Acceleration Of Reaction Research Articles

MXene quantum dots-Co(OH)2 heterojunction stimulated Co2+δ sites for boosted alkaline hydrogen evolution

Persevering structural stability of the active species after phase reconfiguration poses a key challenge for various sustainable catalytic systems. In this study, we construct a robust β-Co(OH)2 electrocatalyst via self-adaptive coordination of MXene quantum dots (MQDs) during phase transition from the Co2(OH)3Cl precursor to β-Co(OH)2 (MQDs/β-Co(OH)2/Co foam). The heterojunction induced the excellent electron transfer, causing the lattice strain of β-Co(OH)2, and the accumulated electrons at the MQDs end regulated the electronic density of Co sites (Co2+δ), reversing the structural instability of β-Co(OH)2 within the applied reduction potential range. Furthermore, density functional theory calculation confirms the role of well-matched heterogeneous interfaces in HER. The result shows the high-valance Co2+δ sites promote adsorption and dissociation of H2O, increasing proton supply and accelerating reaction rate. Concurrently, MQDs facilitate the adsorption of hydrogen intermediates and H2 generation. Our architected catalyst exhibited exceptional alkaline hydrogen evolution reactions (HERs) performance (91 mV@10 mA cm−2) and superior stability outperforms most reported β-Co(OH) 2-based catalysts. Our work demonstrates the efficacy of MQDs as co-catalysts in enhancing the activity and structural stability of catalysts.

Single feed droplet–catalyst particle collision in a liquid containing gas–solid fluidized bed to convert fructose to value-added chemicals

Carbohydrates, comprising C6 sugars, dehydrate to form furfural (FUR) and 5- hydroxymethyl furfural (HMF). HMF is an intermediate for value-added specialty chemicals like 2,5-diformyl furan (DFF) and 2,5-furandi carboxylic acid, a monomer for polyethylene furaonate. Atomizing sugar solutions into catalytic fluidized beds operating beyond the caramelization temperature, Tcarm, accelerates reaction rates while avoiding humins, which are color forming agents characteristic of liquid phase processes. However, droplets partially coat particles in the spray zone and agglomerate due to liquid cohesive forces, which reduces heat transfer rates at the micro-scale and degrades reaction rates at the macro-scale. Here, we developed a CFD model to study the collision between a single feed droplet and a catalytic particle above Tcarm. We focused on evaluating the evaporation rate and heat transfer between the droplet and particle to promote vaporization the liquid feed, and assessing the impact of bed temperature, liquid feed rate, and superficial gas velocity. The highest DFF and furfural selectivity obtained are 17% and 24%, respectively, and these values are correlated to the maximum coke formation and agglomeration of 0.6% and 12g. However, the corresponding heat transfer and mass transfer are among the lowest values of 40% and 0.5W.

Au@AuPd Core-Alloyed Shell Nanoparticles for Enhanced Electrocatalytic Activity and Selectivity under Visible Light Excitation.

Plasmonic catalysis has been employed to enhance molecular transformations under visible light excitation, leveraging the localized surface plasmon resonance (LSPR) in plasmonic nanoparticles. While plasmonic catalysis has been employed for accelerating reaction rates, achieving control over the reaction selectivity has remained a challenge. In addition, the incorporation of catalytic components into traditional plasmonic-catalytic antenna-reactor nanoparticles often leads to a decrease in optical absorption. To address these issues, this study focuses on the synthesis of bimetallic core@shell Au@AuPd nanoparticles (NPs) with ultralow loadings of palladium (Pd) into gold (Au) NPs. The goal is to achieve NPs with an Au core and a dilute alloyed shell containing both Au and Pd, with a low Pd content of around 10 atom %. By employing the (photo)electrocatalytic nitrite reduction reaction (NO2RR) as a model transformation, experimental and theoretical analyses show that this design enables enhanced catalytic activity and selectivity under visible light illumination. We found that the optimized Pd distribution in the alloyed shell allowed for stronger interaction with key adsorbed species, leading to improved catalytic activity and selectivity, both under no illumination and under visible light excitation conditions. The findings provide valuable insights for the rational design of antenna-reactor plasmonic-catalytic NPs with controlled activities and selectivity under visible light irradiation, addressing critical challenges to enable sustainable molecular transformations.

