Loss Of Reactivity Research Articles

Iridium‐Catalyzed Asymmetric Transfer Hydrogenation for Facile Access to Optically Active Dihydrodibenzo‐Fused Azepines

The asymmetric transfer hydrogenation of various dibenzo‐fused azepines including 5H‐dibenzo[b,e][1,4]diazepines, dibenzo[b,f][1,4]thiazepines and 11H‐dibenzo[b,e]azepines using chiral iridium diamine catalysts and HCO2H/NEt3 as the hydrogen source has been accomplished. A rang of chiral 10,11‐dihydro‐5H‐dibenzo[b,e][1,4]diazepines, 10,11‐dihydrodibenzo[b,f][1,4]thiazepine and 6,11‐dihydro‐5H‐dibenzo[b,e]azepines have been prepared in 82‐94% yields with 82‐99% ee. Diversely substituted substrates are suitable for this transformation, and a number of functional groups are tolerated. The enantiocontrol is achieved via judicious choice of catalyst, additive and hydrogen source. The synthetic potential of this reaction is explored through gram‐scale reactions without loss of reactivity and optical purity and further transformations on products.

Temporal variation in p38-mediated regulation of DUX4 in facioscapulohumeral muscular dystrophy

Facioscapulohumeral muscular dystrophy (FSHD) is a degenerative muscle disease caused by loss of epigenetic silencing and ectopic reactivation of the embryonic double homeobox protein 4 gene (DUX4) in skeletal muscle. The p38 MAP kinase inhibitor losmapimod is currently being tested in FSHD clinical trials due to the finding that p38 inhibition suppresses DUX4 expression in preclinical models. However, the role of p38 in regulating DUX4 at different myogenic stages has not been investigated. We used genetic and pharmacologic tools in FSHD patient-derived myoblasts/myocytes to explore the temporal role of p38 in differentiation-induced DUX4 expression. Deletion of MAPK14/11 or inhibition of p38α/β caused a significant reduction in early differentiation-dependent increases in DUX4 and DUX4 target gene expression. However, in MAPK14/11 knockout cells, there remains a differentiation-associated increase in DUX4 and DUX4 target gene expression later in differentiation. Furthermore, pharmacologic inhibition of p38α/β only partially decreased DUX4 and DUX4 target gene expression in late differentiating myotubes. In xenograft studies, p38α/β inhibition by losmapimod failed to suppress DUX4 target gene expression in late FSHD xenografts. Our results show that while p38 is critical for DUX4 expression during early myogenesis, later in myogenesis a significant level of DUX4 expression is independent of p38α/β activity.

Warming exacerbates global inequality in forest carbon and nitrogen cycles

Forests are invaluable natural resources that provide essential services to humanity. However, the effects of global warming on forest carbon and nitrogen cycling remain uncertain. Here we project a decrease in total nitrogen input and accumulation by 7 ± 2 and 28 ± 9 million tonnes (Tg), respectively, and an increase in reactive nitrogen losses to the environment by 9 ± 3 Tg for 2100 due to warming in a fossil-fueled society. This would compromise the global carbon sink capacity by 0.45 ± 0.14 billion tonnes annually. Furthermore, warming-induced inequality in forest carbon and nitrogen cycles could widen the economic gap between the Global South and Global North. High-income countries are estimated to gain US$179 billion in benefits from forest assets under warming, while other regions could face net damages of US$31 billion. Implementing climate-smart forest management, such as comprehensive restoration and optimizing tree species composition, is imperative in the face of future climate change.

Ultrasound-promoted removal of benzylidene and isopropylidene acetal protection of carbohydrates in presence of sulfonated graphene (GR-SO3H) as a sustainable acid catalyst

Sulfonated graphene (GR-SO3H) was prepared and used as an efficient and sustainable catalyst to deprotect O-benzylidene and O-isopropylidene acetal of carbohydrates under ultrasound (US) irradiation. The solid catalyst can recovered by simple filtration and used several times without much loss in reactivity. This methodology not only reduces the reaction time but also increases the yield. Moreover, the work-up and purification procedure is very simple and also effective for large-scale preparation.

