Catalytic Advantage Research Articles

Polyoxometalates@Metal-Organic Frameworks: Synthesis Strategies, Nanostructure Modulation and Application in Biomass Conversion.

Polyoxometalates@metal-organic frameworks (POMs@MOFs) have attracted much attention as multifunctional materials in biomass catalysis. Individual POMs and MOFs are hindered by their respective defects, such as poor stability and single catalytic active site, which make it difficult to realize large-scale applications. However, the combination of POMs and MOFs can be used to maximize the catalytic advantages of each. MOFs with high specific surface area and rich pore structure can effectively stabilize and uniformly disperse POMs, while the introduction of POMs also provides more catalytic possibilities for POMs@MOFs. Therefore, POMs@MOFs with ultra-high porosity, large specific surface area and excellent acid catalytic activity have unique catalytic advantages in the field of biomass catalytic conversion. In this work, we provide an overview of the current development of POMs@MOFs in the field of biomass catalysis. The synthesis strategies of POMs@MOFs are summarized and discussed, highlighting the in-situ synthesis methods. We focus on the nanostructure engineering of POMs@MOFs, and explore the "structure-property" relationship in depth. In addition, the representative work of POMs@MOFs in the catalysis of biomass derivatives is summarized. Filially, the prospects, and challenges for the future development of POMs@MOFs in the field of biomass catalysis are also presented.

Catalytic Advantages of SO3H-Modified UiO-66(Zr) Materials Obtained via Microwave Synthesis in Friedel-Crafts Acylation Reaction.

The catalytic activity and stability of sulfonic-based UiO-66(Zr) materials were tested in the Friedel-Crafts acylation of anisole with acetic anhydride. The materials were prepared using microwave-assisted synthesis, producing microporous materials with remarkable crystallinity and physicochemical features as acid catalysts. Different ratios between both organic ligands, terephthalic acid (H2BDC) and monosodium 2-sulfoterephthalic acid (H2BDC-SO3Na), were used for the synthesis to modulate the sulfonic content. The sulfonic-based UiO-66(Zr) material synthesized with a H2BDC/H2BDC-SO3Na molar ratio of 40/60 exhibited the best catalytic performance in the acidic-catalyzed Friedel-Crafts acylation reaction. This ratio balanced the number of sulfonic acid sites and their accessibility within the UiO-66 microporous structure. The catalytic performance of this material increased remarkably at 200 °C, outperforming reference acids and commercial heterogeneous catalysts such as Nafion-SAC-13 and Amberlyst-70. Additionally, the best sulfonic-based UiO-66(Zr) material proved to be stable in four successive reaction cycles, maintaining both its catalytic activity and its structural integrity.

A Chemically Robust 2D Ni-MOF as an Efficient Heterogeneous Catalyst for One-Pot Synthesis of Therapeutic and Bioactive 2-Amino-3-Cyano-4H-Pyran Derivatives.

Despite possessing numerous catalytic advantages of MOFs, developing 2D frameworks having excellent chemical stability along with new catalytic properties, remains a grand challenge. Herein, by employing a mixed ligand synthetic approach, we have constructed a 2D Ni-MOF, IITKGP-52, which exhibits excellent framework robustness in open air, water, as well as over a wide range of pH solutions (2-12). Benefitting from its robustness and abundant Lewis acidic open metal sites, IITKGP-52 is explored in catalyzing the heterogeneous three-component condensation reaction for the tandem synthesis of bioactive 2-amino-3-cyano-4H-pyran derivatives with low catalytic loading, greater compatibility for a wide range of substrates, excellent recyclability and superior catalytic efficiency than the previously employed homo and heterogeneous systems. IITKGP-52inaugurates the employment of MOF-based catalysts for one-pot synthesis of therapeutic and bioactive 2-amino-3-cyano-4H-pyran derivatives.

Modulation of Electronic Availability in g-C3N4 Using Nickel (II), Manganese (II), and Copper (II) to Enhance the Disinfection and Photocatalytic Properties.