Enhancing fluidity and mechanical properties in Limestone Calcined Clay cements with one-third Portland clinker content

Limestone Calcined Clay Cements (LC3) are attracting considerable attention due to their low CO2 footprints and relatively fast hydration kinetics. LC3-50 formulations (approximately 50 % Portland clinker, 30 % kaolinitic calcined clay, 15 % limestone and 5 % gypsum) are being extensively investigated and the hydration chemistry, rheology, mechanical strength developments and durability performances are starting to be well established. LC3 binders with lower clinker factors are possible, offering an opportunity for further CO2 footprint reduction. However, these blends have been much less studied. This work contributes to fill this gap. Here, a LC3-35 binder (i.e. 35 % Portland clinker content) is investigated and its performances are compared to those of the original Portland cement (PC) and a standard LC3-50 binder. The effects of two superplasticizers and a strength-enhancing admixture are thoroughly investigated in mortars and pastes. Larger calcined clay contents result in an exacerbation of the slump retention problem, but this issue is solved by the use of a new superplasticizer. Moreover, the low mechanical strengths at early ages can be partly mitigated with a C-S-H nucleation seeding admixture. Employing the right admixtures, LC3-35 binders can develop strength values similar to those of neat PC and LC3-50 at 7 and 28 days. The laboratory X-ray powder diffraction results for LC3-35 pastes, when using the strength-enhancing admixture, show that C4AF exhibits an accelerated reaction rate, leading to the formation of larger amounts of AFt and AFm phases. Approximate mass balance calculations are carried out to estimate the metakaolin reaction degree. Finally, an environmental performance indicator is used to place the footprints of the reported binders within the LC3 landscape.

Catalyst-free selective oxidation of C(sp3)-H bonds in toluene on water

The anisotropic water interfaces provide an environment to drive various chemical reactions not seen in bulk solutions. However, catalytic reactions by the aqueous interfaces are still in their infancy, with the emphasis being on the reaction rate acceleration on water. Here, we report that the oil-water interface activates and oxidizes C(sp3)-H bonds in toluene, yielding benzaldehyde with high selectivity (>99%) and conversion (>99%) under mild, catalyst-free conditions. Collision at the interface between oil-dissolved toluene and hydroxyl radicals spontaneously generated near the water-side interfaces is responsible for the unexpectedly high selectivity. Protrusion of free OH groups from interfacial water destabilizes the transition state of the OH-addition by forming π-hydrogen bonds with toluene, while the H-abstraction remains unchanged to effectively activate C(sp3)-H bonds. Moreover, the exposed free OH groups form hydrogen bonds with the produced benzaldehyde, suppressing it from being overoxidized. Our investigation shows that the oil-water interface has considerable promise for chemoselective redox reactions on water without any catalysts.

Label-free and ultrasensitive detection of environmental lead ions based on spatially localized DNA nanomachines driven by hyperbranched hybridization chain reaction

A label-free fluorescent sensing strategy for the rapid and highly sensitive detection of Pb2+ was developed by integrating Pb2+ DNAzyme-specific cleavage activity and a tetrahedral DNA nanostructure (TDN)-enhanced hyperbranched hybridization chain reaction (hHCR). This strategy provides accelerated reaction rates because of the highly effective collision probability and enriched local concentrations from the spatial confinement of the TDN, thus showing a higher detection sensitivity and a more rapid detection process. Moreover, a hairpin probe based on a G-triplex instead of a G-quadruplex or chemical modification makes hybridization chain reaction more controlled and flexible, greatly improving signal amplification capacities and eliminating labeled DNA probes. The enhanced reaction rates and improved signal amplification efficiency endowed the biosensors with high sensitivity and a rapid response. The label-free detection of Pb2+ based on G-triplex combined with thioflavin T can be achieved with a detection limit as low as 1.8 pM in 25 min. The proposed Pb2+-sensing platform was also demonstrated to be applicable for Pb2+ detection in tap water, river water, shrimp, rice, and soil samples, thus showing great potential for food safety and environmental monitoring.

