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The controlled regulation of A-site in rare earth manganate perovskites can orderly arrange the electronic states, leading to the emergence of unique transport properties. However, it is challenging to balance crystal structure stability and property variations during the multi-ion doping. In this study, a series of multivalent manganate perovskites are synthesized by hydrothermal method through the A-site multielement doping, which enables the manganese atoms with varying valence states to orderly arrange at the B site. Powder X-ray diffraction (PXRD) and X-ray absorption spectra (XAS) confirm that the splitting of the K─O hybrid orbitals in the crystal effectively prevents any distortion of the MnO6 octahedron, thereby facilitating the ordered arrangement of Mn (III) -Mn (IV) -Mn (V) at the B-site and promoting superstructure formation. The transient absorption spectra (TAS) reveals that the sequential arrangement of Mn (III) - Mn (IV) - Mn(V) better forms the charge transfer channels, and thereby makes the photodynamic properties of the sample composition-dependent. These photodynamic properties will facilitate the study of exciton-electron coupling behavior in LCKMO crystals during electrical transport.

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Water electrolysis to produce hydrogen (H2) using renewable energy is one of the most promising candidates for realizing carbon neutrality, but its reaction kinetics is hindered by sluggish anodic oxygen evolution reaction (OER). Ruthenium (Ru) in its high-valence state (oxide) provides one of the most active OER sites and is less costly, but thermodynamically unstable. The strong interaction between Ru nanoparticles (NPs) and nickel hydroxide (Ni(OH)2) is leveraged to directly form Ru-Ni(OH)2 on the surface of a porous nickel foam (NF) electrode via spontaneous galvanic replacement reaction. The formation of Ru─O─Ni bonds at the interface of the Ru NPs and Ni(OH)2 (Ru-Ni(OH)2) on the surface oxidized NF significantly enhance stability of the Ru-Ni(OH)2/NF electrode. In addition to OER, the catalyst is active enough for the hydrogen evolution reaction (HER). As a result, it is able to deliver overpotentials of 228 and 15 mV to reach 10 mA cm-2 for OER and HER, respectively. An industry-scale evaluation using Ru-Ni(OH)2/NF as both OER and HER electrodes demonstrates a high current density of 1500 mA cm-2 (OER: 410 mV; HER: 240 mV), surpassing commercial RuO2 (OER: 600 mV) and Pt/C based performance (HER: 265 mV).

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Cerium-based adsorbents possessed unique advantages of valence variability and abundant oxygen vacancies in hexavalent chromium (Cr(VI)) adsorption, but high cost and unstable properties restricted their application in Cr(VI) contained wastewater treatment. Herein, a series of bimetallic adsorbents with different cerium/iron ratios (CeFe@C) were prepared by adding inexpensive Fe into Ce-based adsorbents (Ce@C), and the effect of Fe doping on adsorption properties of Ce@C for Cr(VI) was investigated thoroughly. Compared with pristine Ce@C, CeFe@C exhibited excellent removal performance for Cr(VI), and the improved maximum adsorption capacity reached 75.11 mg/g at 25℃. Benefiting from Fe doping, CeFe@C had good regeneration property, with only 25 % decrease after five adsorption-desorption cycles. Contents of trivalent cerium (Ce(III)) and oxygen vacancies (Ov) in bimetallic adsorbents were positively correlated with divalent iron (Fe(II)) doping, indicating that the formation of Ce(III) and surface defects on Ce@C could be effectively regulated by Fe doping. Density functional theory (DFT) calculation results further proved that the doped Fe enhanced the electron transfer effectively and lowered the energy barriers of Cr(VI) adsorption onto Ce@C surface, strengthening the reduction and complexation to Cr(VI). This study provides new insights for improving the Cr(VI) removal performance by modified Ce-based adsorbents, and further promotes the utilization potentiality of low-cost and low-toxicity Ce-based adsorbents in Cr(VI)-containing wastewater treatment.

