid phase, as they can be removed by simple filtration. Although homogeneous hydrogenation catalysts are highly efficient for PHIP, their sensitivity decreases when anchored on porous supports due to slow substrate diffusion to the active sites and rapid depolarization within the channels. To address this challenge, we explored two-dimensional (2D) metal-organic layers (MOLs) as supports for active Rh complexes with diverse phosphine ligands and tunable hydrogenation activities, taking advantage of accessible active sites and chemical adaptability of the MOLs. By adjusting the electronic properties of phosphines, TPP-MOL-Rh-dppb (TPP = tris(4-carboxylphenyl)phosphine), featuring a κ2-connected di(phosphine) ligand, generated hyperpolarized styrene achieving over 2400-fold signal enhancement and polarization level of 20% for 1H in methanol-d4 solution. The TPP-MOL-Rh-dppb effectively inherited the high efficiency and pairwise addition of its homogenous catalyst while maintaining the heterogeneity of MOL. This work demonstrates the potential of 2D phosphine-functionalized MOLs as heterogenous solid support for HET-PHIP.

Porous Molecular Crystals Derived from Cofacial Porphyrin/Phthalocyanine Heterodimers.

Porphyrin‐based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co‐crystallisation of tetraphenylporphyrin (TPP) with octa(2’,6’‐di‐isopropylphenoxy) phthalocyanine or some of its metal complexes [(dipPhO)8PcM; M = H2, Al‐OH, Ti=O, Mn‐Cl, Fe‐Cl, Co, Ni, Cu, Zn, Ga‐Cl, Ag, In‐Cl or Au‐Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)8PcM, which is driven by the complementary shape and symmetry of the two macrocycles. The (dipPhO)8PcM component directs the crystal structure of the heterodimers to form Phthalocyanine Nanoporous Crystals (PNCs) of similar structure to those formed by (dipPhO)8PcM alone. The incorporation of TPP appears to partially stabilise the PNCs towards the removal of included solvent and for cocrystals containing (dipPhO)8PcCo stability can be enhanced further by the in‐situ addition of 4,4‐bipyridyl to act as a “molecular wall tie”. These stabilised PNC/TPP cocrystals have a Brunauer‐Emmett‐Teller surface area (SABET) of 454 m2 g‐1 and a micropore volume (Vmp) of 0.22 ml g‐1. The reactivity of both macrocycles within the PNC/TPP co‐crystals are demonstrated by in‐situ metal insertion.

Porous Molecular Crystals Derived from Cofacial Porphyrin/Phthalocyanine Heterodimers.

Porphyrin-based porous materials are of growing interest as heterogeneous catalysts especially for reactions that are of importance to sustainability. Here we demonstrate that porous molecular crystals can be prepared by the simple co-crystallisation of tetraphenylporphyrin (TPP) with octa(2',6'-di-isopropylphenoxy) phthalocyanine or some of its metal complexes [(dipPhO)8PcM; M = H2, Al-OH, Ti=O, Mn-Cl, Fe-Cl, Co, Ni, Cu, Zn, Ga-Cl, Ag, In-Cl or Au-Cl]. This process is facilitated by the efficient formation of the supramolecular heterodimer between TPP and (dipPhO)8PcM, which is driven by the complementary shape and symmetry of the two macrocycles. The (dipPhO)8PcM component directs the crystal structure of the heterodimers to form Phthalocyanine Nanoporous Crystals (PNCs) of similar structure to those formed by (dipPhO)8PcM alone. The incorporation of TPP appears to partially stabilise the PNCs towards the removal of included solvent and for cocrystals containing (dipPhO)8PcCo stability can be enhanced further by the in-situ addition of 4,4-bipyridyl to act as a "molecular wall tie". These stabilised PNC/TPP cocrystals have a Brunauer-Emmett-Teller surface area (SABET) of 454 m2 g-1 and a micropore volume (Vmp) of 0.22 ml g-1. The reactivity of both macrocycles within the PNC/TPP co-crystals are demonstrated by in-situ metal insertion.

Heterogeneous Catalysts for Petrochemical Synthesis and Oil Refining, 2nd Edition

Heterogeneous catalysts play a crucial role in the petrochemical synthesis and oil refining industries [...]

Methyl ester production process from palm fatty acid distillate using hydrodynamic cavitation reactors in series with solid acid catalyst.

This study aims to optimize the reduction of free fatty acids (FFAs) in palm fatty acid distillate (PFAD) using hydrodynamic cavitation reactors (HCRs) in series and a solid acid catalyst for biodiesel production. Hydrodynamic cavitation is used to accelerate the esterification of FFAs using a heterogeneous acid catalyst. There are three HCRs units, and each HCR composed of a 3D-printed rotor and stator, is separated by flanges and equipped with a basket for holding Amberlyst-15 catalyst. Through response surface methodology (RSM), the esterification process is optimized by adjusting its optimal parameters, namely, methanol (2-12 wt%), circulation time (30-170min), and rotor speed (1000-3000rpm). The optimal conditions for achieving a maximum methyl ester purity of 89.76 wt% in converting FFA in first-step esterified oil are 9 wt% methanol (molar ratio of methanol to oil of 4:1), 133min of circulation time, and 2000rpm of rotor speed. An 82.48 wt% biodiesel yield is achieved from the HCRs in series under the optimal conditions. Scanning electron microscope images reveal that after the esterification process, there are minor cracks and defects on the catalyst's resin surface, indicating the presence of residual reactants. Further examination of the catalyst after the esterification process, reveals an average absorption pore diameter of 341.41 Å and BET surface area of approximately 41.68 m2/g. Although there were slight physical changes in the catalyst, HCRs technology offers a viable FFA reduction process that could enhance biodiesel production efficiency. Moreover, the optimized conditions achieved in this study contribute to the advancement of biodiesel production processes and provide insights into the performance of the catalyst used.

New Models of Heterogeneous Catalysis for Numerical Study of Flows and Heat Transfer in an Induction HF Plasmatron

New Models of Heterogeneous Catalysis for Numerical Study of Flows and Heat Transfer in an Induction HF Plasmatron