Morphology and valence state evolution of Cu:Unraveling the impact on nitric oxide electroreduction

Ammonia(NH3)serves as a critical component in the fertilizer industry and fume gas denitrification.However,the conventional NH3production process,namely the Haber-Bosch process,leads to considerable energy consumption and waste gas emissions.To address this,electrocatalytic nitric oxide reduction reaction(NORR)has emerged as a promising strategy to bridge NH3consumption to NH3production,harnessing renewable electricity for a sustainable future.Copper(Cu)stands out as a prominent electrocatalyst for NO reduction,given its exceptional NH3yield and selectivity.However,a crucial aspect that remains insufficiently explored is the effects of morphology and valence states of Cu on the NORR performance.In this investigation,we synthesized CuO nanowires(CuO-NF)and Cu nanocubes(Cu-NF)as cathodes through an in situ growth method.Remarkably,CuO-NF exhibited an impressive NH3yield of 0.50±0.02 mg cm^(-2)h^(-1)at-0.6 V vs.reversible hydrogen electrode(RHE)with faradaic efficiency of29,68%±1,35%,surpassing that of Cu-NF(0.17±0.01 mg cm^(-2)h^(-1),16.18%±1.40%).Throughout the electroreduction process,secondary cubes were generated on the CuO-NF surface,preserving their nanosheet cluster morphology,sustained by an abundant supply of subsurface oxygen(s-O)even after an extended duration of 10 h,until s-O depletion ensued.Conversely,Cu-NF exhibited inadequate s-O content,leading to rapid crystal collapse within the same timeframe.The distinctive current-potential relationship,akin to a volcano-type curve,was attributed to distinct NO hydrogenation mechanisms.Further Tafel analysis revealed the exchange current density(i0)and standard heterogeneous rate constant(k0)for CuO-NF,yielding 3.44×10^(-6)A cm^(-2)and 3.77×10^(-6)cm^(-2)s^(-1)when NORR was driven by overpotentials.These findings revealed the potential of CuO-NF for NO reduction and provided insights into the intricate interplay between crystal morphology,valence states,and electrochemical performance.

Valence state effect of Cu on photocatalytic CO_(2)reduction

Copper(Cu)is extensively employed in photocatalytic CO_(2)reduction reactions for the production of high-value products.The valence state of transition metals plays a pivotal role in influencing the catalytic process.However,due to the complex valence state changes of Cu in the CO_(2)reduction reaction,research on its valence state effect is lacking.The current work is to prepare a series of TiO_(2)/CuX with stable Cu valence composition using different copper halides(CuX and CuX_(2),X=Br or Cl)as precursors.The results show that the CuBr_(2)loading leads to Cu^(+)/Cu^(2+) mixed cocatalyst and exhibits the highest activity for CO_(2)photoreduction.The CH4 evolution rate of the TiO_(2)/CuBr_(2)catalyst is as high as 100.59μmol h^(-1)g^(-1),which is 6.6 times that of pristine TiO_(2).The CH4 selectivity reaches 77%.The enhanced catalytic activity and selectivity can be ascribed to the efficient surface adsorption,activation,excellent carrier separation,and transfer ofCu^(+)/Cu^(2+) mixed cocatalyst.Our findings provide a reference for designing highly active Cu-based photocatalysts.

High valence state of Ni and Mo synergism in NiS_(2);MoS_(2)hetero-nanorods catalyst with layered surface structure for urea electrocatalysis

High valence state species are significant in the energy-relevant electrochemical oxidation reactions.Herein,the high active state of Ni^(3+)formation induced by Mo^(6+)and their efficient synergism in NiS_(2)-MoS_(2)hetero-nanorods powder catalyst with the rough layered structure are demonstrated,as proof of concept,for the urea-assisted water electrolysis.This catalyst can be derived from the sulfidation of NiMoO_(4) nanorods that can realize individual metal sulfides sufficiently mixing at a domain size in the nanoscale which creates lots of active sites and nanointerfaces.The high valence state of Mo^(6+)and Ni^(3+)formation and increased conductive phase of 1 T MoS_(2)in the hetero-nanorods compared to the counterpart pure phases are revealed by spectral study and microscopic analysis;high electrochemical surface area and active site exposure are found due to the nano-interface formation and layered rough nanosheets over the surface of nanorods.They show much higher catalytic performance than their pure phases for urea oxidation,including high catalytic activity,stability,charge transfer ability and catalytic kinetics resulting from more active Ni^(3+)species formation and electronic synergism of high valence metals.Transformation of 1 T MoS_(2)to Mo^(6+)and increased amount of Mo^(6+)and Ni^(3+)after stability test indicate their involvement and synergism for the catalysis reaction.The current work offers a novel understanding of the synergistic effect based on the high valence state synergism for heterogeneous catalysts in electrocatalysis.