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The exploitation of multicomponent composites (MCCs) has become the main pathway for obtaining advanced microwave absorption materials (MAMs). Herein, a metal valence state modulation strategy is proposed to tune the electromagnetic (EM) parameters and improve microwave absorption performances. Core@shell hollow carbon microspheres@MoSe2 and hollow carbon microspheres@MoSe2/MoOx MCCs with various mixed-valence states content are well-designed and produced by a simple hydrothermal reaction or/and heat treatment process. The results reveal that the thermal treatment of hollow carbon microspheres@MoSe2 in Ar and Ar/H2 leads to the in situ formation of MoOx and multivalence state, respectively, and the enhanced content of Mo4+ in the designed MCCs greatly boosts their impedance matching characteristics, polarization, and conduction loss capacities, which lead to their evidently improved EM wave absorption properties. Amongst, the as-prepared hollow carbon microspheres@MoSe2/MoOx MCCs achieve an effective absorption bandwidth of 5.80 GHz under a matching thickness of 1.97 mm and minimum reflection loss of -21.49 dB. Therefore, this work offers a simple and universal method to fabricate core@shell hollow carbon microspheres@MoSe2/MoOx MCCs, and a novel and feasible metal valence state modulation strategy is proposed to develop high-efficiency MAMs.

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Electrochemical CO2 reduction reaction (CO2RR) offers a sustainable strategy for producing fuels and chemicals. However, it suffers from sluggish CO2 activation and slow water dissociation. In this work, we construct a (P-O)δ- modified In catalyst that exhibits high activity and selectivity in electrochemical CO2 reduction to formate. A combination of in situ characterizations and kinetic analyses indicate that (P-O)δ- has a strong interaction with K+(H2O)n, which effectively accelerates water dissociation to provide protons. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) measurements together with density functional theory (DFT) calculations disclose that (P-O)δ- modification leads to a higher valence state of In active site, thus promoting CO2 activation and HCOO* formation, while inhibiting competitive hydrogen evolution reaction (HER). As a result, the (P-O)δ- modified oxide-derived In catalyst exhibits excellent formate selectivity across a broad potential window with a formate Faradaic efficiency as high as 92.1 % at a partial current density of ~200 mA cm-2 and a cathodic potential of -1.2 V vs. RHE in an alkaline electrolyte.

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Electrocatalytic carbonylation of CO and CH3OH to dimethyl carbonate (DMC) on metallic palladium (Pd) electrode offers a promising strategy for C1 valorization at the anode. However, its broader application is limited by the high working potential and the low DMC selectivity accompanied with severe methanol self-oxidation. Herein, our theoretical analysis of the intermediate adsorption interactions on both Pd0 and Pd4+ surfaces revealed that inevitable reconstruction of Pd surface under strongly oxidative potential diminishes its CO adsorption capacity, thus damaging the DMC formation. Further theoretical modeling indicates that doping Pd with Cu not only stabilizes low-valence Pd in oxidative environments but also lowers the overall energy barrier for DMC formation. Guided by this insight, we developed a facile two-step thermal shock method to prepare PdCu alloy electrocatalysts for DMC. Remarkably, the predicted Pd3Cu demonstrated the highest DMC selectivity among existing Pd-based electrocatalysts, reaching a peaked DMC selectivity of 93 % at 1.0 V versus Ag/AgCl electrode. (Quasi) in situ spectra investigations further confirmed the predicted dual role of Cu dopant in promoting Pd-catalyzed DMC formation.

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The oxygen evolution reaction (OER) performance of NiCo LDH electrocatalysts can be improved through fluorine doping. The roles of Ni and Co active sites in such catalysts remain ambiguous and controversial. In addressing the issue, this study draws upon the molecular orbital theory and proposes the active center competitive mechanism between Ni and Co. The doped F-atoms can directly impact the valence state of metal atoms or exert an indirect influence through the dehydrogenation, thereby modulating the active center. As the F-atoms are progressively aggregate, the eg orbitals of Ni and Co transition from e2 g to e1 g, and subsequently to e0 g. The corresponding valence state elevates from +2 to +3, and then to +4, signifying an initial increase followed by a subsequent decrease in the electrocatalytic performance. Furthermore, a series of F-NiCo LDH catalysts are synthesized to verify the eg orbital occupancy analysis, and the catalytic OER overpotentials are 303, 243, 240, and 246 mV at the current density of 10 mA cm-2, respectively, which coincides well with the theoretical prediction. This investigation not only provides novel mechanistic insights into the transition and competition of Ni and Co in F-NiCo LDH catalysts but also establishes a foundation for the design of high-performance catalysts.

