Study on trifluoromethanesulfonic acid-promoted synthesis of daidzein: Process optimization and reaction mechanism

Daidzein has been widely used in pharmaceuticals,nutraceuticals,cosmetics,feed additives,etc.Its preparation process and related reaction mechanism need to be further investigated.A cost-effective process for synthesizing daidzein was developed in this work.In this article,a two-step synthesis of daidzein(Friedel–Crafts acylation and[5+1]cyclization)was developed via the employment of trifluoromethanesulfonic acid(TfOH)as an effective promoting reagent.The effect of reaction conditions such as solvent,the amount of TfOH,reaction temperature,and reactant ratio on the conversion rate and the yield of the reaction,respectively,was systematically investigated,and daidzein was obtained in 74.0%isolated yield under optimal conditions.Due to the facilitating effect of TfOH,the Friedel–Crafts acylation was completed within 10 min at 90℃ and the[5+1]cyclization was completed within 180 min at 25℃.In addition,a possible reaction mechanism for this process was proposed.The results of the study may provide useful guidance for industrial production of daidzein on a large scale.

Exploring nitrogen reduction reaction mechanisms in electrocatalytic ammonia synthesis:A comprehensive review

The electrochemical nitrogen reduction reaction(eNRR)holds significant promise as a sustainable alternative to the conventional large-scale Haber Bosch process,offering a carbon footprint-free approach for ammonia synthesis.While the process is thermodynamically feasible at ambient temperature and pressure,challenges such as the competing hydrogen evolution reaction,low nitrogen solubility in electrolytes,and the activation of inert dinitrogen(N_(2))gas adversely affect the performance of ammonia production.These hurdles result in low Faradaic efficiency and low ammonia production rate,which pose obstacles to the commercialisation of the process.Researchers have been actively designing and proposing various electrocatalysts to address these issues,but challenges still need to be resolved.A key strategy in electrocatalyst design lies in understanding the underlying mechanisms that govern the success or failure of the electrocatalyst in driving the electrochemical reaction.Through mechanistic studies,we gain valuable insights into the factors affecting the reaction,enabling us to propose optimised designs to overcome the barriers.This review aims to provide a comprehensive understanding of the various mechanisms involved in eNRR on the electrocatalyst surface.It delves into the various mechanisms such as dissociative,associative,Mars-van Krevelen,lithium-mediated nitrogen reduction and surface hydrogenation mechanisms of nitrogen reduction.By unravelling the intricacies of eNRR mechanisms and exploring promising avenues,we can pave the way for more efficient and commercially viable ammonia synthesis through this sustainable electrochemical process by designing an efficient electrocatalyst.

Synthesis methods and powder quality of titanium monocarbide

Titanium monocarbide(TiC),which is the most stable titanium-based carbide,has attracted considerable interest in the fields of energy,catalysis,and structural materials due to its excellent properties.Synthesis of high-quality TiC powders with low cost and high efficiency is crucial for industrial applications;however major challenges face its realization.Herein,the methods for synthesizing TiC powders based on a reaction system are reviewed.This analysis is focused on the underlying mechanisms by which synthesis methods affect the quality of powders.Notably,strategies for improving the synthesis of highquality powders are analyzed from the perspective of enhancing heat and mass transfer processes.Furthermore,the critical issues,challenges,and development trends of the synthesis technology and application of high-quality TiC powder are discussed.