Degradation Mechanism and Enhanced Stability of Organolithium for Chemical Lithiation

AbstractOrganolithium solutions, especially Li‐arene solutions (LASs) with high reactivity and controllable redox potentials, have gained significant attention because of their wide applications in chemical lithiation, liquid anodes, and battery recycling. However, the sudden loss of reactivity when stored or applied at room temperature is still puzzling and inhibits the application of LASs. In this work, the degradation mechanism of LASs is fully investigated and revealed by combining various experimental characterization and computational simulations. A hierarchical reaction mechanism for lithium biphenyl/2‐methyl tetrahydrofuran (Li‐Bp‐2MT), a lithiation solution used for most anodes, explains degradation and side product formation. Specifically, the dimerization of the active component Li1Bp[2MT]1 forms an inactive dimer that is irreversibly reduced in the presence of locally accumulated highly reductive Li0. This reaction mechanism reveals the atomic origins of lithiation solution deactivation and accounts for all solid and gaseous byproducts. LiH is identified as the dominating solid byproduct, indicating irreversible destruction of the active components and facilitating side reactions producing H2 and CH4. Based on reaction mechanism insights, modifying molecular interactions and reaction kinetics are experimentally shown to inhibit Li0 aggregation kinetics, enhancing long‐term prelithiation performance. This research provides comprehensive guidelines for practical applications of LASs.

Nickel Molybdenum Selenide (NiMoSe2) Nanostructures: A Binary Transition Metal Dichalcogenide for Regioselective Synthesis of 2,3,5‐Tri Substituted Pyrrole Derivatives

AbstractBinary transition metal dichalcogenides (BTMDs) have attracted a lot of researchers to exploit their unique properties for different applications in various fields, mainly in energy and environment. Surprisingly, there are no attempts of utilizing BTMDs materials particularly nickel molybdenum selenide (NiMoSe2) as a catalyst support for organic transformations. Reusable catalysts are better alternatives to the transition metal‐free protocols for the synthesis of heterocyclic compounds. Herein, we report a NiMoSe2 BTMD catalyst with Lewis acidic (transition metal) and strongly basic (selenide) sites for the regioselective synthesis of 2,3,5‐tri(het)aryl‐pyrroles from β‐thioxoketone precursors. The present method is capable of giving the expected products in good to excellent yields (up to 80%). Different substituents like ester, cyano, alkyl, trifluoromethyl, methoxy, and halogens have shown tolerance under optimized reaction conditions. The recyclability and reusability of the catalyst was checked for five catalytic cycles without notable loss in reactivity.

Silica Nanoparticles Decorated with Ceria Quantum Dots Modulate Intra- and Extracellular Reactive Oxygen Species Formation and Selectively Reduce Human A375 Melanoma Cell Proliferation.

