O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts

Water oxidation is one of the most important reactions in natural and artificial energy conversion schemes.In nature,solar energy is converted to chemical energy via water oxidation at the oxygen-evolving center of photosystem II to generate dioxygen,protons,and electrons.In artificial energy schemes,water oxidation is one of the half reactions of water splitting,which is an appealing strategy for energy conversion via photocatalytic,electrocatalytic,or photoelectrocatalytic processes.Because it is thermodynamically unfavorable and kinetically slow,water oxidation is the bottleneck for achieving large-scale water splitting.Thus,developing highly efficient water oxidation catalysts has attracted the interests of researchers in the past decades.The formation of O-O bonds is typically the rate-determining step of the water oxidation catalytic cycle.Therefore,better understanding this key step is critical for the rational design of more efficient catalysts.This review focuses on elucidating the evolution of metal-oxygen species during transition metal-catalyzed water oxidation,and more importantly,on discussing the feasible O-O bond formation mechanisms during the oxygen evolution reaction over synthetic molecular catalysts.

Interfacial reactions and diffusion path in partial transient liquid-phase bonding of Si_3N_4/Ti/Ni/Ti/Si_3N_4

The interfacial reactions in partial transient liquid-phase bonding of Si3N4 ceramics with Ti/Ni/Ti interlayers were studied by means of scanning electron microscopy （SEM）, energy dispersive spectrometry （EDS） and X-ray diffractometry （XRD）. It was shown that the interfacial structure of Si3N4/TiN/Ti5Si3+Ti5Si4 + Ni3Si/ （NiTi ） /Ni3Ti/ Ni was formed after bonding. The activation energies for TiN layer and the mixed reaction layer of Ti5Si3 + Ti5Si4 + Ni3Si are 546. 8 kJ/mol and 543. 9 kJ/mol, respectively. The formation and transition processes of interface layer sequence in the joint were clarified by diffusion path. An important characteristic, which is different from the conventional brazing and soid-state diffusion bonding, has been found, i. e., during the partial transient liquid-phase bonding, not only the reaction layers which have formed grow, but also the diffusion path in the subsequent reaction changes because of the remarkable variation of the concentration on the metal side.

Study on deuteron formation mechanism in nucleon-induced reactions

The mechanism of deuteron formation in neutron-induced reactions is studied within the framework of the isospin-dependent quantum molecular dynamics model,using the GEMINI code.The influence of the n+p→d reaction channel is investigated by analyzing the deuteron production cross sections in the neutron-induced reactions12C(n,d),16O(n,d),and 28Si(n,d),with incident energies of 20-100 MeV.By including the n+p→d reaction channel when modeling the collision,the deuteron production cross sections increase,optimizing the cross-section results and bringing them closer to the experimental data values.This indicates that the n+p→d reaction channel is an important mechanism for enhancing deuteron production.

The Quantum Scattering Study for Ion-pair Formation Reaction Na+I_2→Na^+I_2^- with the LCAC-SW method

The selected-state probabilities of collinear ion-pair formation process Na+I2→Na++I2-on Aten-Laming-Los two-State potential energy surface have been calculated by using LCAC-SW method. The results show that reaction probabilities are oscillatory with collision energy; the threshold energy of this ioniZation reaction is 2.8 ev, which is in modest agreement with experimental result.

Methane Formation by the Reaction of Coalbed Carbon with Water

There is proposed a mechanism of methane and carbon dioxide formation by the direct reaction of carbon with water during catastrophic events in the mining of coal deposits. Thermodynamics of the reaction is dis-cussed.

Studies on Progressive Reactions Leading Formations of Different Types of Barium Ferrites

The present investigation is concerned with the reaction of barium and iron nitrates mixtures using three different molar ratios, 1:1 (Ⅰ), 1:2 (Ⅱ) and 2:1 (Ⅲ) at different temperatures as pointed out from the DTA data. The reaction products exhibit 12 compounds namely, Ba(NO3)2, αFe2O3, Fe3O4, BaFeO3, BaFeO2.9, hexagonal BaFeO3-x, tetragonal BaFeO3-x, BaFe2O4, αBaFe2O4, Ba2Fe6O11, Ba5Fe14O26 and BaFe12O19. The formation of these products depend on the molar ratio between the reactants and the reaction temperature. The reaction products were studied by DTA and TG techniques and characterized by X-ray diffraction patterns, magnetic susceptibility data and scanning electron microscopy, SEM.