Experimentally Delineating the Catalytic Effect of a Single Water Molecule in the Photochemical Rearrangement of the Phenylperoxy Radical to the Oxepin-2(5H)-one-5-yl Radical.

Catalysis plays a pivotal role in both chemistry and biology, primarily attributed to its ability to stabilize transition states and lower activation free energies, thereby accelerating reaction rates. While computational studies have contributed valuable mechanistic insights, there remains a scarcity of experimental investigations into transition states. In this work, we embark on an experimental exploration of the catalytic energy lowering associated with transition states in the photorearrangement of the phenylperoxy radical-water complex to the oxepin-2(5H)-one-5-yl radical. Employing matrix isolation spectroscopy, density functional theory, and post-HF computations, we scrutinize the (photo)catalytic impact of a single water molecule on the rearrangement. Our computations indicate that the barrier heights for the water-assisted unimolecular isomerization steps are approximately 2-3 kcal mol-1 lower compared to the uncatalyzed steps. This decrease directly coincides with the energy difference in the required wavelength during the transformation (Δλ = λ546nm - λ579nm ≡ 52.4-49.4 = 3.0 kcal mol-1), allowing us to elucidate the differential transition state energy in the photochemical rearrangement of the phenylperoxy radical catalyzed by a single water molecule. Our work highlights the important role of water catalysis and has, among others, implications for understanding the mechanism of organic reactions under atmospheric conditions.

COMPARATIVE STUDY OF THE DYNAMIC BEHAVIOR OF BACTERIAL PHOTOREGULATED ADENYLATE CYCLASES BPAC AND OAPAC

Photoregulated adenylate cyclases bPAC and OaPAC are compared using classical molecular dynamics simulations in both states, before and after blue light irradiation. The pathways of signal transduction from the photoreceptor to the catalytic domain are determined. The more pronounced acceleration of the catalytic reaction rate as a result of light irradiation in the case of bPAC is explained both by a shift in equilibrium towards a closed conformation and by a larger number of suboptimal pathways of allosteric signal transduction from photoreceptor to catalytic domain

Stearic acid-coated plasmonic Ag nanoparticles as a dual catalyst for enhanced NiO chemo and photo catalysis

The phenomenon of Localized Surface Plasmon Resonance (LSPR) in plasmonic metal nanoparticles causes a strong absorption of visible light and leads to the generation of hot electrons on the surface and the creation of localized electromagnetic fields near the surface. This characteristic enhances the catalytic performance of a plasmonic metal Ag–NiO nanocomposite (NiO-SNP) when exposed to low-flux visible light irradiation. The NiO-SNP was synthesized using a simple and cost-effective ultrasonication method. Its structural, morphological, and optical properties were analyzed, confirming the formation of nanocomposites. The proximity of stearic acid-coated Ag nanoparticles (SNP) acts as visible light-harvesting antennas, promoting NiO's activity for effectively reducing paracetamol (PM) drugs. The improved catalytic property is attributed to an electron relay effect, while the strong electromagnetic fields generated by irradiated Ag nanoparticles facilitate the concentration of PM molecules at active sites, leading to accelerated reaction rates. NiO-SNP2 demonstrates remarkable PM degradation: 97 % in tap water and 82.6 % in deionized water within 10 min, demonstrating its catalytic effectiveness. The plasmonic SNP mechanism in NiO-SNP1 nanocomposites enhances photocatalytic efficiency by up to 90 %, owing to efficient charge separation and transfer, resulting in a notable 1.5-fold increase in PM degradation. The degradation kinetics follow a pseudo-first-order model, with rate constants (k) ranging from approximately 0.059 to 0.6104 min⁻1, underscoring the crucial role of Ag nanoparticles in enhancing photocatalytic activity and degradation efficiency. Catalysis and visible light photocatalysis are significantly improved with increasing concentrations of NiO and SNP, respectively. This research could inspire a new approach to transforming traditional metal catalysis into plasmonic-metal catalysis.