Nanomaterials show great promise for cancer treatment. Nonetheless, most nanomaterials lack selectivity for cancer cells, damaging healthy ones. Cerium dioxide (ceria, CeO2) nanoparticles have been shown to exert selective toxicity toward cancer cells due to the redox modulating properties they display as their size decreases. However, these particles suffer from poor suspension stability. The efficacy of CeO2 nanoparticles for cancer treatment is hampered by their innate high surface energy, which leads to particle agglomeration and, consequently, reactivity loss. This effect increases as particle size decreases; as such, quantum dots (QDs) suffer most from this phenomenon. In this study, it is proposed that silicon dioxide (silica, SiO2) nanoparticles can provide an inert platform for surface encrusted CeO2 QDs and that the resulting nanocomposite (hereafter QDCeO2/SiO2) not only will exhibit negligible agglomeration compared with CeO2 alone but also will improve the modulation of reactive oxygen species (ROS) leading to selective reduction of human A375 melanoma cell proliferation. The SiO2 nanoparticles had a bimodal size distribution with median particle size of 66 and 168 nm, while the CeO2 quantum dots encrusted on their surface had a size of 3.2 nm. An elevated Ce3+/Ce4+ ratio led to the QDCeO2/SiO2 nanocomposite displaying synergistic superoxide dismutase- and catalase-like activity, favoring the accumulation of ROS at pH 6.5 which translated into QDCeO2/SiO2 exerting selective oxidative stress in, and toward, the melanoma cells. Treatment with 50 μg mL-1 QDCeO2/SiO2 significantly reduced cell proliferation by 27% compared to untreated control cells in the colony formation assay. Treatment with either SiO2 or CeO2 alone did not affect the cell proliferation. These results highlight the benefit of dispersing CeO2 QDs on the surface of core nanoparticles and the resulting enhancement of selective redox reactivity and proliferation arrest when compared to CeO2 nanoparticles alone. Furthermore, the method employed here to encrust CeO2 QDs could lead to the facile synthesis of new nanocomposites with enhanced control of ROS activity, not only for in vitro studies using other cancer cell lines of interest but also in animal models and perhaps leading to clinical trials in melanoma patients.

Design of ant colony planning algorithms for multi-stage grids of distribution networks considering network resilience

Network Destruction Resilience is the ability of a system to maintain good operation in the event of an external attack or internal failure. The resilience of distribution network is crucial to guarantee the reliability of power supply. In this paper, we design a planning algorithm considering network destructibility for the multi-stage ant colony planning problem of distribution networks. The method establishes the multi-stage network planning objective function of distribution network from the perspectives of total investment cost and annual operation cost of multi-node network frame, destruction resistance, active power and reactive network loss of distribution network, etc. Then based on the constraints of the model, the improved ant colony algorithm is used to solve the multi-stage network planning objective function of distribution network, and the results of the anti-termite colony planning of multi-stage network frame of distribution network are obtained. In order to verify the effectiveness of the algorithm, simulation experiments are carried out on real distribution network data. The results show that the proposed ant colony planning algorithm for multi-stage grid frames can effectively improve the destruction resistance of distribution networks, and reduce the total investment cost and annual operation cost of multi-stage grid frames, and reduce the network loss rate data of multi-stage grid frames of distribution networks after application. It provides an effective method for planning the distribution network.

PET Glycolysis to BHET Efficiently Catalyzed by Stable and Recyclable Pd-Cu/γ-Al2O3.

Glycolysis of poly(ethylene terephthalate) (PET) is a prospective way for degradation of PET to its monomer bis(hydroxyethyl) terephthalate (BHET), providing the possibility for a permanent loop recycling. However, most reported glycolysis catalysts are homogeneous, making the catalyst difficult to recover and contaminating the products. Herein, we reported on the Pd-Cu/γ-Al2O3 catalyst and applied it in the glycolysis of PET as catalyst. The formed structure gave Pd-Cu/γ-Al2O3 a high active surface area, which enabled these micro-particles to work more efficiently. The PET conversion and BHET yield reached 99% and 86%, respectively, in the presence of 5 wt% of Pd-Cu/γ-Al2O3 catalyst within 80 min at 160 °C. After the reaction, the catalyst can be quickly separated by filtration, so it can be easily reused without significant loss of reactivity at least five times. Therefore, the Pd-Cu/γ-Al2O3 catalyst may contribute to an economically and environmentally improved large-scale recycling of PET fiber waste.

Disruption of Poly(ADP-ribosyl)ation Improves Plant Tolerance to Methyl Viologen-Mediated Oxidative Stress via Induction of ROS Scavenging Enzymes.

