“Buckets effect”in the kinetics of electrocatalytic reactions

In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.

Deciphering the linear relationship in the activity of the oxygen reduction reaction on Pt electrodes:A decisive role of adsorbates

Despite substantial efforts in developing high-performance catalysts for the oxygen reduction reaction(ORR),the persistent challenge lies in the high onset overpotential of the ORR,and the effect of the elec-trolyte solution cannot be ignored.Consequently,we have systematically investigated the impact of adsorbate species and concentration,as well as solution pH,on the ORR activity on Pt(111)and Pt(poly)electrodes.The results all tend to establish a linear quantitative relationship between the onset potential for ORR and the adsorption equilibrium potential of the adsorbate.This finding indicates the decisive role of adsorbates in the onset potential for ORR,suggesting that the adsorption potential of adsorbates can serve as an intuitive criterion for ORR activity.Additional support for this conclusion is derived from experimental results obtained from the oxygen evolution reaction on Pt(poly)with different adsorbate species and from the hydrogen evolution reaction on Pt(111)with iodine adsorption.We further propose both an empirical equation for the onset potential for ORR and the concept of a potential-regulated adsor-bate shielding effect to elucidate the influence of adsorbates on ORR activity.This study provides new insights into the high onset overpotential of the ORR and offers potential strategies for predicting and enhancingORRactivity inthefuture.

Machine learning molecular dynamics simulations of liquid methanol

As the simplest hydrogen-bonded alcohol,liquid methanol has attracted intensive experimental and theoretical interest.However,theoretical investigations on this system have primarily relied on empirical intermolecular force fields or ab initio molecular dynamics with semilocal density functionals.Inspired by recent studies on bulk water using increasingly accurate machine learning force fields,we report a new machine learning force field for liquid methanol with a hybrid functional revPBE0 plus dispersion correction.Molecular dynamics simulations on this machine learning force field are orders of magnitude faster than ab initio molecular dynamics simulations,yielding the radial distribution functions,selfdiffusion coefficients,and hydrogen bond network properties with very small statistical errors.The resulting structural and dynamical properties are compared well with the experimental data,demonstrating the superior accuracy of this machine learning force field.This work represents a successful step toward a first-principles description of this benchmark system and showcases the general applicability of the machine learning force field in studying liquid systems.

Effects of Storage Time and Hydrogen Peroxide on the Formation of Soy Globulin 15S in 11S Dilute Solutions Investigated by Analytical Ultracentrifugation

Two soy protein 11S fractions with different surface sulfhydryl contents were prepared.Utilizing analytical ultracentrifugation,the effects of storage time and hydrogen peroxide at different concentrations(0.5-100 mmol/L)on the two 11S fractions were investigated.Results show that after removing 2-mercaptoethanol(2-ME)by size exclusion chromatography,the 11S fraction with high surface sulfhydryl content(2.0 mol sulfhydryl/mol 11S)progressively formed 15S and 21S in dilute solutions during storage at 4℃ for 82 days.While,the 11s fraction with low surface sulfhydryl content(0.2 mol sulfhydryl/mol 11S)was stable under the same condition.Moreover,after treating the 11s with high surface sulfhydryl content with 1 mmol/L H_(2)O_(2),the weight percentage of 15S reached the maximum value of 20%.The 15S induced by air and H_(2)O_(2)could be totally converted to 11S with the addition of 10 mmol/L 2-ME,which could be attributed to that the disulfide bond linking two 11S molecules is on the surface of the 15S and easily accessible to the reducing agent 2-ME.This study helps us to deeply understand the formation mechanism of 15S and the stability of 11S.

Modeling and analysis of air combustion and steam regeneration in methanol to olefins processes

