Dual Catalyst System Research Articles

Highly selective production of light aromatics from co-catalytic fast pyrolysis of pre-deoxygenated biomass and hydrogen-rich polyethylene using a dual-catalyst system

Co-catalytic fast pyrolysis of torrefaction deoxygenated pine wood (PW) and high-density polyethylene (HDPE) in dual-catalyst (metal oxidize and zeolite) system is an effective technology to produce renewable bio-aromatics. In this work, the torrefaction deoxygenation pretreatment (TDP) was carried out to remove oxygen element from PW prior to catalytic fast pyrolysis (CFP). 56.90 % oxygen could be removed at TDP temperature of 300 ºC, releasing in the oxygen carrier of CO2, CO, H2O, alcohols, acids, phenols, etc. Then, the synergistic effect between the metal oxide and the HZSM-5 in dual-catalyst system was also investigated. Among these metal oxides (Al2O3, MgO, CaO, ZnO, and Fe2O3) and hierarchical HZSM-5, the dual-catalyst of CaO and hierarchical HZSM-5 (treated by 0.2 M NaOH) was the optimal combination. The layout mode between feedstock and dual catalyst was also optimized. The highest yield of aromatics was produced in layout Mode 8, where the CaO was mixed with torrefied PW, but the hierarchical HZSM-5 and HDPE were laid in separated layers. The mixing of CaO and torrefied PW promoted the conversion of the macromolecular oxygenates into micromolecular oxygenates. Then, these small-molecular oxygenates could enter the hierarchical channel of HZSM-5, being converted into aromatics by undergoing the Diels-Alder reaction.

Direct additive-free N-formylation and N-acylation of anilines and synthesis of urea derivatives using green, efficient, and reusable deep eutectic solvent ([ChCl][ZnCl2]2)

In the current report, we introduce a simple, mild efficient and green protocol for N-formylation and N-acetylation of anilines using formamide, formic acid, and acetic acid as inexpensive, nontoxic, and easily available starting materials just with heating along stirring in [ChCl][ZnCl2]2 as a durable, reusable deep eutectic solvent (DES), which acts as a dual catalyst and solvent system to produce a wide range of formanilides and acetanilides. Also, a variety of unsymmetrical urea derivatives were synthesized by the reaction of phenyl isocyanate with a range of amine compounds using this benign DES in high to excellent yields. [ChCl][ZnCl2]2 showed good recycling and reusability up to four runs without considerable loss of its catalytic activity.

Study on ex-situ catalytic pyrolysis of poplar to produce aromatics over a dual-catalyst system of hydroxyapatite and HZSM-5

The ex-situ catalytic pyrolysis of poplar in a dual-catalyst system of hydroxyapatite (HAP) and HZSM-5 was performed using a bench-scale device to enhance the aromatics production. Results indicated that the introduction of HAP could effectively achieve the deoxygenation of macromolecular oxygenates, which were then converted into hydrocarbon precursors. The combination of HAP and HZSM-5 exceedingly promoted the production of aromatics especially monocyclic aromatics (MAHs) than single HZSM-5. The effects of operating conditions on aromatics yield and distribution were investigated. Under the catalyst layout of mode B, with the optimum conditions reaching the catalytic temperature of 500 °C, HAP to HZSM-5 ratio of 2:4, and catalyst to biomass ratio of 1:1, the maximum aromatics yield of 9.10 wt% was achieved, accompanied by the monocyclic aromatics/polycyclic aromatics ratio enhanced to 2.33. At this point, the synergistic effect for MAHs and total aromatics reached 170.09% and 214.14%, respectively. Compared to the conventional metal oxides, the HAP/HZSM-5 dual-catalyst system exhibited superior performance in aromatics production. Besides, the anti-coking capability of HZSM-5 in the dual-catalyst system was also better than that of pure HZSM-5. This research provided a new perspective for the efficient utilization of biomass energy.