Crystal Chemistry of Iron in Non-Metamict Chevkinite-(Ce): Valence State and Site Occupation Proportions

The ideal formula for chevkinite can be expressed as A4BC2D2Si4O22. It is important to determine the valence state and site occupation proportions for Fe among the B, C, and D octahedral sites as it may help to identify different species in the chevkinite group. Non-metamict chevkinite-（Ce） from Mianxi alkali feldspar-granite, Sichuan Province, China, was investigated using Moessbauer spectroscopy. The Fe^3＋/∑Fe ratio was 39.2%. A significant increase of Fe^3＋ occured during metamictization and annealing for chevkinite-group minerals. In metamict samples Fe tended to lower coordination, According to the correlation between bond length and isomer shift （IS）, the quadrupole doublets with IS = 1.10 and 0.94 mm·s^-1 can be assigned to Fe^2＋ in the B and C octahedral sites, respectively. Based on the correlation between octahedral distortion and quadrupole splitting （QS）, the quadrupole doublets with QS = 0.86 and 0.77 mm·s^-1 can be assigned to Fe^3＋ in the C and D sites, respectively. The simplified formula can be revised as： Ce4Fe^2＋ （Ti, Fe^2＋, Fe^3＋ ）2（Ti, Fe^3＋ ）2Si4（O,OH）22. It indicated that the non-metamict chevkinite-（Ce） belonged to Fe^2＋ end member of the chevkinite group because Fe^2＋ was the predominant component in the B site.

VALENCE STATE OF C AtOMS AND σ_t-η_n SEPARABILITY OF MOLECULAR ORBITALS IN THE (BUCKMINSTER)FULLERENE C_(50)

The valence state of C atoms and the structure of molecular orbitals of the (Buckminster)Fullerene C_(60)have been demonstrated. It has been shown that when a motion-coordinate system is adopted, in which the coordinate origin is at every C atom, the z axis is in the direction of the normal and the (x,y) axes are in the direction of tangents of C_(60)'s spherical surface, 240 valence atomic orbitals of C_(60) can be divided into two groups. All (P_x, P_y)atomic orbitals named as Pt ones and all the other P_z atomic orbitals named as p. ones, That is to say that if we name the molecular orbital linearly combined of P_t atomic orbitals as σ_t and the molecular orbital linearly combined of P_n atomic orbitals as π_n, the 240 valence molecular orbitals are of the property of σ_t-π_n separability. It has also been shown that the frontier and nearby frontier molecular orbitals are π_n ones, and therefore the essential physical and chemical properties of C_(60) are determined by its π_n molecular orbitals.

ON THE VALENCE STATE OF COPPER IN HIGH T_c SUPERCONDUCTOR YBa_2Cu_3O_x

Various optical luminescence spectroscopic techniques were used to characterize the high T_c superconductor YBa_2Cu_3O_x.The emission bands reveal that Cu^(3+) coexist with Cu^(2+) and Cu^+ in this material.

Two-Photon Excited State Dynamics of Dark Rydberg and Bright Valence States in Furan

Two-photon absorption in systems with parity permits access to states that cannot be directly prepared by one-photon absorption. Here we investigate ultrafast internal conversion （IC） dynamics of furan by using this strategy in combination with femtosecond time-resolved photoelectron imaging. The dark Rydberg S1 and bright valence S2 states are simultaneously excited by two photons of 405 nm, and then ionized by two photons of 800nm. The IC from S2 to S1 is clearly observed and extracted from the time dependence of the higher photoelectron kinetic energy （PKE） component. More importantly, the internal conversions to hot So from directly-prepared S1 and secondarily-populated S1 are unambiguously identified by the time-dependence of the lower PKE component. The average lifetime of the S2 and S1 states is measured to be 29 fs. The internal conversions of S2 to S1, S1 to hot So occur on estimated timescales of 15.4 fs and 38 fs, respectively.