Light olefins is the incredibly important materials in chemical industry.Methanol to olefins(MTO),which provides a non-oil route for light olefins production,received considerable attention in the past decades.However,the catalyst deactivation is an inevitable feature in MTO processes,and regeneration,therefore,is one of the key steps in industrial MTO processes.Traditionally the MTO catalyst is regenerated by removing the deposited coke via air combustion,which unavoidably transforms coke into carbon dioxide and reduces the carbon utilization efficiency.Recent study shows that the coke species over MTO catalyst can be regenerated via steam,which can promote the light olefins yield as the deactivated coke species can be essentially transferred to industrially useful synthesis gas,is a promising pathway for further MTO processes development.In this work,we modelled and analyzed these two MTO regeneration methods in terms of carbon utilization efficiency and technology economics.As shown,the steam regeneration could achieve a carbon utilization efficiency of 84.31%,compared to 74.74%for air combustion regeneration.The MTO processes using steam regeneration can essentially achieve the near-zero carbon emission.In addition,light olefins production of the MTO processes using steam regeneration is 12.81%higher than that using air combustion regeneration.In this regard,steam regeneration could be considered as a potential yet promising regeneration method for further MTO processes,showing not only great environmental benefits but also competitive economic performance.

Ultra-soft Desorption Assisted Mass Spectrometry using Picosecond Infrared Laser for the Detection of lons in the Liquid Surface

To identify the species in liquid surface using mass spectrometry,we must eliminate or reduce interferences during the vaporization or desorption of the species from the liquid surface.It is much more challenging to isolate the ionic,larger species from the liquid surface,because of the frangible structures and the higher solvation energies of those species.Here we demonstrate a new mass spectrometry in which the ionic species at the liquid surface can be desorbed with ultrasoft infrared picosecond laser pulses while the liquid surface is not breached.This laser desorption assisted mass spectrometry is not only a powerful tool to detect the fragile species but also promising to investigate vibrational energy transfer dynamics in the liquid surface.

Structure,electronic,and nonlinear optical properties of superalkaline M_(3)O(M=Li,Na)doped cyclo[18]carbon

Cyclo[18]carbon has received considerable attention thanks to its novel geometric configuration and special electronic structure.Superalkalis have low ionization energy.Doping a superalkali in cyclo[18]carbon is an effective method to improve the optical properties of the system because considerable electron transfer occurs.In this paper,the geometry,bonding properties,electronic structure,absorption spectrum,and nonlinear optical(NLO)properties of superalkaline M_(3)O(M=Li,Na)-doped cyclo[18]carbon were studied by using density functional theory.M_(3)O and the C_(18) rings are not coplanar.The C_(18) ring still exhibits alternating long and short bonds.The charge transfer between M_(3)O and C_(18) forms stable[M_(3)O]+[C_(18)]-ionic complexes.C_(18)M_(3)O(M=Li,Na)shows striking optical nonlinearity,i.e.,their first-and second-order hyperpolarizability(βvec andγ||)increase considerably atλ=1907 nm and 1460 nm.

Author Correction to “Saturated Cavity Ring-Down Spectroscopy of ^(12)C^(16)O_(2) near 1.57 μm”

We regret to announce that there is an error in one of fund numbers in the acknowledgements of the paper titled“Saturated Cavity Ring-Down Spectroscopy of ^(12)C^(16)O_(2) near 1.57μm”due to the author’s typing errors.The acknowledgements were published in Chin.J.Chem.Phys.37,17(2024).

Enhanced Photocatalytic Performance of Anatase TiO_(2) by Deposition-Precipitation Treatment

Deposition-precipitation(DP)method is commonly used to prepare the supported metal catalysts.In this study,the modification effect of the mild DP method on the photocatalytic performance of TiO_(2)was investigated.The TiO_(2)samples with DP treatment,as well as Au/TiO_(2)prepared under the same conditions,showed enhanced photocatalytic performance of the degradation of methylene blue(MB).·OH generated by photoexcited holes is identified as the main intermediate reactive species during the degradation reaction.X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)show that TiO_(2)(A)-17 after DP treatment has the most amount of surface OH^(-)_(ad)species.The presence of surface OH^(-)_(ad)species not only changes the surface zeta potential,favoring the attraction of cationic MB;but also depresses the electron-hole recombination,favoring photodegradation of MB by hole-produced·OH.An implication of these findings is that the modification of support properties should be taken into account while preparing supported metal catalysts using DP methods.