Formation cross sections of nuclei with (n,2n) reactions

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Research on prediction model of formation temperature of ammonium bisulfate in air preheater of coal-fired power plant

Ammonium bisulfate(ABS)is a viscous compound produced by the escape NH_(3) in the NO reduction process and SO_(3) in the flue gas at a certain temperature,which can cause the ash corrosion of the air preheater in coal-fired power plants.Therefore,it is essential to study the formation temperature of ABS to prevent the deposition of ABS in air preheaters.In this paper,the SO_(3) reaction kinetic model is used to analyze the SO_(3) generation process from coal combustion to the selective catalytic reduction(SCR)exit stage,and the kinetic model of NO reduction is used to analyze the NH_(3) escape process.A prediction model for calculating the ABS formation temperature based on the S content in coal and NO reduction parameters of the SCR is proposed,solving the difficulty of measuring SO_(3) concentration and NH_(3) concentration in the previous calculation equation of ABS formation temperature.And the reliability of the model is verified by the actual data of the power plant.Then the influence of S content in coal,NH_(3)/NO_(x) molar ratio,different NO_(x) concentrations at SCR inlet,and NO removal efficiency on the formation temperature of ABS are analyzed.

Tuning the O–O bond formation pathways of molecular water oxidation catalysts on electrode surfaces via second coordination sphere engineering

A molecular [Ru(bda)]-type(bda = 2,2’-bipyridine-6,6’-dicarboxylate) water oxidation catalyst with 4-vinylpyridine as the axial ligand(Complex 1) was immobilized or co-immobilized with 1-(trifluoromethyl)-4-vinylbenzene(3 F) or styrene(St) blocking units on the surface of glassy carbon(GC) electrodes by electrochemical polymerization, in order to prepare the corresponding poly-1@GC, poly-1+P3 F@GC, and poly-1+PSt@GC functional electrodes. Kinetic measurements of the electrode surface reaction revealed that [Ru(bda)] triggers the O–O bond formation via(1) the radical coupling interaction between the two metallo-oxyl radicals(I2 M) in the homo-coupling polymer(poly-1), and(2) the water nucleophilic attack(WNA) pathway in poly-1+P3 F and poly-1+PSt copolymers. The comparison of the three electrodes revealed that the second coordination sphere of the water oxidation catalysts plays vital roles in stabilizing their reaction intermediates, tuning the O–O bond formation pathways and improving the water oxidation reaction kinetics without changing the first coordination structures.

Evaluation on the natural gas hydrate formation process

Gas hydrates have endowed with great potential in gas storage,and rapid formation of gas hydrates is critical to use this novel technology.This work evaluated the natural gas hydrate formation process,which was compared from six parameters,including conversion of water to hydrate,storage capacity,the rate of hydrate formation,space velocity(SV)of hydrate reaction,energy consumption and hydrate removal.The literature was selected by analyzing and comparing these six parameters mentioned above,meanwhile placing emphasis on the three parameters of storage capacity,the rate of hydrate formation and space velocity of hydrate reaction.Through analysis and comparison,four conclusions could be obtained as follows.Firstly,the overall performance of the stirring process and the spraying process were better than other processes after analyzing the six parameters.Secondly,the additive types,the reactor structure and the reactor size had influence on the natural gas hydrate formation process.Thirdly,the energy consumption via reciprocating impact in the hydrate formation process was higher than that via stirring,spraying and static higee.Finally,it was one key for hydrate removal to realize the hydrate industrial production.

Overcoming coke formation in high-temperature CO_(2)electrolysis

High-temperature CO_(2)reduction reaction(HT-CO_(2)RR)in solid oxide electrochemical cells(SOECs)features near-unity selectivity,high energy efficiency,and industrial relevant current density for the production of CO,a widely-utilized“building block”in today’s chemical industry.Thus,it offers an intriguing and promising means to radically change the way of chemical manufacturing and achieve carbon neutrality using renewable energy sources,CO_(2),and water.Albeit with the great potential of HT-CO_(2)RR,this carbon utilization approach,unfortunately,has been suffering coke formation that is seriously detrimental to its energy efficiency and operating lifetime.In recent years,much effort has been added to understanding the mechanism of coke formation,managing reaction conditions to mitigate coke formation,and devising coke-formation-free electrode materials.These investigations have substantially advanced the HT-CO_(2)RR toward a practical industrial technology,but the resulting coke formation prevention strategies compromise activity and energy efficiency.Future research may target exploiting the control over both catalyst design and system design to gain selectivity,energy efficiency,and stability synchronously.Therefore,this perspective overviews the progress of research on coke formation in HT-CO_(2)RR,and elaborates on possible future directions that may accelerate its practical implementation at a large scale.

Relationship between the Standard Enthalpy of Formation and the Ratio of Standard Enthalpy of Formation and Exothermic Denitration Decomposition Peak Temperature of M(NTO)_n

A relationship is established, using the least squares method, between the standard enthalpy of formation and the standard enthalpy of formation divided by the exothermic denitration decomposition peak absolute temperature corresponding to β →0.