Recent research progress on mixed valence state tungsten based materials

Synthesis and characterization of tungsten based mixed valence state nanoparticles and their novel applications are reviewed.The mixed valence state tungsten based homogeneous nanomaterials such as bronze structure M_(x)WO_(3)(M=Na^(+),K^(+),Rb^(+),Cs^(+),NH_(4)^(+),etc.)and tungsten sub-oxide W_(18)O_(49) possess excellent infrared(IR)light shielding property,implying their great potential applications on heat ray shielding and indoor energy saving effect in summer season.Also,some novel properties such as electric conductivity,bio thermal therapy function and electrochromic properties of mixed valence state tungsten based materials are introduced.The design of components,formation of composites and structure control of thin films are expected to realize the property enhancement and candidates for practice application as window materials.The multifunc-tionality of the mixed valence state based composites also implies great potential on novel applications of various building materials.

Studies on exposure status of inhabitants to water-arsenic valence states in areas with endemic arsenism in the Datong basin in Shanxi

This study aimed to describe the distribution of water-arsenic(As)valence states and its relationship to areas with endemic arsenism in the Datong basin.Drinking water samples of patients with endemic arsenism and a control group were examined using hydride generation atomic fluorescence spectrometry(HG-AFS).We analyzed the data using SPSS10.0 for Windows.The As(III)/As ratio was 52.1%in the water sample,exceeding the national standard of 0.05 mg/L.The As(III)/As ratio significantly varied among the different stages in the disease-state groups,and with the control group(χ^(2)=22.4,P<0.01).The As(III)/As(V)ratio significantly varied in the four groups(χ^(2)=26.19,P<0.01),with a tendency to increase along with the seriousness of the disease state.The most common type of drinking water arsenic valence state was As(III)in the endemic diseaseareas.Endemic arsenism was positively correlated with As(III).This led us to conclude that the fraction of each water-arsenic valence state should be studied when determining the arsenic content of drinking water.

Experimental study of highly excited even-parity bound states of the Sm atom

In this work, a three-step autoionization detection method and direct photoionization detection method are employed to measure the highly excited even-parity states of the Sm atom in the energy region between 36360 cm^-1 and 40800 cm^-1. Comparisons between the results from the two detection techniques enable us to discriminate the Rydberg states from the valence states in the same energy region with the information of level energies, possible J values and their relative intensities. Furthermore, in the experiment two different excitation schemes are designed to obtain the spectra of highly excited even-parity states of the Sm atom. With a detailed analysis of the experimental data, this work not only confirms the results about many spectral data from the literature with different excitation schemes, but also reports new spectral data on 29 Rydberg states and 23 valence states.

Precisely quantifying bulk transition metal valence evolution in conventional battery electrode by inverse partial fluorescence yield

Precisely quantifying transition metal(TM) redox in bulk is a key to understand the fundamental of optimizing cathode materials in secondary batteries. At present, the commonly used methods to probe TM redox are hard X-ray absorption spectroscopy(hXAS) and soft X-ray absorption spectroscopy(sXAS).However, they are both facing challenges to precisely quantify the valence states of some transition metals such as Mn. In this paper, Mn-L iPFY(inverse partial fluorescence yield) spectra extracted from Mn-L m RIXS(mapping of resonant inelastic X-ray scattering) is adopted to quantify Mn valence states. Mn-L i PFY spectra has been considered as a bulk-sensitive, non-distorted probe of TM valence states.However, the exact precision of this method is still unclear in quantifying practical battery electrodes.Herein, a series of LiMn_(2)O_(4) electrodes with different charge and discharge states are prepared. Based on their electrochemical capacity(generally considered to be very precise), the precision of Mn iPFY in quantifying bulk Mn valence state is confirmed, and the error range is unraveled. Mn-L mRIXS iPFY thus is identified as one of the best methods to quantify the bulk Mn valence state comparing with hXAS and sXAS.