Green Molecular Transformation in Dual Catalysis: Photoredox Activation of Vitamin B12 Using Heterogeneous Photocatalyst.

This concept focuses on dual-catalysis using metal complexes and heterogeneous photocatalysts. Vitamin B12 derivatives are sophisticated metal complexes that facilitate enzymatic reactions in the biological systems. The B12 enzymes inspired reactions catalytically proceed in dual-catalyst systems of B12 derivatives and heterogeneous photocatalysts, such as titanium oxide (TiO2 ) and metal-organic frameworks (MOFs), under light irradiation. The cobalt ions in B12 derivatives are effectively reduced by photoexcited photocatalysts, producing low-valent Co(I) species. The photoinduced nucleophilic Co(I) species react with an alkyl halide to form an organometallic complex with a Co-C bond. The Co-C bond dissociates during photolysis to generate alkyl radicals. Based on this mechanism, dual-catalysis effectively promotes various light-driven organic syntheses and light-driven dehalogenation reactions of toxic alkyl halides. The trends of the dual-catalyst system and recent progress in this field are discussed in this concept.

Bottom-Up Construction of Ni(II)-Incorporated Covalent Organic Framework for Metallaphotoredox Catalysis.

The construction of an all-in-one catalyst, in which the photosensitizer and the transition metal site are close to each other, is important for improving the efficiency of metallaphotoredox catalysis. However, the development of convenient synthetic strategies for the precise construction of an all-in-one catalyst remains a challenging task due to the requirement of precise installation of the catalytic sites. Herein, we have successfully established a facile bottom-up strategy for the direct synthesis of Ni(II)-incorporated covalent organic framework (COF), named LZU-713@Ni, as a versatile all-in-one metallaphotoredox catalyst. LZU-713@Ni showed excellent activity and recyclability in the photoredox/nickel-catalyzed C-O, C-S, and C-P cross-coupling reactions. Notably, this catalyst displayed a better catalytic activity than its homogeneous analogues, physically mixed dual catalyst system, and, especially, LZU-713/Ni which was prepared through post-synthetic modification. The improved catalytic efficiency of LZU-713@Ni should be attributed to the implementation of bottom-up strategy, which incorporated the fixed, ordered, and abundant catalytic sites into its framework. This work sheds new light on the exploration of concise and effective strategies for the construction of multifunctional COF-based photocatalysts.

The modern preparation of menthol and the burgeoning dual catalyst system - The three different synthesis pathways and one significant improvement of menthol

This paper will mainly focus on the modern preparation pathway of menthol, which involves Takasago and BASF, these two traditional pathways. Besides, the unique dual catalyst system will also be talked about in this work. This paper will give the introduction of them, their advantages and disadvantages, moreover, their actual application will also be brought to notice. Menthol is a salient chemical substance that plays an important role in perfume manufacture, and it is actually the source of the special and pleasant smell of many herbs, especially mint. In addition, menthol is also a fundamental raw material in many parts of chemical synthesis due to its unique structure. This research can give summative conclusions about this basic but noteworthy domain.

Tandem Conversion of Fructose to Bio‐diketones Using a Multifunctional Pd‐POPs‐CF3SO3H Catalyst

AbstractTandem conversion of biomass to value‐added fine chemicals is a significant challenge. For instance, the production of fine chemicals from fructose involves conversion to 5‐hydroxymethylfurfural (5‐HMF), followed by another reaction and purification. Dual catalyst systems have been used in nearly every study on the tandem conversion of fructose to bio‐diketones. Therefore, a sole multifunctional heterogeneous catalyst was developed in this study for the tandem conversion of fructose to bio‐diketones, which has not been reported previously. Instrument corrosion and the separation or purification of 5‐HMF were avoided using the multifunctional heterogeneous catalyst, which contained integrated active sites of acid, metal, and anions. The multifunctional CF3SO3H‐functionalized porous‐organic‐polymers(POPs)‐supported Pd catalyst (Pd‐POPs‐CF3SO3H) was prepared using a series of modifications. A bio‐diketone yield of 51.0 % was achieved using Pd‐POPs‐CF3SO3H in the tandem conversion of fructose with an excellent TOF of 88.3 h−1 which is much more efficient than catalyst reported in literatures. Pd‐POPs‐CF3SO3H could be reused at least three times with stable performance. Control experiments and characterization results proved that the high specific surface area, hierarchical pore structure, abundance of CF3SO3−1 anions, and proximity of Pd moieties and acid sites (“The closer the better” principle) led to the decent performance for bio‐diketone.