Carbon nitrides can form coordination compounds or metallic oxides in the presence of transition metals, depending on the reaction conditions. By adjusting the pH to basic levels for mild synthesis with metals, composites like g-C3N4-M(OH)x (where M represents metals) were obtained for nickel (II) and manganese (II), while copper (II) yielded coordination compounds such as Cu-g-C3N4. These materials underwent spectroscopic and electrochemical characterization, revealing their photocatalytic potential to generate superoxide anion radicals-a feature consistent across all metals. Notably, the copper coordination compound also produced significant hydroxyl radicals. Leveraging this catalytic advantage, with band gap energy in the visible region, all compounds were activated to disinfect E. coli bacteria, achieving total disinfection with Cu-g-C3N4. The textural properties influence the catalytic performance, with copper's stabilization as a coordination compound enabling more efficient activity compared to the other metals. Additionally, the determination of radicals generated under light in the presence of dicloxacillin supported the proposed mechanism and highlighted the potential for degrading organic molecules with this new material, alongside its disinfectant properties.

Eggshell membrane-derived electrocatalysts for water electrolysis

Green H2 (GH2) holds significant promise as a renewable energy resource, particularly in addressing the escalating energy demands sustainably. The imperative for economically viable GH2 technologies, primarily via water electrolysis, has spurred extensive research into suitable electrocatalytic materials. Eggshell membrane (ESM) is typically considered a biowaste material obtained from eggs, which are among the most widely consumed foods both domestically and industrially. Many countries legally require the effective treatment of ESM before disposal to prevent environmental contamination. Therefore, we propose upcycling ESM as an electrocatalytic support, forming transition metal-based active sites through chemical and thermal treatment, followed by doping highly reactive Fe sites electrochemically. ESM’s nanofibrous morphology and porous structure confer catalytic advantages. X-ray photoelectron spectroscopy analysis reveals that certain chemical functional groups in the ESM are involved in the spontaneous electrochemical charge transfer and the adsorption of metal ions, contributing to the formation of metal nanoparticles. Furthermore, various anionic chemical elements such as P, O, N, and S, which originate from intrinsic ESM, can participate in electrocatalysis. The Fe sites electrochemically induced on the Ni and Co nanoparticle surfaces in the ESMs demonstrate excellent electrocatalytic activity and durability toward the oxygen and hydrogen evolution reactions, respectively. This study provides a strategy to utilize ESM as an electrocatalytic material for the development of commercially viable electrocatalysts to produce GH2 by transforming biowaste into value-added materials. Moreover, it promotes the investigation of the (electro)chemical functionalities of biomaterials and the correlation between their functions and electrocatalytic activities.

Catalytic Advantage in Otto-like Two-Stroke Quantum Engines.

We demonstrate how to incorporate a catalyst to enhance the performance of a heat engine. Specifically, we analyze efficiency in one of the simplest engine models, which operates in only two strokes and comprises of a pair of two-level systems, potentially assisted by a d-dimensional catalyst. When no catalysis is present, the efficiency of the machine is given by the Otto efficiency. Introducing the catalyst allows for constructing a protocol which overcomes this bound, while new efficiency can be expressed in a simple form as a generalization of Otto's formula: 1-(1/d)(ω_{c}/ω_{h}). The catalyst also provides a bigger operational range of parameters in which the machine works as an engine. Although an increase in engine efficiency is mostly accompanied by a decrease in work production (approaching zero as the system approaches Carnot efficiency), it can lead to a more favorable trade-off between work and efficiency. The provided example introduces new possibilities for enhancing performance of thermal machines through finite-dimensional ancillary systems.