ADP-ribosylation (ADPRylation) is a mechanism which post-translationally modifies proteins in eukaryotes in order to regulate a broad range of biological processes including programmed cell death, cell signaling, DNA repair, and responses to biotic and abiotic stresses. Poly(ADP-ribosyl) polymerases (PARPs) play a key role in the process of ADPRylation, which modifies target proteins by attaching ADP-ribose molecules. Here, we investigated whether and how PARP1 and PARylation modulate responses of Nicotiana benthamiana plants to methyl viologen (MV)-induced oxidative stress. It was found that the burst of reactive oxygen species (ROS), cell death, and loss of tissue viability invoked by MV in N. benthamiana leaves was significantly delayed by both the RNA silencing of the PARP1 gene and by applying the pharmacological inhibitor 3-aminobenzamide (3AB) to inhibit PARylation activity. This in turn reduced the accumulation of PARylated proteins and significantly increased the gene expression of major ROS scavenging enzymes including SOD (NbMnSOD; mitochondrial manganese SOD), CAT (NbCAT2), GR (NbGR), and APX (NbAPX5), and inhibited cell death. This mechanism may be part of a broader network that regulates plant sensitivity to oxidative stress through various genetically programmed pathways.

N, N’-bidentate ligand anchored palladium catalysts on MOFs for efficient Heck reaction

Metal-organic frameworks (MOFs), recognized as advanced catalyst carriers due to their adjustable porous, diverse structure and highly exposed active sites, have earned increasing attention for their potential to address the longevity of catalytic centers. In this manuscript, we have devised and synthesized a multifunctional amino-pyridine benzoic acid (APBA) ligand to replace the modulator ligand of the MOF-808 and disperse the palladium catalytic centers atomically on the MOF-APBA. The resulting single-site catalytic system, Pd@MOF-APBA, demonstrates preeminent efficiency and stability, as evidenced by a high average turnover number (95000) and a low metal residue (4.8 ppm) in the Heck reaction. This catalyst has exhibited recyclability for multiple runs without significant loss of reactivity for gram-scale reactions. The catalyst’s high activity and efficiency can be attributed to the suitable electrical properties and structures of the N, N’-bidentate ligand for the catalytic palladium ions, postponing their deactivations, including leaching and agglomeration.

Metal-Free, PPA-Mediated Fisher Indole Synthesis via Tandem Hydroamination-Cyclization Reaction between Simple Alkynes and Arylhydrazines.

A new variant of Fisher indole synthesis involving Bronsted acid-catalyzed hydrohydrazination of unactivated terminal and internal acetylenes with arylhydrazines is reported. The use of polyphosphoric acid alone either as the reaction medium or in the presence of a co-solvent appears to provide the required balance for activating the C-C triple bond towards the nucleophilic attack of the hydrazine moiety without unrepairable reactivity loss of the latter due to competing amino group protonation. Additionally, the formal hydration of acetylenes to the corresponding ketones occurs under the same conditions, making it an alternative approach for generating carbonyl groups from alkynes.

Energy Efficiency of Steady DC and Half Sine Pulsed DC in the High Voltage Pre-Plasma and Plasma Alkaline Water Electrolysis

The research addresses the contrasting views on the energy efficiency of alkaline water electrolysis using the regular DC vs the pulsed DC. We compare the high voltage steady DC electrolysis with the high voltage half-wave rectified (HWR) AC (or the half Sine pulsed DC, an unexplored form of the pulsed DC) across a wide range of voltage regimes, with a particular focus on the less explored Plasma electrolysis (PE) regime. In addition, the current-voltage characteristics are mapped across the voltage regimes (NE to PE) using a novel high-voltage 3-electrode circuit, which allows better control over the working electrode potential. The experimental design considers critical parameters such as energy efficiency, Faradaic efficiency, and current density, providing a comprehensive evaluation of the regular DC Vs. the half-wave rectified AC electrolysis.Pulsed electrolysis can facilitate bubble removal and ensure timely replenishment of reactant during the low-bias phase and this is expected to diminish over potential losses due to mass transfer resistance. However, the preliminary energy efficiency assessment suggests that the regular DC is ~13% higher at 33 V bias and ~24% higher at 26.5 V bias than the half sine pulsed DC(50 Hz) electrolysis. This suggests that for these particular reaction conditions, the fluctuations in the current leading to reactive losses in the circuit and other internal losses overwhelm any enhancement in the mass transfer characteristic of pulsed electrolysis. The study also points to regimes where significant thermal decomposition results in a significant increase in the apparent Faradaic efficiency.

