Heterogeneous Catalyst Research Articles

Modulating the Aggregation States of a Pd6L4 Cage for Selectivity Flipping during the Stereo-Divergent Semi-Hydrogenation of Alkynes.

An enzyme-mimicking catalytic system has been established using a singular palladium-based octahedral cage as the supramolecular reactor, deftly unlocking off-on-off selectivity in the semi-hydrogenation of alkynes. Water serves as a critical regulator, modulating the catalyst states, reaction rates, and endpoints. The choice of solvent system influences the activity of host-guest binding and the reaction types of homogeneous and heterogeneous catalysis, effectively modifying the reaction steps involved in the Z→E isomerization during the semi-hydrogenation of alkynes. Kinetic and inhibition experiments indicate that the catalyst mimics the binding and activation characteristics of enzymes towards substrates, enabling selective transformations within the confined enzyme-mimicking environment. The utility of this switchable cage-confined catalysis has been demonstrated in the synthesis and modification of complex biologically active molecules with controllable E/Z selectivity. This work sheds light on the design and control of artificial supramolecular counterparts of enzymes, offering fundamental insights into the factors influencing the activity and catalytic selectivity of biological macromolecules.

Polyoxometalates‐Mediated Selectivity in Pt Single‐Atoms on Ceria for Environmental Catalysis

AbstractOptimizing the reactivity and selectivity of single‐atom catalysts (SACs) remains a crucial yet challenging issue in heterogeneous catalysis. This study demonstrates selective catalysis facilitated by a polyoxometalates‐mediated electronic interaction (PMEI) in a Pt single‐atom catalyst supported on CeO2 modified with Keggin‐type phosphotungstate acid (HPW), labeled as Pt1/CeO2‐HPW. The PMEI effect originates from the unique arrangement of isolated Pt atoms and HPW clusters on the CeO2 support. Electrons are transferred from the ceria support to the electrophilic tungsten in HPW clusters, and subsequently, Pt atoms donate electrons to the now electron‐deficient ceria. This phenomenon enhances the positive charge of Pt atoms, moderating O2 activation and limiting lattice oxygen mobility compared to the conventional Pt1/CeO2 catalyst. The resulting electronic structure of Pt combined with the strong and local acidic environment of HPW on Pt1/CeO2‐HPW leads to improved efficiency and N2 selectivity in the degradation of NH3 and NO, as well as increased CO2 yield when inputting volatile organic compounds. This study sheds the light on the design of SACs with balanced reactivity and selectivity for environmental catalysis.

Nano-Pd/SiO2 aerogel catalyst prepared via ambient pressure drying process using perlite powder in hydrogenation and cross-coupling reactions

Perlite, a cheap silica source with abundant reserves in countries such as Türkiye, China, and Greece, was used to produce nano Pd-doped silica aerogel powder for the first time in this study. The microstructure and morphology of the prepared silica aerogel powder were examined using SEM, FE-SEM, and TEM. The phases of the silica aerogel powders were analyzed via XRD (X-ray Diffraction) technique. The chemical bonding of the surface modifier with aerogels was analyzed by Fourier transform infrared spectroscopy (FTIR, Spectrum RX-1, Perkin Elmer). Surface areas, pore volumes, distributions, and particle sizes of the alumina-silica-based aerogel powders with a porous structure were measured using a Micromeritics/ASAP 2020 brand BET (Brunauer, Emmet, and Teller) device in a liquid nitrogen gas environment at 77K.The efficiency of this nano Pd-doped silica aerogel powder was investigated as a heterogeneous catalyst for well-known transformations in organic synthesis, such as alkene hydrogenation and cross-linking reactions. The results indicated that the developed method is chemoselective, reducing only carbon-carbon multiple bonds without affecting C-N or C-O multiple bonds, such as carbonyl and nitrile. The effectiveness of the newly developed catalyst was also investigated in Heck and Suzuki-Miyaura reactions, yielding the targeted products with high efficiency.Thus, an inexpensive, economical, and environmentally friendly method has been developed that is potentially applicable in the hydrogenation and cross-coupling reactions of alkenes.