Pattern formation in superdiffusion Oregonator model

Pattern formations in an Oregonator model with superdiffusion are studied in two-dimensional(2D) numerical simulations. Stability analyses are performed by applying Fourier and Laplace transforms to the space fractional reaction–diffusion systems. Antispiral, stable turing patterns, and travelling patterns are observed by changing the diffusion index of the activator. Analyses of Floquet multipliers show that the limit cycle solution loses stability at the wave number of the primitive vector of the travelling hexagonal pattern. We also observed a transition between antispiral and spiral by changing the diffusion index of the inhibitor.

Studies on Solid State Reactions of Coordination Compounds（LXXI）──Solid State Reactions of o－Aminobenzoic Acid with Copper（Ⅱ） Acetate and Formate at Room Temperature

olid state reactions of o-aminobenzoic acid (HOAB) with Cu (OAc)_2·H_2O,Cu(HCOO)_2 · 4H_2O, anhydrous Cu (OAc)_2 and Cu (HCOO)_2 at room or close toroom temperature have been investigated. The product Cu(OAB)_2 with a high yieldwas synthesized very conveniently compared witb the solution phase method. Thekinetic behavior was studied by means of the isothermal electrical conductivity mea-surement. The reactivity was found to decrease in the order : Cu(OAc)_2· H_2O>Cu(OAc)_2>Cu (HCOO)_2 ·4H_2O>Cu (HCOO)_2, which was attributable to the crystalstructures of the copper salts.

Bimetallic In_(2)O_(3)/Bi_(2)O_(3) Catalysts Enable Highly Selective CO_(2) Electroreduction to Formate within Ultra-Broad Potential Windows

CO_(2)electrochemical reduction reaction(CO_(2)RR)to formate is a hopeful pathway for reducing CO_(2)and producing high-value chemicals,which needs highly selective catalysts with ultra-broad potential windows to meet the industrial demands.Herein,the nanorod-like bimetallic ln_(2)O_(3)/Bi_(2)O_(3)catalysts were successfully synthesized by pyrolysis of bimetallic InBi-MOF precursors.The abundant oxygen vacancies generated from the lattice mismatch of Bi_(2)O_(3)and ln_(2)O_(3)reduced the activation energy of CO_(2)to*CO_(2)·^(-)and improved the selectivity of*CO_(2)·^(-)to formate simultaneously.Meanwhile,the carbon skeleton derived from the pyrolysis of organic framework of InBi-MOF provided a conductive network to accelerate the electrons transmission.The catalyst exhibited an ultra-broad applied potential window of 1200 mV(from-0.4 to-1.6 V vs RHE),relativistic high Faradaic efficiency of formate(99.92%)and satisfactory stability after 30 h.The in situ FT-IR experiment and DFT calculation verified that the abundant oxygen vacancies on the surface of catalysts can easily absorb CO_(2)molecules,and oxygen vacancy path is dominant pathway.This work provides a convenient method to construct high-performance bimetallic catalysts for the industrial application of CO_(2)RR.

Effect of Olefins on Formation of Sulfur Compounds in FCC Gasoline

The effect of olefins on formation of sulfur compounds in FCC gasoline was studied in a small-scale fixed fluidized bed （FFB） unit at temperatures ranging from 400℃ to 500℃, a weight hourly space velocity （WHSV） of 10 h-1, and a catalyst/oil ratio of 6. The results showed that C4--C6 olefins contained in the FCC gasoline could react with HzS to form predominantly thiophenes, alkyl-thiophenes as well as a fractional amount of thiols, while large molecular olefins such as heptene could react with hydrogen sulfide to form benzothiophenes. The amount of sulfur compounds formed at different tem- peratures over different catalysts were in proportion to the mass fractions of olefins in the feedstock, with the amount of sulfur compounds formed over REUSY catalyst exceeding those formed over the shape selective zeolite catalyst owing to the effect of catalyst performance and the impact of catalyst on the degree of olefin conversion. The amount of sulfur compounds generated and their increase reached a maximum at 450℃ and a minimum at 400℃ because of the influence of temperature on the thermodynamic and kinetic constants for formation of sulfur compound as well as on the olefin conversion degree. Based on the above-mentioned study, a reaction network and a model for prediction of sulfur compounds generated upon reaction of olefins in FCC gasoline with HES were established.