12-year continuous biochar application: Mitigating reactive nitrogen loss in paddy fields but without rice yield enhancement

Numerous studies have documented the beneficial effects of short-term biochar application on soil carbon sequestration, greenhouse gas emissions reduction, and ecological functions enhancement. However, concerns persist regarding the impacts on soil reactive nitrogen (N) loss and crop yields under long-term biochar application (more than ten years), due to the irreversibility once biochar is incorporated into soils. This study presents the results of a 12-year field experiment in a rice-wheat rotation system with treatments including a control (CK, no corn straw or biochar), annual corn straw returning (CS, 6 Mg·ha−1·yr−1), and annual application of corn straw biochar pyrolyzed at 400°C at rates of 2.4, 6, and 12 Mg·ha−1·yr−1 (BC1, BC2, and BC3), investigating rice yields (2011–2022) and reactive N loss (2021–2022). The results showed that after 11 years of continuous biochar application until the 2021 rice season, alkaline hydrolysis N (AN, equivalent to an average of 347 kg N ha−1) within the 0–15 cm soil layer in biochar treatments was significantly higher than that of the CK (200 kg N ha−1), attributable to the biochar-induced enhancement of cation exchange capacity (CEC). The application of biochar reduced inorganic N leaching and NH3 volatilization losses by an average of 42.21 % and 30.85 %, respectively. However, N2O emission in the BC3 treatment was over 2 times as high as in the CK. Continuous biochar applications did not increase rice yield over the 12 rice seasons, as excessive soil AN level under biochar application reduced the rice harvest index. The results indicated that continuous biochar application was effective in reducing reactive N losses and increasing plant-available N supply, suggesting a potential to sustain rice production with lower fertilizer N inputs.

Nanostructured Iron (III)-Copper (II) Binary Oxide as a Highly Efficient Magnetically Recoverable Nanocatalyst for Facile One-pot Synthesis of 2, 4, 5-trisubstituted Imidazole and 1, 4-dihydro Pyridine Derivatives under Solvent-free Conditions

Abstract: The Fe (III)-Cu (II) binary oxide magnetic nanocatalyst emerges as an environmentally friendly and highly efficient solid acid catalyst, demonstrating remarkable utility in the one-pot synthesis of 2, 4, 5-trisubstituted imidazole and 1,4-dihydropyridine compounds, all achieved under solvent-free conditions. A facile co-precipitation method was used to synthesize nanostructured Fe-Cu binary oxide. Notably, this Fe-Cu binary oxide magnetic nanocatalyst proves its eco-friendly credentials as an exceptionally efficient and reusable catalyst, offering ease of handling, recovery, and multiple uses with minimal reactivity loss. Furthermore, the Fe (III)-Cu (II) binary oxide magnetic nanocatalyst's magnetic separability enhances its practicality, allowing for effortless catalyst retrieval after reactions. Significantly, the structural characteristics are meticulously elucidated through advanced analytical techniques, including 1H and 13C nuclear magnetic resonance (NMR) spectroscopy. This work presents a versatile and sustainable solution for catalysis, with wide-reaching implications for green chemistry and the development of reusable, efficient catalysts for organic synthesis. The exceptional performance and eco-friendliness of the Fe-Cu binary oxide magnetic nanocatalyst underscore its practical significance. Fe-Cu binary oxide magnetic nanocatalyst exhibits the highest catalytic activity compared to others. The employment of this catalyst consistently delivers excellent yields in the target reactions, highlighting its potential to contribute positively to sustainable chemical processes.