Electrochemical synthesis of trimetallic nickel-iron-copper nanoparticles via potential-cycling for high current density anion exchange membrane water-splitting applications

Hydrogen is known for its elevated energy density and environmental compatibility and is a promising alternative to fossil fuels.Alkaline water electrolysis utilizing renewable energy sources has emerged as a means to obtain high-purity hydrogen.Nevertheless,electrocatalysts used in the process are fabricated using conventional wet chemical synthesis methods,such as sol-gel,hydrothermal,or surfactantassisted approaches,which often necessitate intricate pretreatment procedures and are vulnerable to post-treatment contamination.Therefore,this study introduces a streamlined and environmentally conscious one-step potential-cycling approach to generate a highly efficient trimetallic nickel-iron-copper electrocatalyst in situ on nickel foam.The synthesized material exhibited remarkable performance,requiring a mere 476 mV to drive electrochemical water splitting at 100 mA cm^(-2)current density in alkaline solution.Furthermore,this material was integrated into an anion exchange membrane watersplitting device and achieved an exceptionally high current density of 1 A cm^(-2)at a low cell voltage of2.13 V,outperforming the noble-metal benchmark(2.51 V).Additionally,ex situ characterizations were employed to detect transformations in the active sites during the catalytic process,revealing the structural transformations and providing inspiration for further design of electrocatalysts.

Synthesis of NO by rotating sliding arc discharge reactor with conical-spiral electrodes

The present work investigates the potential applications of nitrogen oxides(NO_(x)),particularly nitric oxide(NO)and nitrogen dioxide(NO_(2)),generated through discharge plasma in diverse sectors such as medicine,nitrogen fixation,energy,and environmental protection.In this study,a rotating sliding arc discharge reactor was initially employed to produce high concentrations of gaseous NO_(x),followed by the utilization of a molybdenum wire redox reactor for NO_(2)-to-NO conversion.The outcomes reveal that the discharge states and generations of NO_(x) are affected by varying parameters,including the applied energies,frequencies and airflow states(1.3-2.6 m/s are the laminar flow,2.6-5.2 m/s are the transition state,5.2-6.5 m/s are the turbulent flow),and the concentrations of NO_(x) within the arc discharge are higher than that in the spark discharge.Moreover,the concentrations of NO,NO_(2) and NO_(x) gradually increased,and the concentration ratios of NO/NO_(2) and NO_(x)/NO_(2) decreased with increasing the applied energy for one cycle from 14.8 mJ to 24.3 mJ.Meanwhile,the concentrations of NO,NO_(2) and NO_(x) gradually decreased,and the concentration ratios of NO/NO_(2) and NO_(x)/NO_(2) first decreased and then increased with increasing the applied frequencies from 5.0 kHz to 9.0 kHz.Further,the concentrations of NO,NO_(2) and NO_(x) gradually decreased,and the concentration ratios of NO/NO_(2) and NO_(x)/NO_(2) first increased and then decreased with increasing the air flow speeds from 1.3 m/s to 6.5 m/s.Lastly,the concentrations of NO increased and NO_(2) decreased with increasing temperature from 25℃ to 400℃ using molybdenum converted.These findings provide experimental support for the application of plasma in the fields of medicine,nitrogen fixation,energy and environmental protection.

Atomically Adjustable Rhodium Catalyst Synthesis with Outstanding Mass Activity via Surface-Li mi ted Cation Exchange

Rh has been widely studied as a catalyst for the promising hydrazine oxidation reaction that can replace oxygen evolution reactions for boosting hydrogen production from hydrazine-containing wastewater.Despite Rh being expensive,only a few studies have examined its electrocatalytic mass activity.Herein,surface-limited cation exchange and electrochemical activation processes are designed to remarkably enhance the mass activity of Rh.Rh atoms were readily replaced at the Ni sites on the surface of NiOOH electrodes by cation exchange,and the resulting RhOOH compounds were activated by the electrochemical reduction process.The cation exchange-derived Rh catalysts exhibited particle sizes not exceeding 2 nm without agglomeration,indicating a decrease in the number of inactive inner Rh atoms.Consequently,an improved mass activity of 30 A mg_(Rh)^(-1)was achieved at 0.4 V versus reversible hydrogen electrode.Furthermore,the two-electrode system employing the same CE-derived Rh electrodes achieved overall hydrazine splitting over 36 h at a stable low voltage.The proposed surface-limited CE process is an effective method for reducing inactive atoms of expensive noble metal catalysts.