A unified discontinuous Galerkin formulation for interfacial multiphysics modeling of thermo-chemically driven fracture

Many engineering and natural materials exhibit coupled thermo-chemo-mechanical phenomena, which can result in embrittlement and fracture. These fractures, in turn, can alter the subsequent thermal, chemical, and mechanical response. We present a theoretical formulation and computational framework for the analysis of thermo-chemically fractured solids, with emphasis on the post-fracture thermal and chemical interfacial behavior. The theoretical model is based on the thermodynamically-consistent formulation of Loeffel and Anand (IJP, 2011). The computational method extends the scalable discontinuous Galerkin/Cohesive Zone Model (DG/CZM) of Radovitzky et al. (CMAME, 2011) to thermo-chemo-mechanics, which facilitates coupled, large-scale simulations of materials and structures containing failed interfaces. In the proposed framework, all balance laws are enforced weakly via the DG formalism, resulting in a unified formulation for multiphysics problems in solids. This naturally enables the incorporation of general interface models, e.g. to account for effects such as the aeolotropic reduction in thermochemical transport due to the presence of fractures, or the acceleration of chemical reactions along crack flanks. The approach is verified against two analytical solutions of boundary value problems drawn from thermo-poro-elasticity and thermally-driven delamination. A scalable, three-dimensional simulation of thermochemically-driven concrete cracking illustrates the complete capabilities of the interfacial multiphysics modeling framework.

Engineering nickel-supported osmium bimetallic nanozymes with specifically improved peroxidase-like activity for immunoassay

Researchers have shown significant interest in modulating the peroxidase-like activity of nanozymes. Among these, bimetallic nanozymes have shown superior peroxidase-like activity over monometallic counterparts, offering enhanced performance and cost-efficiency in nanozyme designs. Herein, bimetallic nanozymes comprising nickel (Ni) and osmium (Os) incorporated into hyaluronate (HA) have been developed, resulting in HA-Nin/Os nanoclusters. Subsequently, comprehensive characterizations have been conducted. Further investigation has revealed that HA-Nin/Os efficiently catalyzed 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation with hydrogen peroxide (H2O2), confirming its peroxidase-like behavior and role as a nanozyme. Impressively, HA-Ni2/Os (Ni/Os = 2:1) displays heightened substrate affinity, accelerated reaction rates, enhanced hydroxyl radical production in acidic conditions, and exhibits activity unit of 1224 U/mg, representing more than two-fold increase compared to non-Ni-supported Os nanozyme. Theoretical calculations indicate that Ni support enhances the peroxidase-like process of Os nanozyme by improving H2O2 adsorption and TMB oxidation. Crucially, the support of Ni does not significantly alter the other enzyme-like activities of Os nanozymes, thereby enabling Ni to selectively enhance their peroxidase-like activity. In terms of application, the peroxidase-like ability of HA-Ni2/Os, facilitated by HA's carboxyl groups enabling crosslinking, proves effective in a squamous carcinoma antigen immunoassay. Moreover, HA-Ni2/Os exhibit reliable stability, promising as a peroxidase substitute. This work underscores the advantages of incorporating Ni into Os, specifically enhancing peroxidase-like activity, highlighting the potential of Os bimetallic nanozymes for peroxidase-based applications.