Copper‐Catalyzed Simultaneous Dehydrogenation and Enantioselective Allylic Oxidation of Alkanes Using Chiral Heterogeneous Ligands to Produce Allylic Esters and Theoretical Investigation of the Mechanism

ABSTRACTA new asymmetric method for preparing chiral allylic esters from various unactivated alkanes through simultaneous dehydrogenation and enantioselective allylic oxidation in the presence of chiral heterogeneous oxazoline–based ligands is reported for the first time. For this purpose, chiral amino oxazoline ligands, synthesized from chiral amino alcohols and cyanogen bromide, were immobilized on modified MCM‐41 mesoporous silica. These chiral heterogeneous ligands were then characterized using Fourier‐transform infrared spectroscopy, thermogravimetric analysis, X‐ray diffraction, scanning electron microscopy, energy‐dispersive X‐ray spectroscopy, and Brunauer–Emmett–Teller and Barrett–Joyner–Halenda techniques. Finally, copper complexes of these ligands were employed in the synthesis of chiral allylic esters, achieving the best result with a 90% yield and 77% enantiomeric excess. Evaluation of the recyclability of the chiral heterogeneous catalysts revealed that they can be reused three times without a noticeable reduction in the results. In addition, the mechanism of formation of the chiral allylic esters was investigated using a density functional theory method.

A Novel Mesoporous SBA‐15 Supported Bifunctional Heterogeneous Catalyst for Base‐Free Transfer Hydrogenation Reaction of Ketones

ABSTRACTAmong the problems encountered in the catalytic transfer hydrogenation reactions of ketones, the base sensitivity of ketones and the corrosive effects of the bases used in the reaction have an important place especially in industrial terms. Although there are various approaches to overcome this problem, solutions based on the intrinsic properties of the catalyst used seem more suitable. Within the scope of this study, a novel heterogeneous catalyst was prepared for the transfer hydrogenation reaction of ketones, which can operate in base‐free environment. To prepare the heterogeneous catalyst, 1,2‐diphenylethane‐1,2‐diamine was first tosylated and then the silyl derivative was synthesized and grafted onto mesoporous silica SBA‐15. Characterizations of the obtained heterogeneous catalyst and SBA‐15 were carried out by X‐ray diffractometer (XRD), N2 sorption, thermogravimetric analysis (TGA), scanning electron microscope (SEM), energy dispersive X‐ray analysis, and Fourier transform infrared (FT‐IR) analysis. The results obtained showed that the functionalized 1,2‐diphenylethane‐1,2‐diamine compound was successfully immobilized into the SBA‐15 structure. Determination of the catalytic activity of the heterogeneous catalyst was carried out in transfer hydrogenation reactions of various aromatic ketones. After determining the optimum reaction conditions with acetophenone, a conversion rate of (70%) was observed in the acetophenone to 1‐phenylethanol reaction that took place without a base. Under same conditions a higher conversion rate of (73%) was observed in the 4′‐chloroacetophenone to 1‐(4‐chlorophenyl)ethanol reaction. In the reactions performed to determine recyclability, after a 70% conversion rate, 61% and 65% conversion rates, respectively, were observed in the reaction from acetophenone to 1‐phenylethanol under the same conditions.

Single-atom Barium Promoter Enormously Enhanced Non-noble Metal Catalyst for Ammonia Decomposition.

As a well-established topic, single-atom catalyst has drawn growing interest for its high utilization of metal. However, researchers prefer to develop various active metals with single-atom form, the intrinsic roles of single-atom promoters are usually underrated, which are significant in boosting reaction activity. In this work, Ba single atoms were in situ prepared in the Co-Ba/Y2O3 catalyst with crystallized BaCO3 as the precursor under the ammonia decomposition reaction condition. The optimized Co-Ba/Y2O3 catalyst achieves extremely high H2 production rate of 138.3 mmolH2·gcat-1·min-1 at very low temperature (500 °C, GHSV = 840,000 mL·g-1·h-1) and Co-Ba/Y2O3 exhibits excellent durability during the 350 h test, which realizes the highest activity among all non-noble catalysts, and reaches or even exceeds numerous reported Ru-based catalysts. Both Y2O3 and Co demonstrate positive interactions with Ba, which significantly facilitates the dispersion of Ba species at high temperatures (≥ 600 °C). Ba single atoms significantly enhance the charge density of Co and form additionally active Co-O-Ba-Y2O3 interfacial sites, which alleviates hydrogen poisoning and decreases the reaction barrier of the N-H bond activation of *NH. The exploration of atomically dispersed promoters is groundbreaking in heterogeneous catalysis, which opens up a whole new domain of catalytic material.