Synergistic effect of heterogeneous single atoms and clusters for improved catalytic performance

Electrocatalytic water splitting provides an efficient method for the production of hydrogen.In electrocatalytic water splitting,the oxygen evolution reaction(OER)involves a kinetically sluggish four-electron transfer process,which limits the efficiency of electrocatalytic water splitting.Therefore,it is urgent to develop highly active OER catalysts to accelerate reaction kinetics.Coupling single atoms and clusters in one system is an innovative approach for developing efficient catalysts that can synergistically optimize the adsorption and configuration of intermediates and improve catalytic activity.However,research in this area is still scarce.Herein,we constructed a heterogeneous single-atom cluster system by anchoring Ir single atoms and Co clusters on the surface of Ni(OH)_(2)nanosheets.Ir single atoms and Co clusters synergistically improved the catalytic activity toward the OER.Specifically,Co_(n)Ir_(1)/Ni(OH)_(2)required an overpotential of 255 mV at a current density of 10 mA·cm^(−2),which was 60 mV and 67 mV lower than those of Co_(n)/Ni(OH)_(2)and Ir1/Ni(OH)_(2),respectively.The turnover frequency of Co_(n)Ir_(1)/Ni(OH)_(2)was 0.49 s^(−1),which was 4.9 times greater than that of Co_(n)/Ni(OH)_(2)at an overpotential of 300 mV.

Coverage Dependent Dissociative Adsorption of HCl on Au(111)

Dissociative adsorption of HCl on Au(111)has become one of unsolved puzzles in surface chemistry.Despite tremendous efforts in the past years,varioustheoretical models still greatly overestimate the zero-coverage initial sticking probabilities(So).To find the origin of the large experiment-theory discrepancy,we have revisited the dissociative adsorption of HCl on Au(111)with a newly designed molecular beam-surface apparatus.The zero-coverage So derived from Cl-coverage measurements with varying HCl doses agree well with previous ones.However,we notice a sharp change of the coverage/dose slope with the HCl dosage at the low coverage regime,which may result in some uncertainties to the fitted So value.This seems consistent with a coverage-dependence of the dissociation barrier predicted by density functional theory at low Cl-coverages.Our results reveal the potential inconsistency of utilizing simulations with finite coverage to compare against experimental data with zero coverage in this system,and provide guidance for improving both experiment and theory in this regard.

Structure and Vibrational Spectroscopy of 2-Methylallyl Alcohol

The intramolecular O−H…πhydrogen bond has garnered significant research interest in recent decades.In this work,we utilized the infrared(IR)-vacuum-ultraviolet(VUV)nonresonant ionization detected IR spectroscopy(NRID-IR)method to study the molecular structure of neutral and cationic 2-methylallyl alcohol(MAA,CH_(2)=C(CH_(3))−CH_(2)−OH).Density functional theory calculations revealed five stable neutral and three stable cationic MAA conformers,respectively.Two neutral MAA conformers are expected to have an O−H…πintramolecular hydrogen bond interaction,based on the structural characterization that the OH group is directed toward the C=C double bond.The IR spectra of both neutral(2700−3700 cm^(−1))and cationic MAA(2500−7200 cm^(−1))were measured,and the anharmonic IR spectra were calculated at the B3LYP-D3(BJ)/def2-TZVPP level.The OH stretching vibration frequency of neutral MAA was observed at 3656 cm−1,slightly lower than those of methanol and ethanol.In contrast,the OH stretching vibration of cationic MAA was red-shifted by about 140 cm^(−1)compared to neutral MAA.The interaction region indicator and natural bond orbital analysis suggest that the O−H…πinteraction in neutral MAA is weak,and may not play a major role in stabilizing the neutral MAA.

Effect of mass transfer and solution composition on the quantification of reaction kinetics by differential electrochemical mass spectrometry

Differential electrochemical mass spectrometry(DEMS)is one of the most powerful techniques for both the mechanistic and kinetic study of complicated electrocatalytic reactions.It can provide information on the nature and yields of the products generated,their production rate,and the structure-activity relationship between the electrocatalysts and the target reactions.The precise calibration of the mass signal is a prerequisite for the accurate evaluation of reaction kinetics.In this work,we use the oxidation reactions of CO and HCOOH to demonstrate how certain conditions,such as the flow rate and solution composition,affect the collection efficiency and ionization probability of the species to be detected.These parameters can affect the determination of the mass calibration constant and the accuracy of the subsequent quantitative DEMS analysis.We show the relationship between the mass calibration constant and the flow rate,and provide strategies for eliminating this and the related problems.

