Site-specific deposition creates electron-rich Pd atoms for unprecedented C-H activation in aerobic alcohol oxidation

Here,we demonstrate a photochemical strategy to site-specifically deposit Pd atoms on Au nanoparticles.The high-sensitivity low-energy ion scattering spectra combined with the X-ray photoelectron spectra reveal that the surface electronic structure of Pd can be continuously regulated by tailoring the Pd-to-Au molar ratio and the location of Pd atoms in Au Pd nanoparticles.It is revealed that electron-rich Pd atoms are considerably more active than the net Pd atoms in aerobic alcohol oxidation.Remarkably,the catalyst with the most electron-rich Pd sites(binding energy downshift:1.0 e V)exhibits an extremely high turnover frequency(~500000 h-1 vs 12000 h-1 for that with net Pd atoms)for solvent-free selective oxidation of benzyl alcohol,which is,to the best of our knowledge,the highest value ever reported.Kinetic studies reveal that electron-rich Pd atoms can accelerate the oxidation of benzyl alcohol by facilitating C-H cleavage,as indicated by the significant reduction in the activation energy as compared to net Pd atoms.

Competition between C-C and C-H Activation in Reactions of Neutral Nickel Atom with Cycloalkanes （n = 3-7）

A theoretical investigation of the reaction mechanisms for C-H and C-C bond activation processes in the reaction of Ni with cycloalkanes C,,H2. （n = 3-7） is carried out. For the Ni ＋ CnH2, （n = 3, 4） reactions, the major and minor reaction channels involve C-C and C-H bond activations, respectively, whereas Ni atom prefers the attacking of C-H bond over the C-C bond in CnH2n （n = 5=7）. The results are in good agreement with the experimental study. In all cases, intermediates and transition states along the reaction paths of interest are characterized, It is found that both the C-H and C-C bond activation processes are proposed to proceed in a one-step manner via one transition state. The overall C-H and C-C bond activation processes are exothermic and involve low energy barriers, thus transition metal atom Ni is a good mediator for the activity of cycloalkanes CnH2n （n = 3 -7）.

Theoretical Study on the C-H Activation in Decarbonylation of Acetaldehyde by NiL_2(L=SO_3CH_3) Using Density Functional Theory

Density functional theory calculations were carried out to explore the potential energy surface（PES） associated with the gas-phase reaction of Ni L2（L=SO3CH3） with acetone. The geometries and energies of the reactants, intermediates, products and transition states of the triplet ground potential energy surfaces of [Ni, O, C2, H4] were obtained at the B3LYP/6-311＋＋G（d,p） levels in C,H,O atoms and B3LYP/ Lanl2 dz in Ni atom. It was found through our calculations that the decabonylation of acetaldehyde contains four steps including encounter complexation, C-C activation, aldehyde H-shift and nonreactive dissociation. The results revealed that C-C activation induced by Ni L2（L=SO3CH3） led to the decarbonylation of acetaldehyde.

Catalytic C-H activation-initiated transdiannulation:An oxygen transfer route to ring-fluorinated tricyclic γ-lactones

Catalytic C–H activation-initiated annulation reactions have emerged as a versatile strategy for the efficient construction of diverse ring structural units and complex cyclic molecules in synthetic chemistry.Herein,we describe a new Rh(Ⅲ)-catalyzed C–H activation-initiated transdiannulation reaction of N,Ndimethyl enaminones with gem-difluorocyclopropenes in the presence of H_(2)O,enabling a facile and oxygen transfer access to ring-fluorinated tricyclicγ-lactones with a 6-5 ring-junction tetrasubstituted stereocenter.This approach features bond-forming/annulation efficiency,good functional group tolerance and complete regioselectivity,which may include a complex process consisting of Rh(Ⅲ)-catalyzed C(sp2)–H activation,cyclic alkene insertion,defluorinated ring-opening of gem-difluorocyclopropane,intramolecular oxygen transfer,intramolecular cyclization and oxidative hydration.