Hollow Nanoreactors for Controlled Photocatalytic Behaviors: Fundamental Theory, Structure–Performance Relationship, and Catalytic Advantages (Small 12/2024)

Hollow Nanoreactors for Controlled Photocatalytic Behaviors: Fundamental Theory, Structure–Performance Relationship, and Catalytic Advantages (Small 12/2024)

Catalysis in action via elementary thermal operations

We investigate catalysis in the framework of elementary thermal operations (ETOs), leveraging the distinct features of such operations to illuminate catalytic dynamics. As groundwork, we establish new technical tools that enhance the computability of state transition rules for ETOs. Specifically, we provide a complete characterisation of state transitions for a qutrit system and special classes of initial states of arbitrary dimension. By employing these tools in conjunction with numerical methods, we find that by adopting a small catalyst, including just a qubit catalyst, one can significantly enlarge the set of state transitions for a qutrit system. This advancement notably narrows the gap of reachable states between ETOs and generic thermal operations. Furthermore, we decompose catalytic transitions into time-resolved evolution, which critically enables the tracking of nonequilibrium free energy exchanges between the system and bath. Our results provide evidence for the existence of simple and practicable catalytic advantage in thermodynamics while offering insight into analysing the mechanism of catalytic processes.

Enhanced catalytic activity and stability of lactate dehydrogenase for cascade catalysis of D-PLA by rational design

Serving as a vital medical intermediate and an environmentally-friendly preservative, D-PLA exhibits substantial potential across various industries. In this report, the urgent need for efficient production motivated us to achieve the rational design of lactate dehydrogenase and enhance catalytic efficiency. Surprisingly, the enzymatic properties revealed that a mutant enzyme, LrLDHT247I/D249A/F306W/A214Y (LrLDH-M1), had a viable catalytic advantage. It demonstrated a 3.3-fold increase in specific enzyme activity and approximately a 2.08-fold improvement of Kcat. Correspondingly, molecular docking analysis provided a supporting explanation for the lower Km and higher Kcat/Km of the mutant enzyme. Thermostability analysis exhibited increased half-lives and the deactivation rate constants decreased at different temperatures (1.47–2.26-fold). In addition, the mutant showed excellent resistance abilities in harsh environments, particularly under acidic conditions. Then, a two-bacterium (E. coli/pET28a-lrldh-M1 and E. coli/pET28a-ladd) coupled catalytic system was developed and realized a significant conversion rate (77.7%) of D-phenyllactic acid, using 10 g/L L-phenylalanine as the substrate in a two-step cascade reaction.

Reinvigorating aza-Michael reactions under ionic liquid catalysis: a greener approach.

Cholinium α-amino carboxylates, which debuted in the ionic liquid arena over a decade ago, exhibit superior stability and suitable physical properties relative to other RTILs. Although synthetic pursuits in such media, leveraging their dual role as solvents and catalysts, have been scarce so far, we herein illustrate their catalytic advantage in aza-Michael reactions in terms of low loading, acceleration and improved yields with respect to conventional conditions and other imidazolium-based ILs. These highly structured salts most likely act through multiple and cooperative non-covalent interactions. These mechanistic features have also been investigated through high-level computational analyses as well.

Catalytic reforming of polypropylene to produce hydrogen: Influence of support characteristics and active metal type in catalyst

Hydrogen production by catalytic pyrolysis of waste plastics has attracted extensive attention in recent years. This paper takes hydrogen production as the starting point. A variety of supported nickel catalysts were developed for the catalytic pyrolysis of polypropylene using a two-stage fixed bed reactor. Based on the better characteristics of bimetallic catalysts, calcium, magnesium, iron doped nickel bimetallic catalysts were prepared to explore the improvement effect of catalytic hydrogen production performance. The micromorphology, structure composition and active substance distribution of different supported catalysts and bimetallic catalysts were measured. The experimental results show that the catalyst with powdered activated carbon as the support has the best catalytic performance of hydrogen production. In a series of molecular sieve catalysts, the smaller the Si/Al ratio of the support, the higher the catalytic performance. Among the bimetallic catalysts, Fe-Ni bimetallic catalysts have better catalytic advantages than Ca-Ni and Mg-Ni bimetallic catalysts, which is closely related to the stable Fe-Ni alloy structure formed on the catalyst surface. In conclusion, the differences in catalytic performance between catalyst support and active metal discussed in this paper will provide theoretical support for the catalytic pyrolysis technology of plastics to produce hydrogen.