Enantioselective Chemodivergent Three-Component Radical Tandem Reactions through Asymmetric Photoredox Catalysis.

Chemodivergent synthesis has been achieved in asymmetric photocatalysis. Under a dual catalyst system consisting of a chiral phosphoric acid and DPZ as a photosensitizer, different inorganic bases enabled the formation of two sets of valuable products from the three-component radical tandem transformations of 2-bromo-1-arylenthan-1-ones, styrenes, and quinoxalin-2(1H)-ones. The key to success was the distinct pKa environment, in which the radicals that formed on the quinoxalin-2(1H)-one rings after two radical addition processes underwent either single-electron oxidation or single-electron reduction. In addition, this work represents the first use of quinoxalin-2(1H)-ones in asymmetric photoredox catalysis.

Asymmetric Olefin Isomerization via Photoredox Catalytic Hydrogen Atom Transfer and Enantioselective Protonation.

Asymmetric olefin isomerization can be appreciated as an ideal synthetic approach to access valuable enantioenriched C═C-containing molecules due to the excellent atom economy. Nonetheless, its occurrence usually requires a thermodynamic advantage, namely, a higher stability of the product to the substrate. It has thus led to rather limited examples of success. Herein, we report a photoredox catalytic hydrogen atom transfer (HAT) and enantioselective protonation strategy for the challenging asymmetric olefin isomerization. As a paradigm, by establishing a dual catalyst system involving a visible light photosensitizer DPZ and a chiral phosphoric acid, with the assistance of N-hydroxyimide to perform HAT, a wide array of allylic azaarene derivatives, featuring α-tertiary carbon stereocenters and β-C═C bonds, was synthesized with high yields, ees, and E/Z ratios starting from the conjugated α-substituted alkenylazaarene E/Z-mixtures. The good compatibility of assembling deuterium on stereocenters by using inexpensive D2O as a deuterium source further underscores the broad applicability and promising utility of this strategy. Moreover, mechanistic studies have provided clear insights into its challenges in terms of reactivity and enantioselectivity. The exploration will robustly inspire the development of thermodynamically unfavorable asymmetric olefin isomerizations.

Catalytic Asymmetric Intermolecular [3 + 2] Photocycloaddition of Cyclopropylamines with Electron-Deficient Olefins.

An enantioselective intermolecular [3 + 2] cycloaddition of N-arylcyclopropylamines with 2-aryl acrylates/ketones and cyclic ketone-derived terminal olefins via asymmetric photoredox catalysis is reported. A dual catalyst system involving DPZ and a chiral phosphoric acid is effective for the transformations, leading to a wide array of valuable cyclopentylamines with high yields, ee's, and drs. Among them, elaborate modulation of the ester group of 2-aryl acrylates was shown to be effective in improving reactivity, thereby enabling the success of the transformations.

Nonstoichiometric Direct Arylation Polymerization of Octafluorobiphenyl with 2,7-Diiodofluorene for Regulating CH Terminals of π-Conjugated Polymer.