Single‐atom Barium Promoter Enormously Enhanced Non‐noble Metal Catalyst for Ammonia Decomposition

As a well‐established topic, single‐atom catalyst has drawn growing interest for its high utilization of metal. However, researchers prefer to develop various active metals with single‐atom form, the intrinsic roles of single‐atom promoters are usually underrated, which are significant in boosting reaction activity. In this work, Ba single atoms were in situ prepared in the Co‐Ba/Y2O3 catalyst with crystallized BaCO3 as the precursor under the ammonia decomposition reaction condition. The optimized Co‐Ba/Y2O3 catalyst achieves extremely high H2 production rate of 138.3 mmolH2·gcat−1·min−1 at very low temperature (500 °C, GHSV = 840,000 mL·g−1·h−1) and Co‐Ba/Y2O3 exhibits excellent durability during the 350 h test, which realizes the highest activity among all non‐noble catalysts, and reaches or even exceeds numerous reported Ru‐based catalysts. Both Y2O3 and Co demonstrate positive interactions with Ba, which significantly facilitates the dispersion of Ba species at high temperatures (≥ 600 °C). Ba single atoms significantly enhance the charge density of Co and form additionally active Co‐O‐Ba‐Y2O3 interfacial sites, which alleviates hydrogen poisoning and decreases the reaction barrier of the N‐H bond activation of *NH. The exploration of atomically dispersed promoters is groundbreaking in heterogeneous catalysis, which opens up a whole new domain of catalytic material.

Synthesis of Benzoic Acids from Electrochemically Reduced CO2 Using Heterogeneous Catalysts.

A method for the synthesis of benzoic acids from aryl iodides using two of the most abundant and sustainable feedstocks, carbon dioxide (CO2) and water, is disclosed. Central to this method is an effective and selective electrochemical reduction of CO2 (eCO2RR) to CO, which mitigates unwanted dehalogenation reactions occurring when H2 is produced via the hydrogen evolution reaction (HER). In a 3-compartment set-up, CO2 was reduced to CO electrochemically by using a surface-modified silver electrode in aqueous electrolyte. The ex-situ generated CO further underwent hydroxycarbonylation of aryl iodides by MOF-supported palladium catalyst in excellent yields at room temperature. The method avoids the direct handling of hazardous CO gas and gives a wide range of benzoic acid derivatives. Both components of the tandem system can be recycled for several consecutive runs while keeping a high catalytic activity.

Efficient paddle-wheel copper cluster-based metal-organic framework for catalytic conversion of CO2 to oxazolidinones under mild conditions

Efficient utilization of CO2 and its conversion into high-value-added products contribute to mitigating environmental issues such as the greenhouse effect. Among these methods, the carboxylation cyclization of CO2 with propargylic amine represents a green and atom-economical approach. Developing cost-effective catalyst that can promote this reaction under mild condition is desirable but challenging. Herein, a unique two-dimensional (2D) metal–organic framework (MOF) {[Cu(QCA)2]∙0.5DMF∙0.5H2O}n (1) (QCA =6-quinolinecarboxylic acid, DMF = N,N-dimethylformamide) have been synthesized and thoroughly characterized. Compound 1 was constructed from paddle-wheel dinuclear copper clusters [Cu2(COO)4] and carboxylate ligands, presenting a two-dimensional framework with new topology. Stability tests indicate that compound 1 undergoes reversible structural changes in different solvents and exhibits good thermal stability. 1 as heterogeneous catalyst enabled the transformation of CO2 and propargylic amine into oxazolidinones under mild conditions with broad substrate generality. In addition, 1 could maintain its catalytic performance with five continuous reactions. This work presents an infrequent example of a 2D noble metal free MOF-based catalyst that shows high catalytic efficiency under mild conditions.