Restructuring of well-defined Pt-based electrode surfaces under mild electrochemical conditions

Since the 1980s,single-crystal Pt electrodes with well-defined surface structures have been deemed stable under mild electrochemical conditions(e.g.,in the potential region of electric double layers,underpotential deposition of hydrogen,or mild hydrogen evolution/OH adsorption)and have served as model electrodes for unraveling the structure-performance relation in electrocatalysis.With the advancement of in situ electrochemical microscopy/spectroscopy techniques,subtle surface restructuring under mild electrochemical conditions has been achieved in the last decade.Surface restructuring can considerably modify electrocatalytic properties by generating/destroying highly active sites,thereby interfering with the deduction of the structure-performance relation.In this review,we summarize recent progress in the restructuring of well-defined Pt(-based)electrode surfaces under mild electrochemical conditions.The importance of the meticulous structural characterization of Pt electrodes before,during,and after electrochemical measurements is demonstrated using CO adsorption/oxidation,hydrogen adsorption/evolution,and oxygen reduction as examples.The implications of present findings for correctly identifying the reaction mechanisms and kinetics of other electrocatalytic systems are also briefly discussed.

Solvent Dependence of Photophysical and Photochemical Behaviors of Thioxanthen-9-one

The photophysical and photochemical behaviors of thioxanthen-9-one(TX)in different solvents have been studied using nanosecond transient absorption spectroscopy.A unique absorption of the triplet state^(3)TX^(∗) is observed,which involves two components,^(3)nπ^(∗) and^(3)ππ^(∗) states.The ^(3)ππ^(∗) component contributes more to the^(3)TX^(∗) when increasing the solvent polarity.The self-quenching rate constant ksq of^(3)TX^(∗)is decreased in the order of CH_(3)CN,CH_(3)CN/CH_(3)OH(1:1),and CH_(3)CN/H_(2)O(1:1),which might be caused by the exciplex formed from hydrogen bond interaction.In the presence of diphenylamine(DPA),the quenching of^(3)TX^(∗)happens efficiently via electron transfer,producing the TX^(⋅−) anion and DPA^(⋅+) cation radicals.Because of insignificant solvent effects on the electron transfer,the electron affinity of the ^(3)nπ^(∗) state is proved to be approximately equal to that of the ^(3)ππ^(∗) state.However,a solvent dependence is found in the dynamic decay of TX^(⋅−) anion radical.In the strongly acid aqueous acetonitrile(pH=3.0),a dynamic equilibrium between protonated and unprotonated TX is definitely observed.Once photolysis,^(3)TXH^(+∗) is produced,which contributes to the new band at 520 nm.

pH Dependence of Photochemical Kinetics of Thioxanthen-9-one from Nanosecond Time-resolved Laser Flash Photolysis

pH dependent uorescence emission of a thioxanthone-based probe has been re-ported recently.The potential deter-minant factors of pH dependence may provide important clues to design novel thioxanthone-based probes in the fu-ture.pH dependence of photochemical kinetics of thioxanthone itself was inves-tigated in this work using nanosecond time-resolved laser ash photolysis.The nanosecond time-resolved transient absorption spectra and kinetics of TX in aqueous acetonitrile were recorded,as well as for a model reaction system including TX with diphenylamine(DPA)as a co-initiator.Besides the well-known absorption peak of ^(3)TX*,other peaks at 417,518,673 and 780 nm,have been reliably attributed to major intermediates in the overall reaction between TX and DPA with photolysis,which has been con rmed to occur along a multistep process.In the strong acidic solution(pH≈3.0),TX and protonated TX ions(TXH^(+))coexist due to protonated equilibrium.Consequently,high proton concentration promotes the predominant decay pathway after photolysis from electron transfer to proton affnity.Subsequently,the di erent primary products,^(3)TXH^(+*)or TX^(·-),proceed di erent secondary reaction channels.In addition,within the wide pH range from weak acid(pH=5.0)to alkaline solution(pH=13.0),the overall reaction mechanism and rates do not show visible changes.