Derivation of Benzothiadiazine-1,1-dioxide Scaffolds via Transition Metal-Catalyzed C-H Activation/Annulation

Comprehensive Summary Benzothiadiazine-1,1-dioxide scaffold is bioactive framework with wild utility and applications.Synthesis of benzothiadiazine-fused isoquinoline derivatives and spiro benzothiadiazine derivatives through transition metal-catalyzed C—H activation/annulation was reported.3-Phenyl-2H-benzothiadiazine-1,1-dioxide was used as the reaction substrate,and vinylene carbonate and 4-diazopyrazolone were used as the coupling reagents,respectively.This strategy provides straightforward access to complex N-heterocycles in a highly efficient and simple manner.

The marriage of dual-acceptor strategy and C-H activation polymerization:naphthalene diimide-based n-type polymers with adjustable molar mass and decent performance

The development of readily accessible high-mobility n-type semiconducting polymers is in great demand for realizing highperformance p-n junction-based organic electronics.In this study,we demonstrate that with the combination of dual-acceptor strategy and C-H direct arylation polymerization(DAr P),unipolar n-type semiconducting polymers can be conveniently synthesized.By tuning the monomer concentration,three dual-acceptor polymers,namely,poly(naphthalene diimide-alt-dithiophenyl pyrrolopyrrole-dione)(PNDI-DPP),poly(naphthalene diimide-alt-dithiophenyl isoindigo)(PNDI-IID),and poly(naphthalene diimide-alt-dithiophenyl bezothiadiazole)(PNDI-BT)can be obtained via C-H activation with decent number average molecular weight of~10 to 30 kg mol^(-1)and relatively narrow polydispersity index of~2.In addition,these polymers are defect-free in nature as evidenced by the nuclear magnetic resonance.Moreover,we attribute the different molar masses of the three copolymers under the same DAr P condition to the differentα-C-H acidity,which may stem from different electronwithdrawing capability of the hydrogenated acceptor units.Furthermore,the influence of the hydrogenated acceptor monomers on the optical,electrochemical and charge transporting properties is comprehensively studied.Among the three dual-acceptor polymers,PNDI-BT demonstrates the highest electron mobilities of up to 0.6 cm^(2)V^(-1)s^(-1)in unipolar n-type organic transistors because of its relatively planar backbone,larger overlaps of the lowest unoccupied molecular orbital and strong H-aggregation.Note that the transistor performance of PNDI-BT synthesized via C-H activation in this study is at least comparable to the one made by conventional C(sp^(2))-C(sp^(2))Stille or Suzuki cross-coupling polymerization.This study demonstrates the presented protocol can be a useful platform for sustainable and convenient synthesis of high-performance n-type semiconducting polymers.

Thermal pretreatment of willow branches impacts yield and pore development of activated carbon in subsequent activation with ZnCl_(2) via modifying cellulose structure

Development of pore structures of activated carbon(AC)from activation of biomass with ZnCl_(2) relies on content and structure of cellulose/hemicellulose in the feedstock.Thermal pretreatment of biomass could induce dehydration and/or aromatization to change the structure of cellulose/hemicellulose.This might interfere with evolution of structures of AC,which was investigated herein via thermal pretreatment of willow branch(WB)from 200 to 360℃and the subsequent activation with ZnCl_(2) at 550℃.The results showed that thermal pretreatment at 360℃(WB-360)could lead to substantial pyrolysis to form biochar,with a yield of 31.9%,accompanying with nearly complete destruction of cellulose crystals and remarkably enhanced aromatic degree.However,cellulose residual in WB-360 could still be activated to form AC-360 with specific surface area of 1837.9 m~2·g^(-1),which was lower than that in AC from activation of untreated WB(AC-blank,2077.8 m~2·g^(-1)).Nonetheless,the AC-200 from activation of WB-200 had more developed pores(2113.9 m~2·g^(-1))and superior capability for adsorption of phenol,due to increased permeability of ZnCl_(2) to the largely intact cellulose structure in WB-200.The thermal pretreatment did increase diameters of micropores of AC but reduced the overall yield of AC(26.8%for AC-blank versus 18.0%for AC-360),resulting from accelerated cracking but reduced intensity of condensation.In-situ infrared characterization of the activation showed that ZnCl_(2) mainly catalyzed dehydration,dehydrogenation,condensation,and aromatization but not cracking,suppressing the formation of derivatives of cellulose and lignin in bio-oil.The thermal pretreatment formed phenolic-OH and C=O with higher chemical innerness,which changed the reaction network in activation,shifting morphology of fibrous structures in AC-blank to“melting surface”in AC-200 or AC-280.