Palladium-Catalyzed Asymmetric Allylic Alkylation of Azlactones: An Efficient Access to Unsaturated Trifluoromethylated α-Amino Acid Derivatives Possessing α-Quaternary Stereogenic Centers

AbstractA new strategy for the asymmetric allylic alkylation of azlactones with α-(trifluoromethyl)allyl acetates catalyzed by Pd(OAc)2/(R)-BINAP is designed and developed, providing access to unsaturated α-quaternary α-amino acid derivatives bearing a trifluoromethyl group and contiguous quaternary and tertiary stereogenic centers. The products are obtained in good yields with exclusive regioselectivity and excellent stereoselective control under relatively mild reaction conditions. A scale-up experiment shows no loss of reactivity or stereoselectivity. The synthetic utility of the current strategy is demonstrated through transformations of a representative product to afford several potentially bioactive species.

Fabrication of magnetic carbohydrate-modified iron oxide nanoparticles (Fe3O4/pectin) decorated with bimetallic Co/Cu-MOF as an effective and recoverable catalyst for the Biginelli reaction.

Due to their biocompatibility, facile recoverability, mechanical and thermal stability, high surface area, and active catalytic sites, magnetic nanocomposites, containing natural polymers and magnetic nanoparticles, have been used to produce supports for catalysts or biocatalysts. Pectin, an important polycarbohydrate, has abundant functional groups with excellent ability to coat the surface of the nanoparticles to fabricate composite and hybrid materials. A novel bimetallic cobalt(ii) and copper(ii)-based metal-organic framework (Co/Cu-MOF) immobilized pectin-modified Fe3O4 magnetic nanocomposite was designed and fabricated. Fe3O4 nanoparticles were modified in situ by pectin and, subsequently, used as a support for growing Co/Cu-MOF [Fe3O4/pectin/(Co/Cu)MOF]. The properties of the nanocomposite were investigated by FT-IR, XRD, SEM, EDS, VSM, STA, and BET. The nanocomposite exhibited both magnetic characteristics and a high surface area, making it a suitable candidate for catalytic applications. Then, the Fe3O4/pectin/(Co/Cu)MOF nanocomposite was utilized in the Biginelli reaction for the production of biologically active dihydropyrimidinones. Due to paramagnetism, Fe3O4/pectin/(Co/Cu)MOF was easily recovered and reused in six cycles without significant loss in reactivity. This green method comprises several benefits, such as mild reaction conditions, free-solvent media, high yields, easy workup, short reaction times and reusability of the prepared catalyst.

Micro-particle-clay aided microporous support for removal of hydrocarbon toxicity from petroleum refinery wastewater in single-slope solar distillation

The removal of toxic hydrocarbon pollutants is not sustainable via conventional treatment technology. This research investigates the feasibility of a solar distillation (SSD) system to eliminate soluble hydrocarbon salts, stubborn organics, and separation of oil emulsion from petroleum refinery wastewater (PRW). The PRW collected from the petroleum refinery facility and hydrophilic micro-particle clay (MP-clay) samples were characterized following the ASTM and SEM techniques. The treatment process for the removal of total dissolved salts (TDS), biological oxygen demand (BOD), and separation of oil emulsion was monitored in the SSD still using MP-clay aided microporous filter support, at varying MP-clay concentrations (0.5–3.5 mg/L), pH (6.6–7.3), temperature (27–80 0C), and exposure time (1–18hrs) respectively. The results showed MP-clay as self-assembled monolayers on microporous support with a 98 % reduction in BOD concentration under optimum conditions: pH of 7.3, contact time of 9 hours, and MP-clay concentration of 3.2 mg/L. The TDS concentration decreased by 94 % at the optimal exposure time (15hrs) and temperature (48 0C) in SSD still. The investigation also examined the recyclability of MP-clay for oil content accumulation and water separation. The findings demonstrated MP-clay on reuse retained 90.5 % of its activity in water separation and established MP-clay can be operated to the optimum of 3 cycles, each lasting 60 minutes. After this period, reactivity loss becomes severe owing to lipase leakage and substrate obstruction. The research findings will help harness solar energy for environmentally friendly and cost-effective PRW remediation.