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The development of an efficient electrocatalyst for HMF oxidation to FDCA has been in the early stages. Herein, the NiNPs/GO-Ni-foam is fabricated as an electrocatalyst for FDCA production. However, the electrocatalytic performance of the untreated NiNPs/GO-Ni-foam is observed with moderate Faradaic efficiency (FE) (73.0%) and FDCA yield (80.2%). By electrochemically treating the NiNPs/GO-Ni-foam in an alkaline solution with positive potential at different treatment durations, the degree of NiOOH on metal surfaces is changed. The distinctive electrocatalytic activity obtained when using the different NiOOH degrees allows to understand the crucial impact of NiOOH species in HMF electrooxidation. Enhancing the portion of the NiOOH phase on the electrocatalyst surface improves electrocatalytic activity in terms of FE and FDCA yield up to 94.8±4.8% and 86.9±4.1%, respectively. Interestingly, as long as the NiOOH portion on the electrocatalyst surface is preserved or regenerated, the electrocatalyst performance can be intact even after several catalytic cycles. The theoretical study via density functional theory (DFT) also agrees with the experimental observations and confirms that the NiOOH phase facilitates the electrochemical transformation of HMF to FDCA through the HMFCA pathway, and the potential limiting step of the overall reaction is the oxidation of FFCA to FDCA.

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The construction of materials with rapid electron transfer is considered an effective method for enhancing electrochemical activity in electroanalysis. It has been widely demonstrated that valence changes in transition metal ions can promote electron transfer and thus increase electrochemical activity. Recently, valence-variable transition metal oxides (TMOs) have shown popular application in electrochemical analysis by using their abundant valence state changes to accelerate electron transfer during electrochemical detection. In this review, we summarize recent research advances in valence changes of TMOs and their application in electrochemical analysis. This includes the definition and mechanism of valence change, the association of valence changes with electronic structure, and their applications in electrochemical detection, along with the use of density functional theory (DFT) to simulate the process of electron transfer during valence changes. Finally, the challenges and opportunities for developing and applying valence changes in electrochemical analysis are also identified.

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CONTEXT: Why are the halonium cations so effective in forming strongly-bound complexes? We directed our research to address this question and we present electrostatic potential data for the valence-state halogen atoms X and halonium cations X+, where X = Cl, Br, I. The electron densities and electrostatic potentials of the halonium cations show considerably greater anisotropy than do the valence state halogens. The distances from the electrostatic potential surface maxima to the halogen nuclei are about 0.5 Å smaller than the distances from the electrostatic potential surface minima to the nuclei, giving the halonium cations each a more disk-like shape than the corresponding neutral valence state halogens. Their surface electrostatic potentials are totally consistent with the directionalities of halonium cations in complexes and the strengths of their interactions. To add perspective to this brief report, we have included calculations of the isotropic cation K+ and noble gas Kr. METHODS: The calculations of the electrostatic potentials of the valence states of the halogen atoms Cl, Br and I and the halonium cations Cl+, Br+ and I+, as well as K+ and Kr, on 0.001 au contours of their electronic densities were carried out with Gaussian O9 and the Wave Function Analysis - Surface Analysis Suite (WFA-SAS) at the M06-2X/6-31 + G(d,p) and M06-2X/3-21G* levels.