Visible-light deposition of CrO_(x) cocatalyst on TiO_(2):Cr valence regulation for superior photocatalytic CO_(2)reduction to CH_(4)

Photodeposition is widely adopted for implanting metal/metal oxide cocatalysts on semiconductors.However,it is prerequisite that the photon energy should be sufficient to excite the host semiconductor.Here,we report a lower-energy irradiation powered deposition strategy for implanting CrO_(x) cocatalyst on TiO_(2).Excitingly,CrO_(x)-400 implanted under visible-light irradiation significantly promotes the CH4 evolution rate on TiO_(2)to 8.4μmolg·^(-1)h^(-1) with selectivity of98%from photocatalytic CO_(2)reduction,which is 15 times of that on CrO_(x)-200 implanted under UV-visible-light irradiation.Moreover,CrO_(x)-400 is identified to be composed of higher valence Cr species compared to CrO_(x)-200.This valence states regulation of Cr species is indicated to provide more active sites for CO_(2) adsorption/activation and to modulate the reaction mechanism from single Cr site to Cr-Cr dual sites,thus endowing the superior CH_(4)production.This work demonstrates an alternative strategy for constructing efficient metal oxides cocatalysts on wide bandgap semiconductor.

Formation of unusual Cr^5+charge state in CaCr0.5Fe0.5O3 perovskite

A new oxide CaCr0.5Fe0.5O3 was prepared under high pressure and temperature conditions. It crystallizes in a B-site disordered Pbnm perovskite structure. The charge combination is determined to be Cr^5＋/Fe^3＋ with the presence of unusual Cr^5＋ state in octahedral coordination, although Cr^4＋ and Fe^4＋ occur in the related perovskites CaCrO3 and CaFeO3. The randomly distributed Cr^5＋ and Fe^3＋ spins lead to short-range ferromagnetic coupling, whereas an antiferromagnetic phase transition takes place near 50 K due to the Fe^3＋-O-Fe^3＋ interaction. In spite of the B-site Cr^5＋/Fe^3＋ disorder, the compound exhibits electrical insulating behavior. First-principles calculations further demonstrate the formation of CaCr0.5^5＋Fe0.5O3 charge combination, and the electron correlation effect of Fe^3＋ plays an important role for the insulting ground state. CaCr0.5Fe0.5O3 provides the first Cr^5＋ perovskite system with octahedral coordination, opening a new avenue to explore novel transition-metal oxides with exotic charge states.

The mechanism of hydrogen abstraction by high valence transition metal oxo compounds

We present here a systematic theoretical study to explore the underlying mechanisms of the H abstraction reaction from methane. Various abstracting agents have been modeled, using oxygen radicals and a set of high valence metal oxo compounds. Our calculations demonstrate that although H abstraction from CH3-H by metal oxoes can be satisfactorily fitted into the Polanyi correlation on the basis of oxygen radicals, the mechanisms behind are significantly different. The frontier orbital analyses show that there are three electrons and three active orbitals (3e, 3o) involved in H abstraction by oxygen radicals; whereas an additional orbital of pi(M-O)* is involved in H abstraction by M = O, resulting in a (4e, 4o) interaction. In terms of valence bond state correlation diagram, we find that H abstraction by a metal oxo may benefit from the contribution of ionic resonance structures, which could compensate the penalty of opening the M-O pbond. We believe that these findings can help to design more effective catalysts for the activation of light alkanes. (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.

A universal charge-compensating strategy for high-energy-density pseudocapacitors

For pseudocapacitive electrode materials(PseEMs),despite much progress having been made in achieving both high power density and high energy density,a general strategy to guide the enhancement of intrinsic capacitive properties of PseEMs remains lacking.Here,we demonstrate a universal chargecompensating strategy to improve the charge-storage capability of PseEMs intrinsically:ⅰ) in the electrolyte with anion as charge carriers(such as OH-),reducing the multivalent cations of PseEMs into lower valences could create more reversible low-to-high valence redox cou ples to promote the intercalation of the anions;ⅱ) in the electrolytes with cation as charge carriers(such as H^(+),Li^(+),Na^(+)),oxidizing the multivalent cations of PseEMs into higher valences could introduce more reversible high-to-low valence redox couples to promote the intercalation of the cations.And we demonstrated that the improved intrinsic charge-storage capability for PseEMs originates from the increased Faradaic charge storage sites.