Nonstoichiometric direct arylation polycondensation of 2,2',3,3',5,5',6,6'-octafluorobiphenyl with excess of 2,7-diiodo-9,9-dioctyl-9H-fluorene is demonstrated. Pd/Ag dual-catalyst system under water/2-methyltetrahydrofuran biphasic conditions enables direct arylation under mild conditions and promotes the intramolecular transfer of a Pd catalyst walking through the fluorene moiety. The nonstoichiometric direct arylation polycondensation under the optimized reaction conditions produces the corresponding π-conjugated polymer with a high molecular weight and terminal octafluorobiphenyl units at both ends.

Photoexcited NiII-Aryl Complex-Mediated Giese Reaction of Aryl Bromides.

A Giese reaction of aryl bromides with electron-deficient alkenes was developed, enabled by a dual catalyst system containing NiII complex and IrIII photocatalyst. This protocol could accommodate a variety of aryl bromides and electron-deficient alkenes, delivering the conjugate adducts in up to 97% yield. The utilization of photoexcited (dtbbpy)NiII(aryl)Br intermediate as an aryl radical source allows this novel transformation of aryl halides, thus expanding the chemical space of excited nickel catalysis.

Catalytic pyrolysis of biomass to produce aromatic hydrocarbons in a cascade dual-catalyst system: Design of red mud based catalyst assisted by the analysis of variance

Theoretical and experimental study on the catalytic pyrolysis of rape straw was carried out for the production of aromatic hydrocarbons using the composite red mud (RM) and zeolite HZSM-5 catalyst as the combined catalysts. In the orthogonal tests and analysis of variance (ANOVA), it was originally established that Fe2O3 and CaO acted as the active metal oxides in the red mud, which played the notable role in the production of benzene, toluene and xylene (BTX) as hydrocarbon fuels. Subsequently, the physicochemical property of the Fe2O3 and CaO loaded red mud (Fe2O3-RM and CaO-RM) was investigated and their performance in the catalytic pyrolysis of rape straw combined with HZSM-5 were investigated. It was revealed that the further cracking of the primary pyrolysis gas was promoted with more active Fe2O3 involved, and the heavy component was converted into the light fraction entering HZSM-5 for deoxygenation and aromatization to produce aromatic hydrocarbons. The yield of BTX over Fe2O3-RM was boosted by 10.15 wt% compared with the original red mud catalyst, while that of BTX was further promoted to 11.37 wt% over the composite red mud catalyst with 6% CaO loading. In addition to the strong bond-breaking performance of CaO, calcium carboxylate was easily generated and then decomposed to form CaCO3 and ketones, and then BTX were produced from ketones over HZSM-5 by deoxygenation and aromatization. In this study, the high-performance red mud-based catalysts was designed and utilized in the thermochemical conversion of biomass, providing a potential way for the utilization of two solid wastes, rape straw and red mud to produce hydrocarbon fuels in a high-valued way.

Base-acid relay catalytic upgrading of coal pyrolysis volatiles over CaO and HZSM-5 catalysts

The relay catalytic upgrading of coal pyrolysis volatiles employing different layouts of basic CaO and acidic HZSM-5 zeolite was proposed to improve the tar quality as well as alleviate catalyst deactivation. The synergistic effect is found in relay catalytic upgrading of coal pyrolysis volatiles over dual CaO and HZSM-5 catalysts system. The relay CaO-HZSM-5 layout is better compared to layouts of relay HZSM-5-CaO, mixed CaO/HZSM-5, and their independent employments. The relay CaO-HZSM-5 layout ensures the highest light fraction in tar with 70.1 % and the minimized carbon deposition over HZSM-5 while remaining a relatively high tar yield (7.8 wt %). Meanwhile, the contents of aromatics and phenols in tar increase by 221 % and 164 % compared with the blank test (without catalyst), respectively. In this scenario, CaO promotes the cracking of large molecules in tar to form more olefins and small molecules firstly, which subsequently diffuses into micropores of HZSM-5 zeolite to produce more aromatics by dehydrocyclization. In addition, the roles of pre-cracking and pre-deoxidation of volatiles over CaO reduce the possibility of the polycondensation reactions of large molecules over acidity sites of HZSM-5 zeolite, thus lowering the carbon deposition over zeolite. These findings suggest that the base-acid relay catalytic upgrading of volatiles during coal pyrolysis will be a promising strategy to increase the tar quality and slow down catalyst deactivation.