Porous TiFe_(2) intermetallic compound fabricated via elemental powder reactive synthesis

Porous intermetallics show potential in the field of filtration and separation as well as in the field of catalysis.Herein,porous Ti Fe2intermetallics were fabricated by the reactive synthesis of elemental powders.The phase transformation and pore formation of porous TiFe2intermetallics were investigated,and its corrosion behavior and hydrogen evolution reaction(HER)performance in alkali solution were studied.Porous TiFe2intermetallics with porosity in the range of 34.4%-56.4%were synthesized by the diffusion reaction of Ti and Fe elements,and the pore formation of porous TiFe2intermetallic compound is the result of a combination of the bridging effect and the Kirkendall effect.The porous TiFe2samples exhibit better corrosion resistance compared with porous 316L stainless steel,which is related to the formation of uniform nanosheets on the surface that hinder further corrosion,and porous TiFe2electrode shows the overpotential of 220.6 and 295.6 mV at 10 and 100 mA·cm-2,suggesting a good catalytic performance.The synthesized porous Fe-based intermetallic has a controllable pore structure as well as excellent corrosion resistance,showing its potential in the field of filtration and separation.

Continuous,efficient and safe synthesis of 1-oxa-2-azaspiro[2.5]octane in a microreaction system

1-Oxa-2-azaspiro[2.5]octane,as one of N-H oxaziridines,is a selective electrophilic aminating agent for N-,S-,C-,and O-nucleophiles.It has the features of stereoselectivity and the absence of formation of strongly acidic or basic byproducts,leading to considerable interest in the development of organic synthetic methods.Currently,the economically feasible route of production of 1-oxa-2-azaspiro[2.5]octane is the reaction of cyclohexanone with ammonia and sodium hypochlorite.However,due to strong exothermic reactions,massive gas release and heterogeneous reaction,the controllability,efficiency and safety of the reaction are in great difficulty using batch technology.In this paper,a microreaction system containing predispersion,reaction and phase separation was introduced into the preparation of 1-oxa-2-azaspiro[2.5]octane.The research results showed that precise control of the process including droplet dispersion,temperature control,reaction time control and fast continuous phase separation,was the key to process intensification.Under optimal conditions,the concentration of 1-oxa-2-azaspiro[2.5]octane in product obtained by microreaciton system(~2.0 mol·L^(-1))was much higher than that obtained by batch technology(0.2-0.4 mol·L^(-1)),which demonstrated that the continuous-flow synthesis would be a more efficient substitute for batch synthesis.Meanwhile,the results of the derivation experiments also showed that the aminating agent solution with higher concentration was more advantageous in the applications.

Selective synthesis of nitrate from air using a plasma-driven gas-liquid relay reaction system

The direct oxidation of nitrogen is a potential pathway to achieving the zero-carbon-emission synthesis of nitric acid or nitrate, because it does not involve ammonia synthesis and additional ammonia oxidation processes. However, the slow kinetics of nitrogen oxidation and the difficult selective control of oxidation products hinder the development of this process. In this study, a plasma-driven gas-liquid relay reaction system was developed to overcome these limitations. A typical feature of this reaction system is that it can efficiently generate NO_x under plasma exposure;moreover, the specific anions in the absorption solution can be oxidized to strong oxidants capable of relay oxidation of low-valence nitrogen oxides. This feature allows for the deep oxidation of nitrogen, thus enabling the oxidation products of nitrogen to exist in high-valence states in the absorption solution. For experimental verification, we achieved the 100% selective synthesis of nitrate under plasma exposure, with air as the supply gas and a sodium sulfate solution as the absorption solution.