Acid mine drainage activation mechanism on lime-depressed pyrite flotation from copper sulfide ore

The lime-depressed pyrite from Cu differential flotation tailings with acid mine drainage(AMD)as a natural activator was recovered.The effect of AMD on lime-depressed pyrite flotation was investigated by a series of laboratory flotation tests and surface analytical techniques.Flotation test results indicated that AMD could effectively activate the pyrite flotation with a sodium butyl xanthate(SBX)collector,and a high-quality sulfur concentrate was obtained.Pulp ion concentration analysis results indicated that AMD facilitated desorption of Ca~(2+)and adsorption of Cu~(2+)on the depressed-pyrite surface.Adsorption measurements and contact angle analysis results confirmed that adding AMD improved the adsorption amount of SBX collector on the pyrite surface and increased the contact angle by 31°.Results of Raman spectroscopy and X-ray photoelectron spectroscopy analysis indicated that AMD treatment promoted the formation of hydrophobic species(S~0 hydrophobic entity and copper sulfides)and the removal of hydrophilic calcium and iron species on the pyrite surface,which reinforced the adsorption of collector.The findings of the present research provide important theoretical basis and technical support for a cleaner production of copper sulfide ores.

Zonal activation of molecular carbon dioxide and hydrogen over dual sites Ni-Co-MgO catalyst for CO_(2) methanation:Synergistic catalysis of Ni and Co species

An in-depth mechanism in zonal activation of CO_(2)and H2molecular over dual-active sites has not been revealed yet.Here,Ni-Co-MgO was rationally constructed to elucidate the CO_(2)methanation mechanism.The abundant surface nickel and cobalt components as active sites led to strong Ni-Co interaction with charge transfer from nickel to cobalt.Notably,electron-enriched Coδ-species participated in efficient chemisorption and activation of CO_(2)to generate monodentate carbonate.Simultaneously,plentiful available Ni0sites facilitated H2dissociation,thus CO_(2)and H2were smoothly activated at zones of Coδ-species and Ni0,respectively.Detailed in situ DRIFTS,quasi situ XPS,TPSR,and DFT calculations substantiated a new formate evolution mechanism via monodentate carbonate instead of traditional bidentate carbonate based on synergistic catalysis of Coδ-species and Ni0.The zonal activation of CO_(2)and H2by tuning electron behaviors of double-center catalysts can boost heterogeneous catalytic hydrogenation performance.

Using microglia-derived extracellular vesicles to capture diversity of microglial activation phenotypes following neurological injury

Microglia are one of the three glial cell populations in the central nervous system(CNS),along with astrocytes and oligodendrocytes.While microglia are unique among brain cells due to their hematologic origin and perform immune functions similar to peripheral macrophages,they are not simply macrophages of the CNS.

Strategies to achieve effective nitrogen activation

Ammonia serves as a crucial chemical raw material and hydrogen energy carrier.Aqueous electrocatalytic nitrogen reduction reaction(NRR),powered by renewable energy,has attracted tremendous interest during the past few years.Although some achievements have been revealed in aqueous NRR,significant challenges have also been identified.The activity and selectivity are fundamentally limited by nitrogen activation and competitive hydrogen evolution.This review focuses on the hurdles of nitrogen activation and delves into complementary strategies,including materials design and system optimization(reactor,electrolyte,and mediator).Then,it introduces advanced interdisciplinary technologies that have recently emerged for nitrogen activation using high-energy physics such as plasma and triboelectrification.With a better understanding of the corresponding reaction mechanisms in the coming years,these technologies have the potential to be extended in further applications.This review provides further insight into the reaction mechanisms of selectivity and stability of different reaction systems.We then recommend a rigorous and detailed protocol for investigating NRR performance and also highlight several potential research directions in this exciting field,coupling with advanced interdisciplinary applications,in situ/operando characterizations,and theoretical calculations.