Chronoamperometric investigations on electrochemical synthesis of iron nitrides in molten salt system

A systematic investigation of the electrochemical iron nitride synthesis in a LiCl/KCl salt melt at 723 K shows an optimum of ϵ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\epsilon$$\\end{document}-Fe3\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_3$$\\end{document}N1+x\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_{1+x}$$\\end{document} formation in the range of 2.2 to 2.3 V and for γ′\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\gamma '$$\\end{document}-Fe4\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_4$$\\end{document}N between 2.4 and 2.5 V enabling the control of the desired iron nitride phase by setting the supplied terminal voltage. The product formation of iron nitrides starts when the electrochemical window is reached, which could be verified by linear sweep voltammetry. Hence, a maximum of nitrogen content in the formed iron nitride phases is observed for 2.27 V. During elongated synthesis periods, convection emerges as the predominant transport mechanism hindering an accelerated reaction rate with higher overpotential applied. Real-time analysis of the background current allows conclusions about the remaining nitride concentration. Additionally, there is concurrent iron nitride formation at the electrode surface through nitride adsorption and autonucleation-induced precipitation of iron and nitride ions. The analysis of the amount of sediment in comparison to the layer thickness of the nitrided working electrode suggests that the autonucleation mechanism dominates over the adsorption mechanism with increasing overpotential and can be further enhanced by this feature.Graphical abstract

Potential-dependent photo-electro-catalysis coupling mechanism for methanol oxidation: A case study over Pt/Cu-Nb2O5 nanorod arrays

The sluggish methanol oxidation kinetics has seriously hindered the development of direct methanol fuel cells. Photo-electro-catalysis is expected to accelerate reaction rates, yet suffers from lack of efficient photoelectrocatalysts and more importantly, less understanding on photo-electro-catalysis mechanism. Herein, a unique Cu-Nb2O5 nanorod array with excellent light adsorption and charge transfer ability, on which supports Pt nanoparticles, is constructed for photo-electrocatalytic methanol oxidation reaction (MOR). Systematical investigation discovers a potential-dependent photo-electro-catalysis coupling mechanism, i.e., at lower potential bias where the Fermi level of semiconductor (Ef,s) is beyond the Fermi level of Pt (Ef,Pt), electrons transferring from Pt to semiconductor is switched off, so semiconductor Cu-Nb2O5 alone takes a dominant role for both methanol and water activation; at higher potential bias where Ef,s is below Ef, Pt, electrons flowing from Pt to semiconductor is switched on, so methanol dehydrogenation on Pt surface is allowed energetically. Further investigation on the MOR processes prompts us to propose a MOR pathway that methanol dehydrogenates on Pt surface, with the aid of *OH from the photo-activated water on Cu-Nb2O5 to proceed via formaldehyde, formic acid to carbon dioxide, resulting to a low apparent activation energy and fast kinetics of MOR as compared to its counterpart Pt/Nb2O5. This work not only provides an efficient photoelectrocatalyst for methanol oxidation, but also sheds lights on the underlying photo-electro-catalysis coupling mechanism over semiconductor–metal catalysts.

PEG modification increases thermostability and inhibitor resistance of Bst DNA polymerase.

Polyethylene glycol modification (PEGylation) is a widely used strategy to improve the physicochemical properties of various macromolecules, especially protein drugs. However, its application in enhancing the performance of enzymes for molecular biology remains underexplored. This study explored the PEGylation of Bst DNA polymerase, determining optimal modification reaction conditions. In comparison to the unmodified wild-type counterpart, the modified Bst DNA polymerase exhibited significantly improved activity, thermal stability, and inhibitor tolerance during loop-mediated isothermal amplification. When applied for the detection of Salmonella in crude samples, the modified enzyme demonstrated a notably accelerated reaction rate. Therefore, PEGylation emerges as a viable strategy for refining DNA polymerases, helping in the development of novel molecular diagnostic reagents.