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Despite having favorable energetics and tunable optoelectronic properties, utilization of BaTiO3 (BTO) for photocatalytic reactions is limited by its absorption only in the ultraviolet region. To address this challenge, BTO is doped with iridium (Ir) to induce visible light absorption. The visible light-induced photocatalytic H2 generation efficiency is enhanced by 2 orders of magnitude on selective conversion of the Ir valence state from Ir4+ to Ir3+. To understand such intriguing behavior, valence state-dependent changes in the optoelectronic, structural, and surface properties and electronic band structure are comprehensively investigated. The effect of electron occupancy change between Ir4+ (t2g5 eg0) and Ir3+ (t2g6 eg0) and their energetic positions within the band gap is found to significantly influence H2 generation. Besides this, converting Ir4+ to Ir3+ enhanced the photocathodic current and lowered the onset potential. Results aid in designing photocatalysts to efficiently use low-energy photons for enhancing solar H2 production in these emerging BTO-based photocatalysts. Collectively, the observations made in this work highlight the promising application of Ir3+:BTO in z-scheme photocatalysis.

RESUMEN

The burgeoning field of optoelectronic devices necessitates a mechanism that gives rise to a large contrast in the electrical and optical properties. A SmTe film with a NaCl-type structure demonstrates significant differences in resistivity (over 105) and band gap (approximately 1.45 eV) between as-deposited and annealed films, even in the absence of a structural transition. The change in the electronic structure and accompanying physical properties is attributed to a rigid-band shift triggered by a valence transition (VT) between Sm2+ and Sm3+. The stress field within the SmTe film appears closely tied to the mixed valence state of Sm, suggesting that stress is a driving force in this VT. By mixing the valence states, the formation energy of the low-resistive state decreases, providing nonvolatility. Moreover, the valence state of Sm can be regulated through annealing and device-operation processes, such as applying voltage and current pulses. This investigation introduces an approach to developing semiconductor materials for optoelectrical applications.

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We investigated the changes in the structural and luminescent properties of Eu-ion-doped A2SiO4 (A2SiO4:Eu, A = Ba, Sr, and Ca) by annealing in oxidizing and reducing atmospheres. The initially synthesized samples displayed distinct, intense red emissions at approximately 600 and 700 nm, which can be attributed to the presence of Eu3+ ions. The emission intensity of Eu3+ was the strongest in Ca2SiO4:Eu, which exhibited the lowest lattice symmetry among the three samples. Remarkably, following annealing in a reducing atmosphere (H2), the previously observed red emission vanished, and instead, a strong green emission at around 500 nm, which is characteristic of Eu2+ ions. Because of the two occupation sites of the Eu ions in A2SiO4, the emission of Eu2+ strongly depends on the excitation wavelength, which is the most evident in Ca2SiO4:Eu. Conversely, after annealing in an oxidizing atmosphere (O2), the emission in the green region was suppressed and the emission in the red region returned. The reversible transition between two oxidation states occurred repeatedly by alternating H2 and O2 annealing, resulting in good color tunability in wide visible region with a simple ambient annealing process in a single compound.

RESUMEN

Cu and graphene oxide composites (Cu-GO) were designed by anchoring Cu+ via oxygen groups in GO based on the heavy co-relationships of copper (Cu) anode electrocatalytic activity with Cu valence state. With the consumption of oxygen groups under various pyrolysis temperatures, the Cu valence state changed from Cu ions (as CuCl2 and CuCl) to Cu oxide (CuO and Cu2O) and the final metallic Cu. In which the Cu+ in CuCl was more favorable for electrocatalytic oxidation than other Cu valence states. Due to the dramatic contribution of 1O2 and active chlorine, 100% degradation efficiency was achieved using tetracycline hydrochloride (TCH) as the target pollutant. Cu+ showed a selective preference for 1O2 and active chlorine triggering, rather than metallic Cu. Under the attack of 1O2 and active chlorine, the degradation intermediates of TCH were then provided by LC-MS results. The final results not only prove the feasibility of the Cu-GO/electrocatalysis system for pollution control but also shed light on the anode design via Cu valence state modulation.