Selective synthesis of carbon monoxide via formates in reverse water–gas shift reaction over alumina-supported gold catalyst

Thermal decomposition of formic acid on SiO2, CeO2 and γ-Al2O3 was studied as an elementary step of reverse water–gas shit reaction（RWGS） over supported Au catalysts. γ-Al2O3 showed the highest CO selectivity among the tested oxides in the decomposition of formic acid. Infrared spectroscopy showed the formation of four formate species on γ-Al2O3： three η~1-type and one μ~2-type species, and these formates decomposed to CO at 473 K or higher. Au-loaded γ-Al2O3 samples were prepared by a depositionprecipitation method and used as catalysts for RWGS. The supported Au catalyst gave CO with high selectivity over 99% from CO2 and H2, which is attributed to the formation of formates on Au and subsequent decomposition to CO on γ-Al2O3.

Identification of relevant active sites and a mechanism study for reverse water gas shift reaction over Pt/CeO_2 catalysts

Reverse water gas shift (RWGS) reaction can serve as a pivotal stage in the CO2 conversion processes, which is vital for the utilization of CO2. In this study, RWGS reaction was performed over Pt/CeO2 catalysts at the temperature range of 200-500 degrees C under ambient pressure. Compared with pure CeO2, Pt/CeO2 catalysts exhibited superior RWGS activity at lower reaction temperature. Meanwhile, the calculated TOF and E-a values are approximately the same over these Pt/CeO2 catalysts pretreated under various calcination conditions, indicating that the RWGS reaction is not affected by the morphologies of anchored Pt nanoparticles or the primary crystallinity of CeO2. TPR and XPS results indicated that the incorporation of Pt promoted the reducibility of CeO2 support and remarkably increased the content of Ce 3 + sites on the catalyst surface. Furthermore, the CO TPSR-MS signal under the condition of pure CO2 flow over Pt/CeO 2 catalyst is far lower than that under the condition of adsorbed CO2 with H-2 -assisted flow, revealing that CO2 molecules adsorbed on Ce3+ active sites have difficult in generating CO directly. Meanwhile, the adsorbed CO2 with the assistance of H-2 can form formate species easily over Ce3+ active sites and then decompose into Ce3+-CO species for CO production, which was identified by in-situ FTIR. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B. V. and Science Press. All rights reserved.

Reactions of Laser Ablation-magnesium Plasma with Methanol Clusters

The laser ablation-molecular beam（LA-MB） method is useful for studying the reactions of metal ions with molecular clusters. Reactions of magnesium plasma with methanol clusters were studied by using this method. A specially designed reaction cell was used as a fast flow reactor operated under thermal conditions, and the reaction products were measured with a time-of-flight（TOF） mass spectrometer. Surprisingly, several series of cluster ions with complex sizes and intensity distributions were obtained when the laser ablating was applied to different parts of the molecular beam. In the front part of the molecular beam, strong Mg^＋ （CH3OH）n（ n = 0-5） and weak H^＋ （CH3OH）n（ n = 0-5 ） cluster ions were observed with relatively small cluster sizes ; in the middle part of the molecular beam, the main cluster ions were H^＋ （ CH3OH）n （ n = 6-17 ） and H^＋（ H2O） 2 （ CH3OH）n（ n = 6-17 ） with a relatively large cluster size and a weak intensity; in the back part of the molecular beam, two new series of cluster ions, MgO^＋ （ H2O） （ CH3 OH）n（ n = 6-10 ） and MgOCH3^＋ （ CH3OH）n（ n = 6-10）, were obtained and accompanied by weak H^＋（CH3OH）n（n = 4-7） and H^＋（ H2O）2 （CH3OH）n（ n = 3-6）. The formation mechanisms and speed characteristics of the cluster ions are discussed in this article.

Bifunctional PdPt bimetallenes for formate oxidation-boosted water electrolysis

Small-molecule electrooxidation-boosted water electrolysis(WE)is an energy-saving method for hydrogen(H2)production.Herein,PdPt bimetallenes(PdPt BMLs)are obtained through the simple galvanic replacement reaction.PdPt BMLs reveal 2.93-fold enhancement in intrinsic electroactivity and 4.53-fold enhancement in mass electroactivity for the formate oxidation reaction(FOR)with respect to Pd metallenes(Pd MLs)at 0.50 V potential due to the synergistic effect.Meanwhile,the introduction of Pt atoms also considerably increases the electroactivity of PdPt BMLs for hydrogen evolution reaction(HER)with respect to Pd MLs in an alkaline medium,which even exceeds that with the use of commercial Pt nanocrystals.Inspired by the outstanding FOR and HER electroactivity of bifunctional PdPt BMLs,a two-electrode FOR-boosted WE system(FOR-WE)is constructed by using PdPt BMLs as the cathode and the anode.The FOR-WE system only requires an operational voltage of 0.31 V to achieve H2 production,which is 1.48 V lower than that(ca.1.79 V)with the use of the traditional WE system.