The impact of maternal immune activation on the morphology and electrophysiological properties of postnatally-born neurons in the offspring

Pregnancy comes with a combination of physical changes and physiological immunosuppression that increases the susceptibility of women to pathogens and in turn,rises the prevalence of infectious diseases.

Experimental study on the activation of coal gasification fly ash from industrial CFB gasifiers

Coal gasification fly ash(CGFA)is an industrial solid waste from the coal circulating fluidized bed(CFB)gasification process,and it needs to be effectively disposed to achieve sustainable development of the environment.To realize the application of CGFA as a precursor of porous carbon materials,the physicochemical properties of three kinds of CGFA from industrial CFB gasifiers are analyzed.Then,the activation potential of CGFA is acquired via steam activation experiments in a tube furnace reactor.Finally,the fluidization activation technology of CGFA is practiced in a bench-scale CFB test rig,and its advantages are highlighted.The results show that CGFA is characterized by a high carbon content in the range of 54.06%–74.09%,an ultrafine particle size(d50:16.3–26.1 μm),and a relatively developed pore structure(specific surface area SSA:139.29–551.97 m^(2)·g^(-1)).The proportion of micropores in CGFA increases gradually with the coal rank.Steam activation experiments show that the pore development of CGFA mainly includes three stages:initial pore development,dynamic equilibrium between micropores and mesopores and pore collapse.The SSA of lignite fly ash(LFA),subbituminous fly ash(SBFA)and anthracite fly ash(AFA)is maximally increased by 105%,13%and 72%after steam activation;the order of the largest carbon reaction rate and decomposition ratio of steam among the three kinds of CGFA is SBFA>LFA>AFA.As the ratio of oxygen to carbon during the fluidization activation of LFA is from 0.09 to 0.19,the carbon conversion ratio increases from 14.4%to 26.8%and the cold gas efficiency increases from 6.8%to 10.2%.The SSA of LFA increases by up to 53.9%during the fluidization activation process,which is mainly due to the mesoporous development.Relative to steam activation in a tube furnace reactor,fluidization activation takes an extremely short time(seconds)to achieve the same activation effect.It is expected to further improve the activation effect of LFA by regulating the carbon conversion ratio range of 27%–35%to create pores in the initial development stage.

Tuning beneficial calcineurin phosphatase activation to counterα-synuclein toxicity in a yeast model of Parkinson’s disease

Calcineurin(CN)is a calcium-and calmodulindependent serine/threonine that has been studied in many model organisms including yeast,filamentous fungi,plants,and mammals.Its biological functions range from ion homeostasis and virulence in lower eukaryotes to T-cell activation in humans by human nuclear factors of activated T-cells.CN is a heterodimeric protein consisting of a catalytic subunit,calcineurin A(Cna1p),which contains an active site with a dinuclear metal center,and a regulatory Ca^(2+) binding subunit called calcineurin B(Cnb1p)required to activate Cna1p.The calcineurin B subunit has been highly conserved through evolution:For example,the mammalian calcineurin B shows 54%identity with calcineurin B from Saccharomyces cerevisiae.

Properties of Activated Carbons from Sugarcane Leaves and Rice Straw Derived Charcoals by Activation at Low Temperature via KMnO_(4)Pre-Oxidation-Hydrolysis