Noble-Metal-Free C-H Allylation of Tetrahydroisoquinolines Using a Cobalt-Organophotoredox Dual Catalyst System.

Metallaphotoredox-catalyzed allylation represents an emerging synthetic methodology that enables allylic substitution using nucleophilic radical species. The C-H allylation of N-aryl tetrahydroisoquinolines is an innovative example in this area and allows access to synthetically useful precursors for the further derivatization of tetrahydroisoquinolines. However, previous methods have required the use of noble metals, which has hampered their application due to concerns over their sustainability. Here we report the C-H allylation of N-aryl tetrahydroisoquinolines using a cobalt/organophotoredox dual catalyst system. Based on precedent, control experiments and controlled irradiation experiments, a mechanism for the cobalt/photoredox-catalyzed allylation that involves a π-allyl cobalt complex is proposed.

Product regulation and catalyst deactivation during ex-situ catalytic fast pyrolysis of biomass over Nickel-Molybdenum bimetallic modified micro-mesoporous zeolites and clays

Ni-Mo bimetallic modified micro-mesoporous zeolite catalysts were prepared and employed in the process of ex-situ catalytic fast pyrolysis (CFP) of poplar to produce liquid fuel. Clay catalysts were incorporated to further improve the products quality. The mass yield of monocyclic aromatic hydrocarbons (MAHs) increased under the catalysis of composite catalysts AZM and NiMo/AZM. HAP&Zeolite dual catalyst system reduced coke yield of NiMo/AZM to 5.01 wt%. Through real-time monitoring of gas products, the catalytic performance of zeolites began to decrease after the ratio of biomass and catalyst was more than 1. A series of characterization results futher demonstrated that AZM and NiMo/AZM possessed more stable catalytic ability and higher catalytic activity during the whole CFP process. N2 adsorption–desorption measurement and Raman characterization illustrated the formation and structure of coke, catalyst deactivation and the protective mechanism of mesopores on micropores.

Solvent-free dehydration, cyclization, and hydrogenation of linalool with a dual heterogeneous catalyst system to generate a high-performance sustainable aviation fuel

The development of efficient catalytic methods for the synthesis of bio-based, full-performance jet fuels is critical for limiting the impacts of climate change while enabling a thriving modern society. To help address this need, here, linalool, a terpene alcohol that can be produced via fermentation of biomass sugars, was dehydrated, cyclized, and hydrogenated in a one-pot reaction under moderate reaction conditions. This sequence produced a biosynthetic fuel mixture primarily composed of 1-methyl-4-isopropylcyclohexane (p-menthane) and 2,6-dimethyloctane (DMO). The reaction was promoted by a catalyst composed of commercial Amberlyst-15, H+ form, and 10% Pd/C. Two other terpenoid substrates (1,8-cineole and 1,4-cineole) were subjected to the same conditions and excellent conversion to high purity p-menthane was observed. The fuel mixture derived from linalool exhibits a 1.7% higher gravimetric heat of combustion and 66% lower kinematic viscosity at −20 °C compared to the limits for conventional jet fuel. These properties suggest that isomerized hydrogenated linalool (IHL) can be blended with conventional jet fuel or synthetic paraffinic kerosenes to deliver high-performance sustainable aviation fuels for commercial and military applications.