Copper(I) Complexes of Amide Functionalized Bisphosphine: Proximity Enhanced Metal-Ligand Cooperativity and Its Catalytic Advantage in C(sp3)-H Bond Activation of Unactivated Cycloalkanes in Dehydrogenative Carboxylation Reactions.

The reactions of amide functionalized bisphosphine, o-Ph2PC6H4C-(O)N(H)C6H4PPh2-o (1) (BalaHariPhos), with copper salts is described. Treatment of 1 with CuX in a 1:1 molar ratio yielded chelate complexes of the type [CuX{(o-Ph2PC6H4C(O)N(H)C6H4PPh2-o)}-κ2-P,P] (X = Cl, 2; Br, 3; and I, 4), which on subsequent treatment with KOtBu resulted in a dimeric complex [Cu(o-Ph2PC6H4C(O)(N)C6H4PPh2-o)]2 (5). Interestingly, complexes 2-4 showed weak N-H···Cu interactions. These weak H-bonding interactions are studied in detail both experimentally and computationally. Also, CuI complexes 2-5 were employed in the oxidative dehydrogenative carboxylation (ODC) of unactivated cycloalkanes in the presence of carboxylic acids to form the corresponding allylic esters. Among complexes 2-5, halide-free dimeric CuI complex 5 showed excellent metal-ligand cooperativity in the oxidative dehydrogenative carboxylation (ODC) in the presence of carboxylic acids to form the corresponding allylic esters through C(sp3)-H bond activation of unactivated cycloalkanes. Mechanistic details of the catalytic process were established by isolating the precatalyst [Cu{(o-Ph2PC6H4C(O)(NH)C6H4PPh2-o)-κ2-P,P}(OOCPh)] (6) and fully characterized by mass spectrometry, NMR data, and single-crystal X-ray analysis. Density functional theory-based calculations further provided a quantitative understanding of the energetics of a series of H atom transfer steps occurring in the catalytic cycle.

Hollow Nanoreactors for Controlled Photocatalytic Behaviors: Fundamental Theory, Structure-Performance Relationship, and Catalytic Advantages.

Hollow nanoreactors (HoNRs) have regarded as an attractive catalytic material for photocatalysis due to their exceptional capabilities in enhancing light harvesting, facilitating charge separation and transfer, and optimizing surface reactions. Developing novel HoNRs offers new options to realize controllable catalytic behavior. However, the catalytic mechanism of photocatalysis occurring in HoNRs has not yet been fully revealed. Against this backdrop, this review elaborates on three aspects: 1) the fundamental theoretical insights of HoNRs-driven photocatalytic kinetics; 2) structure-performance relationship of HoNRs to photocatalysis; 3) catalytic advantages of HoNRs in photocatalytic applications. Specifically, the review focuses on the fundamental theories of HoNRs for photocatalysis and their structural advantages for strengthening light scattering, promoting charge separation and transfer, and facilitating surface reaction kinetics, and the relationship between key structural parameters of HoNRs and their photocatalytic performance is in-depth discussed. Also, future prospects and challenges are proposed. It is anticipated that this review paper will pave the way for forthcoming investigations in the realm of HoNRs for photocatalysis.

Phospholipid-derived Au and Au–Cu suspensions as efficient peroxide and borohydride activators for organic molecules degradation: Performance and sustainable catalytic mechanism

In the contemporary context, executing light-oxidant- and reductant-driven reactions in solution-phase processes remains challenging mainly due to the lack of general tools for understanding the reactive potential of nano-functional catalysts. In this study, dual-active nanometals (Au and Cu doped with Au) capped within soy lecithin (SL), were developed and characterized, combining flexibility with the catalytic advantages and stability of liquid-phase catalysts. The as-synthesized SL-Au (LG) and SL-Au-Cu (LGC) catalysts were efficiently degraded rhodamine B (RB, 100%) in the presence of H2O2 under light irradiation (350 W lamp) at wide pH range (3–7) within 4.5 h and p-nitrophenol (p-NP, >90% degradation at pH 7) in the presence of NaBH4 under normal stirring with slower kinetics (∼72 h). RB degradation followed a pseudo-second-order kinetic model with a higher r2, and p-NP degradation followed first-order kinetics. The active sites embedded within the structural order of SL arrangement displayed elevated catalytic activity, which was further enhanced by the movement of intermediate/excited states and charged elements within the metal suspended in the phospholipid (LG and LGC). The self-regulating tunability of the physicochemical characteristics of these catalysts provides a convenient and generalizable platform for the transformation of modern dual-active (redox) catalysts into dynamic homogeneous equivalents.