Activated carbon preparation from sugarcane leaves and rice straw by carbonization(250℃–400℃)and activation at 500℃were studied.The effects of pre-oxidation,hydrolysis of derived charcoals by boiled KMnO4 aqueous solution were evaluated.The derived charcoals products were pretreated using oxidation-hydrolysis with 1–5 wt.%KMnO4 at 100℃and then activated at 500℃.The derived charcoal and activated carbon products were characterized by FTIR,XRD,SEM-EDS and BET.Iodine number and methylene blue number of derived products were also used for the analysis of the products.It was found that fabricated charcoal materials made at 350℃–400℃possess good characteristics with low content of surface functional groups and high carbon content.After pre-oxidation-hydrolysis and activation at 500℃,the resulting derived activated carbon materials from charcoals with 400℃carbonization temperature have high content of oxygen containing surface functional groups such as Mn-O,Si-O,Si-O-Si,C-O,or O-H.In addition,MnO2 accumulated on the surface of the derived activated carbon products.The surface area and pore volume of the activated carbon products have also increased with increasing of KMnO4 concentration from 1 to 3 wt.%and then decreased with 5 wt.%used during activation.Therefore,activated carbon products made by pre-oxidation-hydrolysis with 3 wt.%KMnO4 were used for Fe(Ⅲ)adsorption experiments.It was found that Fe(Ⅲ)adsorption on the activated carbon materials can be fitted with both the Freundlich and the Langmuir models.The calculated maximum Fe(Ⅲ)adsorption capacities of sugarcane leaves derived activated carbon and rice straw derived activated carbon products were 50.00 and 39.37 mg/g,respectively.It was shown that the effect of pre-oxidation-hydrolysis by KMnO4 and activation at 500℃are beneficial for activated carbon preparation with environmentally friendly and low-cost simplified operation.

Brain-wide activation involved in 15 mA transcranial alternating current stimulation in patients with first-episode major depressive disorder

Background Although 15 mA transcranial alternating current stimulation(tACS)has a therapeutic effect on depression,the activations of brain structures in humans accounting for this tACS configuration remain largely unknown.Aims To investigate which intracranial brain structures are engaged in the tACS at 77.5 Hz and 15 mA,delivered via the forehead and the mastoid electrodes in the human brain.Methods Actual human head models were built using the magnetic resonance imagings of eight outpatient volunteers with drug-naïve,first-episode major depressive disorder and then used to perform the electric field distributions with SimNIBS software.Results The electric field distributions of the sagittal,coronal and axial planes showed that the bilateral frontal lobes,bilateral temporal lobes,hippocampus,cingulate,hypothalamus,thalamus,amygdala,cerebellum and brainstem were visibly stimulated by the 15 mA tACS procedure.Conclusions Brain-wide activation,including the cortex,subcortical structures,cerebellum and brainstem,is involved in the 15 mA tACS intervention for first-episode major depressive disorder.Our results indicate that the simultaneous involvement of multiple brain regions is a possible mechanism for its effectiveness in reducing depressive symptoms.

Study of the reaction mechanism for preparing powdered activated coke with SO_(2)adsorption capability via one-step rapid activation method under flue gas atmosphere

In this study,the impact of different reaction times on the preparation of powdered activated carbon(PAC)using a one-step rapid activation method under flue gas atmosphere is investigated,and the underlying reaction mechanism is summarized.Results indicate that the reaction process of this method can be divided into three stages:stage I is the rapid release of volatiles and the rapid consumption of O_(2),primarily occurring within a reaction time range of 0-0.5 s;stage II is mainly the continuous release and diffusion of volatiles,which is the carbonization and activation coupling reaction stage,and the carbonization process is the main in this stage.This stage mainly occurs at the reaction time range of 0.5 -2.0 s when SL-coal is used as material,and that is 0.5-3.0 s when JJ-coal is used as material;stage III is mainly the activation stage,during which activated components diffuse to both the surface and interior of particles.This stage mainly involves the reaction stage of CO_(2)and H2O(g)activation,and it mainly occurs at the reaction time range of 2.0-4.0 s when SL-coal is used as material,and that is 3.0-4.0 s when JJ-coal is used as material.Besides,the main function of the first two stages is to provide more diffusion channels and contact surfaces/activation sites for the diffusion and activation of the activated components in the third stage.Mastering the reaction mechanism would serve as a crucial reference and foundation for designing the structure,size of the reactor,and optimal positioning of the activator nozzle in PAC preparation.