Microbial synthesis of N, P co-doped carbon supported PtCu catalysts for oxygen reduction reaction

Developing highly efficient and stable platinum-based electrocatalyst for oxygen reduction reaction(ORR) is critical to expediting commercialization of fuel cells.Herein,several PtCu alloy nanocatalysts supported on N,P co-doped carbon(PtCu/NPC) were prepared by microbial-sorption and carbonization-reduction.Among them,PtCu/NPC-700 ℃ exhibits excellent catalytic performance for ORR with a mass activity of 0.895 A mg_(pt)^(-1)(@0.9 V) which is 8.29 folds of commercial Pt/C.Additionally,the ECSA and MA of PtCu/NPC-700℃ only decrease by 14.2% and 18.7% respectively,while Pt/C decreases by 35.2% and 52.8% after 10,000 cycles of ADT test.Moreover,the PtCu/NPC-700℃ catalyst emanates a maximum power density of 715 mW cm^(-2) and only 11.1% loss of maximum power density after 10,000 ADTs in single-cell test,indicating PtCu/NPC-700℃ also manifests higher activity and durability in actual single-cell operation than Pt/C.This research provides an easy and novel strategy for developing highly active and durable Pt-based alloy catalyst.

Synthesis strategies of covalent organic frameworks: An overview from nonconventional heating methods and reaction media

Covalent organic frameworks(COFs), as an emerging class of porous crystalline materials constructed by covalent links between the building monomers, have gained tremendous attention. Over the past 15 years, COFs have made rapid progress and substantial development in the chemistry and materials fields. However, the synthesis of COFs has been dominated by solvothermal methods for a long time and it usually involves high temperature, high pressure and toxic organic solvents, which created many challenges for environmental considerations. Recently,the exploration of new approaches for facile fabrication of COFs has aroused extensive interest. Hence, in this review, we comprehensively describe the synthetic strategies of COFs from the aspects of nonconventional heating methods and reaction media. In addition, the advantages,limitations and properties of the preparation methods are compared. Finally, we outline the main challenges and development prospects of the synthesis of COFs in the future and propose some possible solutions.

Binary molten salt in situ synthesis of sandwich-structure hybrids of hollowβ-Mo2C nanotubes and N-doped carbon nanosheets for hydrogen evolution reaction

Focused exploration of earth-abundant and cost-efficient non-noble metal electrocatalysts with superior hydrogen evolution reaction(HER)performance is very important for large-scale and efficient electrolysis of water.Herein,a sandwich composite structure(designed as MS-Mo2C@NCNS)ofβ-Mo2C hollow nanotubes(HNT)and N-doped carbon nanosheets(NCNS)is designed and prepared using a binary NaCl–KCl molten salt(MS)strategy for HER.The temperature-dominant Kirkendall formation mechanism is tentatively proposed for such a three-dimensional hierarchical framework.Due to its attractive structure and componential synergism,MS-Mo2C@NCNS exposes more effective active sites,confers robust structural stability,and shows significant electrocatalytic activity/stability in HER,with a current density of 10 mA cm-2 and an overpotential of only 98 mV in 1 M KOH.Density functional theory calculations point to the synergistic effect of Mo2C HNT and NCNS,leading to enhanced electronic transport and suitable adsorption free energies of H*(ΔGH*)on the surface of electroactive Mo2C.More significantly,the MS-assisted synthetic methodology here provides an enormous perspective for the commercial development of highly active non-noble metal electrocatalysts toward efficient hydrogen evolution.

Microwave direct synthesis and thermoelectric properties of Mg_(2)Si by solid-state reaction

In order to reduce the oxidation and volatilization caused by Mg element in the traditional methods for synthesizing Mg2Si compounds,Mg2Si thermoelectric materials were prepared by solid state reaction and microwave radiation techniques.Structure and phase composition of the materials were investigated by X-ray diffraction.The electrical conductivity,Seebeck coefficient and thermal conductivity were measured as a function of temperature from 300 to 700 K.It is found that high purity Mg2Si powders can be obtained with excessive content of 8% Mg from the stoichiometric Mg2Si at 853 K and 2.5 kW for 30 min.A maximum dimensionless figure of merit,ZT,of about 0.13 was obtained for Mg2Si at 600 K.