Innovative application of plasma-activated water in the inactivation of Escherichia coli: Temperature-dependent chemical processes leading to the synergistic microbicidal effect

Plasma-based technologies, including plasma-activated water (PAW), offer the capability to deactivate microorganisms on fruits and vegetables, preserving their sensory and nutritional quality. Although many studies have reported a synergistic microbicidal effect between PAW and mild heating, the underlying chemical processes driving these effects remain unexplored. Our study aims to evaluate the microbicidal capacity of two PAW types, one containing NO2− (PAW-N) and the other H2O2 (PAW-H), as well as their mixture (PAW-M), at different temperatures, and to elucidate the underlying temperature-dependent chemical processes. Using E. coli DH5α as the target microorganism, we measured colony-forming units under varying exposure times for each PAW type and their mixture at 8 and 28 °C. Additionally, we determined the time-dependent concentrations of NO2−, H2O2, and NO3− in the mixture, and calculated the reaction rate constant for peroxynitrous acid generation. The kinetic study revealed a fivefold increase in the reaction constant between H2O2 and NO2− in PAW-M at 28 °C compared to 8 °C, leading to a significant rise in hydroxyl radical production. The microbicidal efficacy of PAW-M exceeded that of individual PAWs or temperatures. Moreover, this effect was significantly enhanced by mild heating, resulting in log reductions of 0.24, 0.34, 2.3 (at 8 °C) and 0.74, 2.3, 3.6 (at 28 °C) for PAW-H, PAW-N, and PAW-M, respectively, after a 10-min exposure. In conclusion, the synergistic effect between PAW and mild heating may be attributed to the accelerated reaction rate of peroxynitrous acid formation in an acidic medium, leading to heightened hydroxyl radical generation.

One-pot Synthesis of PdCuAg and CeO2 Nanowires Hybrid with Abundant Heterojunction Interface for Ethylene Glycol Electrooxidation.

Introducing CeO2 into Pd-based nanocatalysts for electrocatalytic reactions is a good way to solve the intermediate toxicity problem and improve the catalytic performance. Here we reported a simple strategy to synthesize the PdCuAg and CeO2 nanowires hybrid via a one-pot synthesis process under strong nanoconfined effect of specific surfactant as templates. Owing to the structural (ultrathin nanowires, abundant heterojunction/interfaces between metal and metal oxide) and compositional (Pd, Cu, Ag, CeO2) advantages, the hybrid showed significantly enhanced catalytic activity (6.06 A mgPd -1) and stability, accelerated reaction rate, and reduced activation energy toward electrocatalytic ethylene glycol oxidation reaction.

Pt/Ni single-atom alloy boosts mechano-pyrolysis of alkane into hydrogen

Mechanochemistry approach was utilized to solve the carbon deposition during alkane pyrolysis process. Pt/Ni single-atom alloy (SAA) was constructed on Ni balls surface as catalyst and grinding medium simultaneously, and physical collision of metallic balls generated mechanical energy to remove the deposited carbon and accelerate reaction rates. XANES spectra proved Pt/Ni SAA structure on the Ni ball surface, and its turnover frequency (TOF) was 1530 h−1 under 1 atm and 450 °C without by-products. An extremely long lifetime of methane pyrolysis at least 350 h on stream has been obtained. This Pt/Ni SAA was also active for mechano-pyrolysis of ethane/propane, and DFT calculations confirmed that the improvement of catalytic efficiency originated from the d-band center up-shifting under mechanic stress on Pt/Ni SAA surface. This mechanical catalysis study provides an alternative route for clean hydrogen production and a strategy for deposited carbon removal under mechanical conditions.