Progressive Fabrication of a Pt‐Based High‐Entropy‐Alloy Catalyst toward Highly Efficient Propane Dehydrogenation

High‐entropy alloys (HEAs) have emerged as burgeoning heterogeneous catalysts due to their vast material space, unique structure, and superior stability. However, the dominant trial‐and‐error approaches hamper the exploration of efficient catalysts, necessitating the development of rational design strategies. Here, we report a progressive approach to the design and fabrication of HEA catalysts guided by alloying effects toward propane dehydrogenation. Cu, Sn, Au, and Pd are selected and demonstrated to induce dilution, encapsulation, surface enrichment, and inhomogeneity effects on Pt. The fabricated HEA, PtCuSnAuPd/SiO2, exhibits excellent activity, selectivity, and stability. The propylene formation rates reach 256 and 390 molC3H6 gPt−1 h−1 at 550 and 600 °C, respectively. Systematic characterizations reveal that the random elemental mixing, structural stability, and high Pt exposure promote the exposure of abundant stable isolated Pt sites. This work comprehensively explores the rational design and fabrication of HEA catalysts from a unique perspective, offering opportunities for developing advanced catalysts.

Heterogeneously Catalyzed Reductive Depolymerization of Lignin to Value-Added Chemicals.

Lignin is an abundant renewable source of aromatics, but its complex heterogeneous structure poses challenges for its depolymerization and valorization. Heterogeneously catalyzed reductive depolymerization (HCRD) has emerged as a promising approach, utilizing heterogeneous catalysts to facilitate selective bond cleavage in lignin and hydrogen transfer to stabilize the products under mild conditions. This review provides a comprehensive understanding of the hydrogen transfer mechanisms in HCRD, involving different hydrogen sources, including molecular hydrogen, alcohols, formic acid, etc., and the native hydrogen donor groups in lignin. The interaction between hydrogen sources and catalyst design is explored, emphasizing how catalyst characteristics must align with specific hydrogen transfer pathways to optimize efficiency and selectivity. Precious metal-based and non-precious metal-based catalysts are examined, highlighting advances that enhance hydrogen activation and transfer. Comparative analyses of hydrogen sources reveal distinct advantages and limitations. The significance of HCRD in lignin valorization and the development of integrated biorefineries is underscored, emphasizing its potential to contribute to a sustainable bioeconomy through improved process integration and economic viability.

Synthesis of Fe3O4 Derived from Acid Mine Drainage (AMD) Sludge and Catalytic Degradation of Tetracycline.

Acid mine drainage (AMD) sludge is waste generated in the process of acid mine wastewater treatment, and the use of AMD sludge to prepare Fe3O4 to activate H2O2 degradation pollutants is an effective means of resource utilization. In this study, the heterogeneous catalyst Fe3O4-based composites were synthesized by a one-step method using AMD sludge as a raw material, and the Fe3O4-based materials before and after catalysis were characterized by powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), and scanning electron microscopy (SEM). The effects of several key factors (pH values, H2O2 content, TC concentration, and Fe3O4 content) of tetracycline (TC) degradation were evaluated. The results revealed that the TC removal rate reached up to 95% within 120 min under optimal conditions (pH 3; H2O2, 5 mmol/L; TC concentration, 25 mg/L; Fe3O4 content, 1g/L). Moreover, •OH and •O2- radicals were generated during the Fenton-like degradation process, and the plausible degradation mechanism was discussed. Besides, the Fe3O4 catalyst exhibited fantastic stability after five cycles. In conclusion, this study is expected to promote the resource utilization of industrial sludge and provide a new material for the treatment of antibiotic-contaminated wastewater.

Progressive Fabrication of a Pt-Based High-Entropy-Alloy Catalyst toward Highly Efficient Propane Dehydrogenation.