Structural rather than catalytic role for mitochondrial respiratory chain supercomplexes

Mammalian mitochondrial respiratory chain (MRC) complexes are able to associate into quaternary structures named supercomplexes (SCs), which normally coexist with non-bound individual complexes. The functional significance of SCs has not been fully clarified and the debate has been centered on whether or not they confer catalytic advantages compared with the non-bound individual complexes. Mitochondrial respiratory chain organization does not seem to be conserved in all organisms. In fact, and differently from mammalian species, mitochondria from Drosophila melanogaster tissues are characterized by low amounts of SCs, despite the high metabolic demands and MRC activity shown by these mitochondria. Here, we show that attenuating the biogenesis of individual respiratory chain complexes was accompanied by increased formation of stable SCs, which are missing in Drosophila melanogaster in physiological conditions. This phenomenon was not accompanied by an increase in mitochondrial respiratory activity. Therefore, we conclude that SC formation is necessary to stabilize the complexes in suboptimal biogenesis conditions, but not for the enhancement of respiratory chain catalysis.

Structural rather than catalytic role for mitochondrial respiratory chain supercomplexes.

Mammalian mitochondrial respiratory chain (MRC) complexes are able to associate into quaternary structures named supercomplexes (SCs), which normally coexist with non-bound individual complexes. The functional significance of SCs has not been fully clarified and the debate has been centered on whether or not they confer catalytic advantages compared with the non-bound individual complexes. Mitochondrial respiratory chain organization does not seem to be conserved in all organisms. In fact, and differently from mammalian species, mitochondria from Drosophila melanogaster tissues are characterized by low amounts of SCs, despite the high metabolic demands and MRC activity shown by these mitochondria. Here, we show that attenuating the biogenesis of individual respiratory chain complexes was accompanied by increased formation of stable SCs, which are missing in Drosophila melanogaster in physiological conditions. This phenomenon was not accompanied by an increase in mitochondrial respiratory activity. Therefore, we conclude that SC formation is necessary to stabilize the complexes in suboptimal biogenesis conditions, but not for the enhancement of respiratory chain catalysis.

Electrochemical investigation of a facile MoO3/NiO/PdO/Pd nano electrode material for supercapacitor applications

AbstractBACKGROUNDOwing to the significance of metal oxide nanomaterials for energy storage supercapacitors, sustainable, cost‐effective and scalable synthesis of facile nanomaterials is a great challenge in the current era. Here, we have hydrothermally synthesized and functionalized a facile ternary metal oxides (MoO3/NiO/PdO/Pd) nanomaterial using the green phyto‐organic reducing plus stabilizing reagent Euphorbia cognata Boiss foliar extract (FE). The aqueous‐prepared FE was reacted with metal precursors and during this process, free octodrine and cyclobutanol organic functional groups of FE were incorporated as stabilizing agents.RESULTSThe synthesized MoO3/NiO/PdO/Pd demonstrated an optical band gap energy of 1.6 eV. Supercapacitor measurements of prepared MoO3/NiO/PdO/Pd were carried out on nickel (Ni) foam‐modified electrodes via charge–discharge (GCD), cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). CV measurements have been recorded at the range of scan rates (2–300 mV s−1) and it was found that the nanocomposite‐modified Ni foam showed a specific capacitance of 257 F g−1 at a scanning rate of 2 mV s−1. Furthermore, from the GCD investigation, it was revealed that 175 F g−1 was achieved at 0.5 A g−1 with a discharge current‐based energy density of 7.2 Wh kg−1. The fabricated electrode showed a 0.4 Ω resistance value from the impedance Nyquist plot.CONCLUSIONThe study concluded that the MoO3/NiO/PdO/Pd nanocomposite with the smaller synergistic band gap and catalytic advantage of phytostabilizing agents revealed exceptional capacitive properties, validating its potential as a supercapacitor electrode. © 2023 Society of Chemical Industry (SCI).