Exploring a surface-capping role of carboxymethyl cellulose for the synthesis of silver nanoparticles via the induction period in a catalytic hydrogenation

The present study reported a dual role as a reducing agent and a stabilizer of carboxymethyl cellulose (CMC), a natural origin biopolymer, for the synthesis of silver nanoparticles (AgNPs) via a chemical reduction method. The operating parameters were optimized and established involving pH, reaction time, reaction temperature, AgNO3 molar concentration, CMC/Ag molar ratio. The formation of monodisperse AgNPs in the assistance of a CMC surface-capping agent thanks to an electrostatic stabilization effect was evidenced by ultraviolet-visible spectroscopy (UV–Vis), Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), and transmission electron microscope (TEM). The aqueous solution consisting of AgNPs in roughly spherical shape with a mean particle size of 24.3 nm was stable in ambient condition at least 2 months. The role of CMC as a surface-capping agent was also explored via the catalytic hydrogenation of methyl orange (MO) towards aromatic amines in the presence of NaBH4 at room temperature, revealing the induction period of 12 min before accelerating reaction rate in the next 18 min. At room temperature, such a catalytic hydrogenation of MO in water obeyed the pseudo first-order kinetic model with a rate constant of 0.2435 min−1 using 2.5 ppm CMC-capped AgNPs catalyst, and the reuse performance was remained in 5 consecutive cycles. To sum up, the present work shed light on a surface-capping role of carboxymethyl cellulose for the synthesis of silver nanoparticles by both physicochemical and catalytic studies.

Unveiling the Synergistic Role of Frustrated Lewis Pairs in Carbon-Encapsulated Ni/NiOx Photothermal Cocatalyst for Enhanced Photocatalytic Hydrogen Production.

The development of high-density and closely spaced frustrated Lewis pairs (FLPs) is crucial for enhancing catalyst activity and accelerating reaction rates. However, constructing efficient FLPs by breaking classical Lewis bonds poses a significant challenge. Here, this work has made a pivotal discovery regarding the Jahn-Teller effect during the formation of grain boundaries in carbon-encapsulated Ni/NiOx (Ni/NiOx@C). This effect facilitates the formation of high-density O (VO) and Ni (VNi) vacancy sites with different charge polarities, specifically FLP-VO-C basic sites and FLP-VNi-C acidic sites. The synergistic interaction between FLP-VO-C and FLP-VNi-C sites not only reduces energy barriers for water adsorption and splitting, but also induces a strong photothermal effect. This mutually reinforcing effect contributes to the exceptional performance of Ni/NiOx@C as a cocatalyst in photothermal-assisted photocatalytic hydrogen production. Notably, the Ni/NiOx@C/g-C3N4 (NOCC) composite photocatalyst exhibits remarkable hydrogen production activity with a rate of 10.7 mmol g-1 h-1, surpassing that of the Pt cocatalyst by 1.76 times. Moreover, the NOCC achieves an impressive apparent quantum yield of 40.78% at a wavelength of 380nm. This work paves the way for designing novel defect-state multiphase cocatalysts with high-density and adjacent FLP sites, which hold promise for enhancing various catalytic reactions.

Physicochemical synergistic effect of microwave-assisted Co-pyrolysis of biomass and waste plastics by thermal degradation, thermodynamics, numerical simulation, kinetics, and products analysis

Understanding the physicochemical synergistic effect of microwave-assisted co-pyrolysis (MACP) of biomass and waste plastics is crucial for efficient conversion and improving the quality of bio-oil. Thermal degradation, thermodynamics, and numerical simulation of co-pyrolysis of the corncob (CC) and polystyrene (PS) were conducted. Results showed that the co-pyrolysis of CC and PS had a positive physical synergistic and compatible effect in reducing energy consumption and accelerating reaction rate. The reaction kinetics analysis and pyrolysis products analysis found that the co-pyrolysis of CC and PS had a positive chemical synergistic effect. The co-pyrolysis both effectively reduced the pyrolysis activation energy and improved the yield and quality of bio-oil. Significantly, the sample of CC/PS (1:2) had the highest yield of bio-oil (52.3 wt%) and the highest relative content of aromatics (95.0 area%) in co-pyrolysis, while 450 °C was the most ideal pyrolysis temperature. This work indicated that the MACP of CC and PS showed a positive physicochemical synergistic effect, and provided theories and approaches for the production of bio-oil from the biomass and waste plastics by MACP.