Ultra-high specific surface area activated carbon from Taihu cyanobacteria via KOH activation for enhanced methylene blue adsorption

Cyanobacteria-based activated carbon(CBAC)was successfully prepared by pyrolysis-activation of Taihu cyanobacteria.When the impregnation ratio and activated temperature were 2 and 800-C,respectively,the optimal CBACs possessed an ultra-high specific surface(2178.90 m^(2)·g^(-1))and plenty of micro-and meso-pores,as well as a high pore volume(1.01 cm^(3)·g^(-1)).Ascribed to ultra-high surface area,π-π interaction,electrostatic interaction,as well as hydrogen-bonding interactions,the CBACs displayed huge superiority in efficient dye removal.The saturated methylene blue adsorption capacity by CBACs could be as high as 1143.4 mg·g^(-1),superior to that of other reported biomass-activated carbons.The adsorption was endothermic and modeled well by the pseudo-second-order kinetic,intra-particle diffusion,and Langmuir models.This work presented the effectiveness of Taihu cyanobacteria adsorbent ascribed to its super large specific surface area and high adsorption ability.

Screening the optimal Co_(x)/CeO_(2)(110)(x=1–6)catalyst for methane activation in coalbed gas

The challenges posed by energy and environmental issues have forced mankind to explore and utilize unconventional energy sources.It is imperative to convert the abundant coalbed gas(CBG)into high value-added products,i.e.,selective and efficient conversion of methane from CBG.Methane activation,known as the“holy grail”,poses a challenge to the design and development of catalysts.The structural complexity of the active metal on the carrier is of particular concern.In this work,we have studied the nucleation growth of small Co clusters(up to Co_(6))on the surface of CeO_(2)(110)using density functional theory,from which a stable loaded Co/CeO_(2)(110)structure was selected to investigate the methane activation mechanism.Despite the relatively small size of the selected Co clusters,the obtained Co_(x)/CeO_(2)(110)exhibits interesting properties.The optimized Co_(5)/CeO_(2)(110)structure was selected as the optimal structure to study the activation mechanism of methane due to its competitive electronic structure,adsorption energy and binding energy.The energy barriers for the stepwise dissociation of methane to form CH3^(*),CH2^(*),CH^(*),and C^(*)radical fragments are 0.44,0.55,0.31,and 1.20 eV,respectively,indicating that CH^(*)dissociative dehydrogenation is the rate-determining step for the system under investigation here.This fundamental study of metal-support interactions based on Co growth on the CeO_(2)(110)surface contributes to the understanding of the essence of Co/CeO_(2) catalysts with promising catalytic behavior.It provides theoretical guidance for better designing the optimal Co/CeO_(2) catalyst for tailored catalytic reactions.

Mechanistic insights into stepwise activation of malachite for enhancing surface reactivity and flotation performance

Malachite is a common copper oxide mineral that is often enriched using the sulfidization-xanthate flotation method.Currently,the direct sulfidization method cannot yield copper concentrate products.Therefore,a new sulfidization flotation process was developed to promote the efficient recovery of malachite.In this study,Cu^(2+) was used as an activator to interact with the sample surface and increase its reaction sites,thereby strengthening the mineral sulfidization process and reactivity.Compared to single copper ion activation,the flota-tion effect of malachite significantly increased after stepwise Cu^(2+) activation.Zeta potential,X-ray photoelectron spectroscopy(XPS),time-of-flight secondary ion mass spectroscopy(ToF-SIMS),scanning electron microscopy and energy dispersive spectrometry(SEM-EDS),and atomic force microscopy(AFM)analysis results indicated that the adsorption of S species was significantly enhanced on the mineral surface due to the increase in active Cu sites after Cu^(2+) stepwise activation.Meanwhile,the proportion of active Cu-S spe-cies also increased,further improving the reaction between the sample surface and subsequent collectors.Fourier-transform infrared spec-troscopy(FT-IR)and contact angle tests implied that the xanthate species were easily and stably adsorbed onto the mineral surface after Cu^(2+) stepwise activation,thereby improving the hydrophobicity of the mineral surface.Therefore,the copper sites on the malachite sur-face after Cu^(2+) stepwise activation promote the reactivity of the mineral surface and enhance sulfidization flotation of malachite.