High-entropy alloys (HEAs) have emerged as burgeoning heterogeneous catalysts due to their vast material space, unique structure, and superior stability. However, the dominant trial-and-error approaches hamper the exploration of efficient catalysts, necessitating the development of rational design strategies. Here, we report a progressive approach to the design and fabrication of HEA catalysts guided by alloying effects toward propane dehydrogenation. Cu, Sn, Au, and Pd are selected and demonstrated to induce dilution, encapsulation, surface enrichment, and inhomogeneity effects on Pt. The fabricated HEA, PtCuSnAuPd/SiO2, exhibits excellent activity, selectivity, and stability. The propylene formation rates reach 256 and 390 molC3H6 gPt-1 h-1 at 550 and 600 °C, respectively. Systematic characterizations reveal that the random elemental mixing, structural stability, and high Pt exposure promote the exposure of abundant stable isolated Pt sites. This work comprehensively explores the rational design and fabrication of HEA catalysts from a unique perspective, offering opportunities for developing advanced catalysts.

Microenvironment Control over Electrocatalytic Activity of g-C3N4/2H-MoS2 Superlattice-like Heterostructures for Hydrogen Evolution.

Microenvironments in heterogeneous catalysis have been recognized as equally important as the types and amounts of active sites for regulating catalytic activity. Two-dimensional (2D) nanospaces between van der Waals (vdW) gaps of layered materials provide an ideal microenvironment to create novel functionalities. Here, we explore a facile method for fabricating g-C3N4/2H-MoS2 superlattice-like heterostructures based on thermochemical intercalation and polymerization reactions of formamide within enlarged vdW gaps of 2H-MoS2 nanosheets without any transfer process. DFT calculations demonstrate that the interlayer electron-electron correlations due to the intercalation effect of g-C3N4, rather than high-κ dielectric environments, lead to the improvement of intrinsic conductivity of 2H-MoS2 nanosheets. As the proof of concept in applications for the electrocatalysis field, the heterostructure for hydrogen electrochemical reaction (HER) exhibits high stability and catalytic activity in both acid and alkaline media, such as a quite low onset overpotential of 98 mV, a high exchange current density of 77.6 μA cm-2, and a small Tafel slope (52.9 mV dec-1) in an acid medium. The enhanced HER activity is attributed to the improved conductivity and nanoconfinement effect of 2D nanospaces that decrease the reaction activation energy and activate the inert basal planes.

Transition Metal Catalyzed Deuteration via Hydrogen Isotope Exchange

Direct hydrogen isotope exchange represents a distinctive strategy for deuterium labelling, where the protium is directly replaced by deuterium. In this graphic review, we summarized the progress in deuteration via transition metal catalyzed hydrogen isotope exchange. The review was organized according to the mechanism of C-H bond activation in the homogeneous catalysis, and the heterogeneous catalysis was also discussed according to the catalyst type. Representative mechanistic processes were depicted, and proven cases for tritiation were also highlighted.

Synergistic degradation of refractory organic pollutant by underwater bubbling plasma combined with heterogeneous Fenton process

Excessive discharge of the refractory organic pollutants endangers the development of the society and economy, thus seeking an efficient wastewater abatement method is an urgent need. Herein, Iron (Ⅱ) sulfide (FeS) was employed as the heterogeneous catalyst and coupled with underwater bubbling plasma (UBP) for the elimination of the refractory organic pollutant, malachite green (MG). FeS catalyst was synthesized using the solvothermal method and subsequently characterized comprehensively, focusing on its microstructure, specific surface area, chemical bonds and elements valence states. The UBP system combined with FeS (UBP/FeS) exhibited the robust synergism with a maximum synergistic factor of 1.89. The MG degradation percentage and rate constant were up to 94.7% and 0.237 min−1 within 12 min. The parameter experiments revealed that FeS dosage, pulse frequency, initial MG concentration and solution conductivity of 150 mg/L, 56 Hz, 5 mg/L and 21.8 μS/cm, respective, were more conducive for MG elimination. The MG removal efficiency reached 86.2% after five consecutive applications of FeS. Reactive substances including ·OH, ·O2−, eaq, O3 and H2O2 were confirmed to contribute to MG elimination. Additionally, the conversion circle between ≡ Fe(Ⅱ) and ≡ Fe(Ⅲ) promoted the catalytic conversion of H2O2 and O3 into ∙OH. The comparison of UV–vis spectra and total organic carbon of MG solution before and after reaction revealed the superior degradation of MG in the UBP/FeS system. Hypotheses regarding to the decomposition pathways of MG were formulated based on the identified intermediates. The toxicity level of MG solution was lightened after reaction. The above results indicate that UBP/FeS has the advantages of quick degradation and high efficiency, representing a promising approach for refractory pollutants treatment.