Selective production of aromatics from catalytic pyrolysis of biomass wastes: Effects of feedstock properties and key oxygenated intermediates on aromatics formation

The catalytic pyrolysis is a promising method for obtaining value-added aromatics, especially benzene, toluene and xylene (BTX). For different biomass-based materials, the dual catalyst system composed of CaO-based and ZSM-5-based catalysts showed an obvious selectivity for the BTX production. This study chose CaO derived from organic calcium precursors (Org-CaO) and nano-sized ZSM-5 (NZSM-5), and comprehensively investigated the effects mechanism of biomass components on the formation pathways of BTX via Py-GC/MS. Under the catalysis of NZSM-5, the BTX yields were only 7.8–30%. The BTX yields on Org-CaO/NZSM-5 were as follows: lipid (63.1%) > hemicellulose (55.4%) > cellulose (40.2%) > lignin (21.7%). Typical pyrolysis intermediates were employed to quantitatively reveal the intermediate reactions. Pyrolysis intermediates exhibited low BTX-forming reactivity over NZSM-5. The pre-catalysis of Org-CaO selectively converted part undesired intermediates (fatty acids and furans) into BTX precursors (short-chain olefins and ketones), facilitating the remarkable increase of BTX yield in the subsequent NZSM-5 catalysis process. However, the pre-catalysis of Org-CaO can hardly make the ring opening reaction of lignin-derived phenolic compounds that have very low reactivity on NZSM-5, and thence high-lignin biomass obtained low BTX production during catalytic pyrolysis by Org-CaO/NZSM-5. These findings afforded a new route for increasing the BTX yields by directionally forming BTX precursors or controlling biomass components.

Formulation of two monofunctional catalysts for CH4 upgrading

Natural gas will play a significant role in the transition from fossil to green(er) energy production. Its major component, methane (CH4) is an attractive resource to co-generate hydrogen (H2) and added value chemicals (important building blocks such as olefins and aromatics) for petrochemistry. We highlight the advantage of using a novel dual catalyst system containing a monofunctional Al-free metallic single site catalyst referred as S-Mo (Si/Al ∼ ∝) where Mo is atomically dispersed in the zeolitic framework and a monofunctional acidic H-ZSM-5 catalyst referred as S-Al (SiAl = 128) to achieve superior yields of high value products. Under severe reaction (850 ºC) and regeneration (700 ºC) conditions, the Mo-S catalyst is stable and does not suffer from irreversible structural damage by losing its Mo atomic dispersion, and deactivation by coke deposition, thus ensuring steady catalytic performances in multi-cycle catalytic tests. Conversely, the current bifunctional catalysts prepared by Mo impregnation on an acidic catalyst suffer from irreversible damage during coke combustion due to the formation of Al₂(MoO₄)₃ or AlMoO6 Anderson entities. This new approach opens novel and promising pathways to develop methane upgrading processes based on the physical separation and operation of a non-deactivating metallic catalyst and a regenerable acidic catalyst.

Enhanced production of monocyclic aromatic hydrocarbons by catalytic pyrolysis of rape straw in a cascade dual-catalyst system of modified red mud and HZSM-5

Catalytic pyrolysis of rape straw was carried out on a dual-catalyst system to produce benzene, toluene, xylene (BTX), realized by promoted cracking of large-molecule pyrolysis vapor over red mud (RM) and followed by selectively catalytic conversion over HZSM-5. With the pyrolysis temperature of 550 °C and the catalyst/biomass mass ratio of 2:1, the yield of BTX in bio-oil reached the maximum of 10.27 wt%. The coking resistance of HZSM-5 in the cascade catalytic system was obviously better than pure HZSM-5. The pretreatment of RM by calcination and acid washing was also performed. The unstable components of RM like cancrinite were decomposed during the calcination. Besides, the content of active metal oxides in RM after acid washing increased by removing Na2O and CaO. Its specific surface area was promoted, due to the new micropores caused by the dispersion of dissolved metal oxides. RM treated with 3 mol/L hydrochloric acid presented the highest specific surface area of 55.24 m2/g while the maximized yield of BTX of 12.91 wt%. Therefore, the dual-catalyst system might be an effective method to dispose and high valued use of rape straw and RM as solid wastes with significant environmental impact to promote carbon neutrality.