Optimization of reaction for synthesis of polyisobutylene amine between amination agent and epoxy polyisobutylene

An optimization study on the amination reaction of epoxy polyisobutylene for synthesis of polyisobutylene amine is presented. The experimental results indicate that n-butanol and ethylenediamine are the suitable solvent and amination agents for the reaction, respectively. The reaction yield of the amination reaction is notably increased with the enhanced molar ratio of either n-butanol against epoxy polyisobutylene or ethylenediamine against epoxy polyisobutylene. Also, the yield is enhanced with increasing temperature and time during the experimental range. Strikingly, the yield reaches as high as 91. 30% under optimal conditions; with the molar ratio of ethylenediamine, n-butanol and PIBO of 10∶ 6∶ 1, the reaction temperature of 150 ℃ and the reaction time of 6 h. In addition, the yield of the reaction is slightly decreased with the enhanced water content of the system. Accordingly, the mass concentration of water should be controlled within 1. 7% during the reaction.

Recent advances in quantum dot catalysts for hydrogen evolution:Synthesis,characterization,and photocatalytic application

Photocatalytic water splitting is beneficial for the effective mitigation of global energy and environmental crises.Owing to multi-exciton generation,impressive light harvesting,and excellent photochemical properties,the quantum dot(QD)-based catalysts reveal a considerable potential in photocatalytic hydrogen(H_(2))production compared with bulk competitors.In this review,we summarize the recent advances in QDs for photocatalytic H_(2) production by enumerating different synthetic and characterization strategies for QDs.Various QDs-based photocatalysts are introduced and summarized in categories,and the role of different QDs in varied systems,as well as the mechanism and key factors that enhance the photocatalytic H_(2) generation performance,is discussed.Finally,conclusions and future perspectives in the exploration of highly efficient QDs-based photocatalysts for innovative applications are highlighted.

Synthesis, performance and structure characterization of glyoxal-monomethylolurea-melamine (G-MMU-M) co-condensed resin

In order to reduce the formaldehyde emission of formaldehyde-based wood adhesive from the source,it is aimed to develop a novel co-condensed resin of glyoxal-monomethylolurea-melamine(G-MMU-M).A series of G-MMU-M resins with various formulations of raw materials were successfully prepared.The basic properties and bonding performance of the G-MMU-M resins were determined.Furthermore,the structures of resins were characterized by FTIR,^(13)C NMR,XPS,and ESI-MS.The results show that the prepared G-MMU-M resin remains stable for 30 d,meanwhile,the dry and wet bonding strength of the plywoods bonded with the resins,solid content and viscosity are influenced greatly by the addition amount of melamine and MMU/G molar ratio.The G-MMU-M resins with MMU/G molar ratio of 0.9:1.0 and 8% melamine exhibit the highest dry and bonding strength of 1.98 MPa and 1.27 MPa,increased by 34% and 63%,respectively,in comparison with glyoxal-monomethylolurea(G-MMU)resin.In the G-MMU-M resins,there were four main oligomers including M—CH(—^(+)CH-MMU)-O-MMU,M-CH(—CH_(2)OH)-MMU-O-MMU,M—CH(—OH)—^(+)CH-MMU-O-MMU,and M—CH(—^(+)CH-MMU)-MMU-p-G.

Iron Atom-Cluster Strategy Synthesis of Hierarchically Porous Fe-N-C Catalysts for Proton Exchange Membrane Fuel Cells

Developing nonprecious metal-nitrogen-doped carbon(M-N-C)catalysts with high activity and stability is critical to their widespread use in fuel cells;however,these catalysts still face considerable challenges.Herein,a novel iron atom-cluster strategy for the synthesis of iron-based N-C catalyst comprising Fe nanoparticles(Fe NPs)surrounded by Fe-N_(x) sites is developed for oxygen reduction reactions in an acidic fuel cell.Iron oxide NPs were incorporated into zeolitic imidazolate framework-8(ZIF-8)-derived carbon materials and pyrolyzed at high temperatures using NaCl as a modifi er to produce Fe NPs and Fe-N_(x) composite active sites.The half-wave potential of the optimized Fe_(NP)/FeNC-NaCl material was substantially improved to 0.81 V.Furthermore,even after 15,000 cycles,the half-wave potential of the catalyst remained essentially unchanged.As a cathode catalyst for fuel cells,it realized a high peak power density of 436 mW/cm^(2)under a practical H_(2)-air atmosphere.Therefore,this study presents a new approach for designing and synthesizing electrocatalytic materials with high catalytic activity and stability.