Enhancing the dynamic electron transfer of Au species on wormhole-like TS-1 for boosting propene epoxidation performance with H_(2) and O_(2)

Engineering unique electronic structure of catalyst to boost catalytic performance is of prime scientific and industrial importance.Herein,the identification of intrinsic electronic sensitivity for direct propene epoxidation was first achieved over highly stable Au/wormhole-like TS-1 catalyst.Results show that the electron transfer of Au species can be regulated by manipulating the dynamic evolutions and contents of Au valence states,thus resulting in different catalytic performance in 100 h time-on-stream.By DFT calculations,kinetic analysis and multicharacterizations,it is found that the Au^(0) species with higher electronic population can easily transfer more electrons to activate surface O_(2) compared with Au^(1+) and Au^(3+) species.Moreover,there is a positive correlation between Au^(0) content and activity.Based on this correlation,a facile strategy is further proposed to boost Au^(0) percentage,resulting in the reported highest PO formation rate without adding promoters.This work harbors tremendous guiding significance to the design of highly efficient Au/Ti-containing catalyst for propene epoxidation with H_(2) and O_(2).

In-situ reconstruction of catalysts in cathodic electrocatalysis: New insights into active-site structures and working mechanisms

Cathodic electrocatalytic reactions, such as hydrogen evolution and CO_(2)/N_(2) reduction, are the key processes that store intermittent electricity into stable chemical energy. Although a great progress has been made to boost activity and selectivity via elaborative catalyst design, the structure–property relationships have not been sufficiently understood in the context of surface reconfiguration under working conditions. Recent efforts devoted to tracking dynamic evolution of electrocatalysts using in-situ and/or operando techniques gave new insights into the real structure and working mechanism of active sites,and provided principles to design better catalysts. The achievement of cathodic electrocatalysts in this subject is herein summarized, focusing on the correlations between reconstructed surface and electrocatalytic performance. Briefly, the thermodynamics of reconstruction at cathodes is discussed at first, and then the representative progresses in H_(2) evolution and CO_(2)/N_(2) reduction are introduced in sequence to acquire insights into electrochemical processes on in-situ reconfigured surfaces or interfaces. Finally, a perspective is offered to guide future investigations. This review is anticipated to shed some new light on in-depth understanding cathodic electrocatalysis and exploiting prominent electrocatalysts.

Hydrothermal Synthesis and Characterization of Ce_(1-x)Mn_xO_(2-δ) Solid Solutions

Nanocrystals of Ce1-xMnxO2-δ（x=0.00,0.05,0.10,0.15,and 0.20） were synthesized by a hydrothermal reaction route.The solid solutions crystallized in a cubic fluorite structure with a particle size in the range of 11～15 nm.The incorporation of Mn ions in CeO2 resulted in a lattice volume reduction.Mn ions showed a mixed valence state of ＋2,＋3 and ＋4 in CeO2 lattice.An obvious red-shift of the absorption threshold edge was observed from the UV-visible spectrum.Compared with the bulk CeO2,Ce1-xMnxO2-δ nanocrystals exhibited a lower releasing oxygen temperature as indicated by TPR technique.

铂基催化剂用于柴油烃氧化(英文)

The catalytic performance of Pt-based catalysts for the total oxidation of hydrocarbons was investigated.The activity of supported Pt catalysts(Pt/Al2O3,Pt/ZrO2,Pt/TiO2,and Pt/H-ZSM-5)depends on the metal oxide support.Pt/Al2O3 showed the highest catalytic activity when the catalysts were aged at 750°C for 50 h in air.The activity of Pt/Al2O3 was dependent on the valence state of the Pt surface.Pt/Al2O3 with the Pt surface in the metallic state was more active than with the surface in the cationic state.The surface density of acid and basic sites on the Al2O3 support controlled the valence state of the Pt surface and stability of the Pt particles in the highly dispersed state,respectively.

A-site ordered perovskite CaCu3Cu2Ir2O(12-δ) with square-planar and octahedral coordinated Cu ions

A novel CaCu_3Cu_2Ir_2O_（12-δ） polycrystalline sample was synthesized at 8 GPa and 1373 K.Rietveld structural analysis shows that this compound crystallizes in an AA＇_3B_4O_（12）-type A-site ordered perovskite structure with space group Im-3.Xray absorption spectra reveal a ＋2-charge state for both the square-planar and octahedral coordinated Cu ions,and the valence state of Ir is found to be about ＋5.Although the A-site Ca and the A＇-site Cu^（2＋） are 1：3 ordered at fixed atomic positions,the distribution of B-site Cu^（2＋） and Ir^（5＋） is disorderly.As a result,no long-range magnetic ordering is observed at temperatures down to 2 K.Electrical transport and heat capacity measurements demonstrate itinerant electronic behavior.The crystal structure is stable with pressure up to 35.7 GPa at room temperature.