Concentration-Dependent Effect of Nickel Ions on Amyloid Fibril Formation Kinetics of Hen Egg White Lysozyme:a Raman Spectroscopy Study

Nickel,an important transi-tion metal element,is one of the trace elements for hu-man body and has a crucial impact on life and health.Some evidences show the excess exposure to metal ions might be associated with neurological diseases.Herein,we applied Raman spectroscopy to study the Ni(II)ion effect on kinetics of amyloid fibrillation of hen egg white lysozyme(HEWL)in thermal and acidic conditions.Using the well-known Raman indicators for protein tertiary and secondary structures,we monitored and analyzed the concentration effect of Ni(II)ions on the unfolding of tertiary structures and the transformation of sec-ondary structures.The experimental evidence validates the accelerator role of the metal ion in the kinetics.Notably,the additional analysis of the amide I band profile,combined with thioflavin-T fluorescence assays,clearly indicates the inhibitory effect of Ni(II)ions on the formation of amyloid fibrils with organizedβ-sheets structures.Instead,a more significant promotion influence is affirmed on the assembly into other aggregates with disordered struc-tures.The present results provide rich information about the specific metal-mediated protein fibrillation.

Restructuring of 4H Phase Au Nanowires and its Catalytic Behavior toward CO Electro-oxidation

Au nanowires in 4H crystalline phase(4H Au NWs)are synthesized by colloid solution methods.The crys-talline phase and surface structure as well as its performance toward electrochemical oxidation of CO be-fore and after removing adsorbed oleylamine molecules(OAs)intro-duced from its synthesis are evaluat-ed by high-resolution transmission electron microscopy(HR-TEM),X-ray diffraction(XRD),underpoten-tial deposition of Pb(Pb-upd)and cyclic voltammetry.Different methods,i.e.acetic acid cleaning,electrochemical oxidation cleaning,and diethylamine replacement,have been tried to remove the adsorbed OAs.For all methods,upon the removal of the adsorbed OAs,the morphology of 4H gold nanoparticles is found to gradually change from nanowires to large dumbbell-shaped nanoparticles,accompanying with a transition from the 4H phase to the face-centered cubic phase.On the other hand,the Pb-upd results show that the sample sur-faces have almost the same facet composition before and after removal of the adsorbed OAs.After electrochemical cleaning with continuous potential scans up to 1.3 V,CO electro-oxida-tion activity of the 4H Au sample is significantly improved.The CO electro-oxidation activi-ty is compared with results on the three basel Au single crystalline surfaces reported in the lit-erature,possible origins for its enhancement are discussed.

Photothermal Catalytic Selective Oxidation of Isobutane to Methacrylic Acid over Keggin-Type Heteropolyacid

Thermal and photothermal catalytic selec-tive oxidation of isobutane to methacrylic acid(MAA)are comparatively studied over a keggin-type Cs2.9Cu0.34V0.49PMo12O40 het-eropolyacid acid.An introduction of light was observed to enhance both the i-C4H10 conversion and the MAA selectivity,and consequently the MAA formate rate,particularly at low temperatures.Characterization re-sults show that oxidation of methacrolein(MAL)to MAA is the rate-limiting step while UV light illumination promotes the oxidation ofσ-bonded MAL with OH groups toσ-bonded MAA on the catalyst surface.These results demonstrate a synergistic effect of thermal cataly-sis and photocatalysis in selective oxidation of isobutane to MAA,which suggests photother-mal catalysis as a promising strategy to catalyze the selective oxidation of higher hydrocar-bons at relative mild reaction conditions.

Ion-Velocity Imaging Study of Dissociative Charge Exchange Reactions between Ar^(+)and trans-/cis-Dichloroethylene

Dissociative charge exchange re-actions between Ar^(+)ion and trans-/cis-dichloroethylene(trans-/cis-C_(2)H_(2)Cl_(2))are investi-gated with the ion-velocity imag-ing technique.The dechlorinated product C_(2)H_(2)Cl^(+)is the predomi-nant,and most of this product show the spatial distribution around the target,implying that the dissociation occurs in the large impact-parameter collision and via the energy resonant charge transfer.Meanwhile,a few C_(2)H_(2)Cl^(+)locate around the center-of-mass,which is at-tributed to the fragmentation of intimate association between C_(2)H_(2)Cl_(2)and Ar^(+)or in the small impact-parameter collision.The product C_(2)HCl_(+)exhibits the velocity distribution fea-tures similar to those of C_(2)H_(2)Cl_(+).The rarest product C_(2)HCl_(2)+shows the distributions around the molecular target,due to the quick dehydrogenation after the energy-resonant charge transfer in the large impact-parameter collision.