Synthesis and catalytic advantage of a hierarchical ordered macroporous KIT-6 silica

Ordered mesoporous silicas are important technological materials in catalysis, sorption and separation science, however new architectures are desired to improve in-pore accessibility. Here we report the first synthesis of an ordered macroporous KIT-6, obtained by optimizing the ratios of Pluronic P123: sodium dodecyl sulfate cosurfactants, and a 400 nm polystyrene nanosphere macropore template. The macroporous KIT-6 possesses 370 nm macropores in a face-centered cubic arrangement, surrounded by a silica framework comprised of cubic Ia3¯d three-dimensional, intertwined 5 nm mesopore channels. Propylsulfonic acid (PrSO3H) functionalization affords a macroporous KIT-6 solid acid catalyst whose hierarchical pore network permits rapid diffusion and esterification of fatty acids, conferring a five-fold enhancement for palmitic acid esterification compared with a conventional mesoporous PrSO3H/KIT-6, and 33% rate enhancement vs. an ordered macroporous PrSO3H/SBA-15.

Pincer Platinum(II) Hydrides: High Stability Imparted by Donor-Flexible Pyridylidene Amide Ligands and Evidence for Adduct Formation before Protonation

Donor-flexible ligands are an emerging class of noninnocent ligands. Their ability to adapt their donating strength toward a metal center has had numerous catalytic advantages yet has never been utilized to stabilize and isolate intermediate complexes within these processes. We demonstrate through the use of a pincer ligand containing two donor-flexible pyridylidene amide (PYA) arms in coordination with platinum(II) that this ligand adaptability revealed remarkably stable hydride and formate complexes. These are typically fleeting catalytic intermediates within formic acid dehydrogenation and CO2 hydrogenation catalytic cycles. The PYA platinum hydride complexes are indefinitely stable in air, while formate complexes show no sign of β-hydrogen elimination. This robustness allowed us to investigate hydride protonation as a seemingly simple reaction, though in-depth kinetic analysis reveals a pre-equilibrium step prior to platinum hydride protonation. This initial step has been attributed to adduct formation and is slower than the protonation, and therefore a relevant aspect when designing catalytic cycles for hydrogen release and its microscopic reverse, viz., hydrogen uptake.

Polymeric aluminum porphyrin: Controllable synthesis of ultra-low molecular weight CO2-based polyols

Carbon dioxide-based polyols with ultra-low molecular weight (ULMW, Mn < 1000 g/mol) are emergent polyurethane precursors with economic and environmental benefits. However, the lack of effective proton-tolerant catalytic systems limits the development of this field. In this work, the polymeric aluminum porphyrin catalyst (PAPC) system was applied to the copolymerization of CO2 and propylene oxide, where sebacic acid, bisphenol A, poly(ethylene glycol), and water were used as chain transfer agents to achieve the controlled synthesis of CO2-polyols. The molecular weight of the resulting CO2-polyols could be facilely regulated in the range of 400–930 g/mol at low catalyst loadings, fully demonstrating its catalytic advantages of high activity, high product selectivity, and excellent proton tolerance of PAPC. Meanwhile, the catalytic efficiency of PAPC could reach up to 2.1–5.2 kg/g under organic CTA conditions, even reaching 1.9 kg/g using water as the CTA. The cPC content could be controlled within 1.0 wt% under the optimized conditions, indicating the excellent controllability of the PAPC system. ULMW CO2-polyols combines the advantages of low viscosity (∼3000 mPa s at 25 °C), low glass transition temperature (∼−73 °C), and high carbonate unit content (∼40%), which is important for the development of high-performance polyurethanes.