Reactive nitrogen losses from Canadian agricultural soils over 36 years

Agriculture is a major source of reactive nitrogen (Nr) losses through ammonia (NH3) volatilization, nitrous oxide (N2O) emissions and nitrate (NO3−) leaching. A Canadian Agricultural Nitrogen Budget for Reactive N (CANBNr) model was developed to estimate the nitrogen (N) balance in soils, including N removals by harvested crops and Nr losses for the years 1981–2016 across Canada. Annual N inputs to farmland include commercial fertilizer N, livestock manure N, symbiotic and asymbiotic biological N fixation and atmospheric N deposition of NOx and NH3. The total annual N input for Canadian farmland was 5528 Gg N (103.2 kg N ha−1) in 2016 where N removal by crops and Nr accounted for 72.5 % (74.9 kg N ha−1) and 13.4 % (13.9 kg N ha−1), respectively. The Nr losses from N2O emissions, NH3 volatilization and NO3− leaching accounted for 64 Gg N (1.2 kg N ha−1), 330 Gg N (6.2 kg N ha−1) and 348 Gg N (6.5 kg N ha−1), which represents between1.2–6.3 % of total N input. A total of 777 Gg N (14.5 kg N ha−1) remained in the soil as surplus N (14.1 % of total N input), which could be available to subsequent crops in dryer regions but might be subject to N2O loss through nitrification or denitrification processes or NO3− leaching following heavy rains in humid regions. Nitrous oxide and ammonia emissions increased over a 36-year period due to increased fertilizer N inputs. The percentage of N inputs that was estimated to be lost as Nr increased from 17.9 % in 1981 to the peak level of 19.8 % in 2001 and then declined to 13.4 % in 2016. Total N removal by crops increased at a greater rate than N input during the 2001–2016 period resulting in an increased N uptake by crops over the last 15 years. The improved management of fertilizer N for agricultural systems represents a key opportunity for both farmers and policy makers to further reduce Nr losses from Canadian farmland without negatively impacting productivity.

Zr-decorated hyper-cross-linked polymers for highly selective upgrading of furfural to furfuryl alcohol

In the present study, the ultra-large specific surface area Zr-decorated hyper-cross-linked polymers (HP) were firstly developed for the catalytic production of furfuryl alcohol (FOL) from furfural (FAL) using isopropanol as both the hydrogen source and solvent. Comprehensive characterizations were performed to uncover the basic physicochemical properties. The as-prepared Zr/HP showed large specific surface area of ∼1000 m2/g, good dispersion of Zr species, plentiful acidity and basicity. 2.5Zr/HP presented the highest activity in the FAL-to-FOL transformation, wherein 97.4 % FAL conversion and 92.9 % FOL yield were achieved within 2 h at 160 °C. The recycling experiments revealed that the as-fabricated Zr-decorated hyper-cross-linked polymers presented good recyclability without significant loss of reactivity even after two consecutive cycles, owing to the strong interaction between hyper-cross-linked polymers and grafted Zr species. Kinetical analysis verified that the activation energy for transfer hydrogenation of FAL could be lowered to a certain degree, especially in the case of lower Zr loadings. More gratifyingly, the Zr-decorated hyper-cross-linked polymers were capable of catalyzing other unsaturated compounds with high conversion rates. In addition, the plausible pathway for the FAL-to-FOL transformation over Zr-decorated hyper-cross-linked polymers was proposed.