Catalytic CO2 Desorption from MEA Solution of Al-FeOOH Composite Catalysts’ Desorption Performance, Structure–Activity Relationship, and New Mechanism

In order to reduce the massive heat duty of amine-based CO2 capture technology, an AlOOH/FeOOH composite catalyst (AF-M/N) was synthesized to speed up the CO2 desorption rates and reduce the heat duty of an aqueous MEA solution. The catalysis of AF-M/M from 1/9 to 9/1 was investigated comprehensively, with characterization of the catalytic desorption with heat duty and desorption factors. Results indicated the special composite catalyst (AF-1/9) possessed optimized catalysis with a relative heat duty of 78.7% and a desorption factor of 0.0037 × 10−3 (mol CO2/L2 kJ min) and relative desorption factor of 194.7%. The structure–activity correlations indicated that the mesopore surface area (MSA), which reached 329 m2/g, and Brϕnsted/Lewis acid ratio (B/L ratio) of 0.11 were the most important factors for enhancing catalysis. Furthermore, molecular simulations were conducted for the catalytic carbamate breakdown mechanism, focusing on the “isomerization” of “carbamate acid” vs. “Zwitterion” as the key step. From the DFT study, the isomerization was most likely to proceed with H2O as catalyst via intermolecular proton transfer instead of intramolecular proton transfer, with an activation energy Ea of 85.9 kJ/mol. With the aid of AlOOH the isomerization was further facilitated due to stabilized Zwitterion, and the Ea decreased to 69.2 kJ/mol. The results not only synthesized a new heterogeneous catalyst but also revealed the map of “isomerization” on a molecular level. Such a discovery indicates that water-assisted proton transfer is advantageous for catalytic carbamate breakdown.

Elaboration and characterization of Zn1−xCoxFe2O4 spinel ferrites magnetic material: application as heterogeneous catalysts in styrene oxidation

Elaboration and characterization of Zn1−xCoxFe2O4 spinel ferrites magnetic material: application as heterogeneous catalysts in styrene oxidation

Selectivity of a Bioreceptor Element of the Sensor Based on an Organosilicon Material and Microorganism Cells

The yeast cells from Ogataea polymorpha, Blastobotrys adeninivorans, and Debaryomyces hansenii were immobilized on an organosilicon material by the sol-gel method, resulting in a hybrid biocatalyst. The catalytic activity of the immobilized mixture of microorganisms was evaluated using it as a bioreceptor element in a biosensor. The proposed biohybrid material, consisting of the yeast association immobilized on the organosilicate sol-gel matrix, exhibited broad substrate specificity. Thus, the immobilization of multiple yeast strains provides a heterogeneous catalyst able to biologically oxidize a wide range of organic compounds commonly found in wastewater and surface water.

Integrated Ziegler‐Natta/Brookhart‐Ni Catalysts for the Synthesis of Sutured Polar High‐Impact Polypropylenes

The direct synthesis of polar high‐impact polypropylenes using industrially‐preferred heterogeneous catalysts is challenging due to the poisoning of polar functional groups towards metal center and the high stereo‐selectivity requirement. In this work, dual‐site catalysts combining Ziegler‐Natta and Brookhart‐Ni catalysts were used to produce polar polyolefin ionomers, followed by polar high‐impact polypropylenes containing isotactic polypropylene and branched polyethylene as toughening agents. Three combination modes between these catalysts were investigated, including mixed, core‐shell, and integrated types. The integrated dual‐site catalyst achieved the optimal material properties because the polyolefin ionomer acted as a suture molecule that stitched different components into a whole network. This produced sutured polar high‐impact polypropylenes with excellent mechanical properties and compatibility with polar substances. The restraining effect of the suture molecules greatly reduced the release of microplastic particles after aging. Moreover, the obtained polar high‐impact polypropylene can serve as an efficient compatibilizer to recycle polyethylene/polypropylene mixed‐waste plastics. This work provides an appealing and potentially practical strategy to upgrade the widely used polypropylenes and to alleviate the ever‐growing plastic pollution issue.