Scalable solid-phase synthesis of defect-rich graphene for oxygen reduction electrocatalysis

Defect-engineered carbon materials have been emerged as promising electrocatalysts for oxygen reduction reaction(ORR)in metal-air batteries.Developing a facile strategy for the preparation of highly active nanocarbon electrocatalysts remains challenging.Herein,a low-cost and simple route is developed to synthesize defective graphene by pyrolyzing the mixture of glucose and carbon nitride.Molecular dynamics simulations reveal that the graphene formation is ascribed to two-dimensional layered feature of carbon nitride,and high compatibility of carbon nitride/glucose systems.Structural measurements suggest that the graphene possesses rich edge and topological defects.The graphene catalyst exhibits higher power density than commercial Pt/C catalyst in a primary Zn-air battery.Combining experimental results and theoretical thermodynamic analysis,it is identified that graphitic nitrogen-modified topological defects at carbon framework edges are responsible for the decent ORR performance.The strategy presented in this work can be can be scaled up readily to fabricate defective carbon materials.

Precisely Controlled Synthesis of Pt-Pd Octahedral Nanoframes as a Superior Catalyst towards Oxygen Reduction Reaction

Pt-based nanoframes represent a class of promising catalysts towards oxygen reduction reaction. Herein, we, for the first time, successfully prepared Pt-Pd octahedral nanoframes with ultrathin ridges less than 2 nm in thickness. The Pt-Pd octahedral nanoframes were obtained through site-selected deposition of Pt atoms onto the edge sites of Pd octahedral seeds, followed by selective removal of the Pd octahedral cores via chemical etching. Due to that a combination of three-dimensional opens geometrical structure and Pt-skin surface compositional structure, the Pt-Pd octahedral nanoframes/C catalyst shows a mass activity of 1.15 A/mgPt towards oxygen reduction reaction, 5.8 times enhancement in mass activity relative to commercial Pt/C catalyst （0.20 A/mgPt）. Moreover, even after 8000 cycles of accelerated durability test, the Pt-Pd octahedral nanoframes/C catalyst still exhibits a mass activity which is more than three times higher than that of pristine Pt/C catalyst.

Reaction Mechanism,Synthesis and Characterization of Urea-glyoxal(UG) Resin

The reaction mechanism of glyoxal （G） with urea （U） under weak acid condition was theoretically investigated at PW91/DNP/COSMO of quantum chemistry using density functional theory （DFT） method. The results show that the addition reaction of G with U under the conditions mainly involves the reactions of U with protonated glyoxal （p-G）, protonated 2,2-dihy- droxyacetaldehyde （p-G 1） and protonated bis-hemdiol （p-G2） to form two important carbocation reactive intermediates of C-p-UG and C-p-UG1, and two important hydroxyl compounds of UG and UG1. These compounds play important roles in the formation of UG resin. According to the result of quantum chemical calculation, UG resin was synthesized successfully under weak acid conditions. The UG resin was characterized by matrix assisted laser desorption ionization time of flight mass spectrometry （MALDI-TOF-MS）, ultraviolet and visible spectroscopy （UV-vis）, Fourier transform infrared spectroscopy （FT1R） and nuclear magnetic resonance spectroscopy （13CNMR and 1HNMR）. These instrumental analytical results agree with each other and further confirm the addition reaction pathway of glyoxal with urea proposed by quantum chemical calculation.