Asunto(s)

RESUMEN

Electrochemical water splitting is a promising approach for producing sustainable and clean hydrogen. Typically, high valence state sites are favorable for oxidation evolution reaction (OER), while low valence states can facilitate hydrogen evolution reaction (HER). However, here we proposed a high valence state of Co3+ in Ni9.5 Co0.5 -S-FeOx hybrid as the favorable center for efficient and stable HER, while structural analogues with low chemical states showed much worse performance. As a result, the Ni9.5 Co0.5 -S-FeOx catalyst could drive alkaline HER with an ultra-low overpotential of 22 mV for 10 mA cm-2 , and 175 mV for 1000 mA cm-2 at the industrial temperature of 60 °C, with an excellent stability over 300 h. Moreover, this material could work for both OER and HER, with a low cell voltage being 1.730 V to achieve 1000 mA cm-2 for overall water splitting at 60 °C. X-ray absorption spectroscopy (XAS) clearly identified the high valence Co3+ sites, while in situ XAS during HER and theoretical calculations revealed the favorable electron capture at Co3+ and suitable H adsorption/desorption energy around Co3+ , which could accelerate the HER. The understanding of high valence states to drive reductive reactions may pave the way for the rational design of energy-related catalysts.

RESUMEN

The electronic properties, in particular, the occupation number of 5f electrons and the valence state of U ions in uranium sesquinitride (U2 N3 ) are studied by using density functional theory (DFT) calculations merged with dynamical mean-field theory (DMFT). The results demonstrate that j=5/2 and j=7/2 manifolds are in the weakly correlated metallic and weakly correlated insulating regimes, respectively. The quasi-particle weights indicate that LS coupling scheme is more feasible for 5f electrons, which are not in the orbital-selective localized state. The weighted summation of the occupation probabilities of 5fn (n=0,1,2,3,4) atomic configurations suggests that 5f electrons have the inter-configuration fluctuation, or the mixed-valence state for U ions, together with an average occupation number of 5f electrons n5f ∼2.234, which is in good agreement with the electron localization function (ELF) and occupation analysis based on other DFT-based calculations. The 5fn -mixing-driven inter-configuration fluctuation might originate from the dual nature of 5f electrons, and the flexible electronic configuration of U ions. Finally, the so-called quasiparticle band structure is also discussed.

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Hexavalent chromium (Cr(VI)) is a toxic heavy metal and its mobility and bioaccessibility in soils are influenced by soil properties. In this study, the soil pH and organic carbon contents of Ultisol, Alfisol, and Inceptisol were adjusted before they were polluted with 230 mg kg-1 Cr(VI). Alkaline digestion, sequential extraction, and an in vitro experiment were conducted to study the valence state, species, and bioaccessibility of Cr in the soils. The results showed that a high soil pH was not favorable for reduction of Cr(VI); therefore the Cr(VI) and exchangeable Cr contents were positively related to soil pH. Soil organic carbon promoted the reduction of Cr(VI). Almost all Cr(VI) was reduced to Cr(III) when the soil organic carbon content reached 10 g kg-1. Chromium bioaccessibility in simulated gastric and intestinal phase solutions was influenced by Cr(VI) and Cr(III) adsorption/desorption, dissolution/precipitation, and redox reactions. Chromium bioaccessibility differences between the gastric and intestinal phases were associated with the Cr(VI)/Cr(III) ratio. Acidic conditions and a high organic carbon content promoted the conversion of Cr(VI) to Cr(III). When soil pH was increased from 4.01 to 5.85, Cr(VI) in Alfisol without the addition of humic acid increased from 96.38 to 174.78 mg kg-1, the exchangeable Cr proportion increased from 9.7% to 22.6%, and Cr bioaccessibility increased from 41.29% to 49.14% in the gastric phase and from 41.32% to 48.24% in the intestinal phase. When the organic carbon content increased from 3.95 to 9.28 g kg-1 in Alfisol, Cr(VI) content decreased from 167.66 to 20.52 mg kg-1, which led to a decrease in Cr bioaccessibility from 49.15% to 13.8% in the gastric phase and from 45.85% to 7.67% in the intestinal phase. Therefore, acidic conditions and increasing soil organic carbon levels can reduce the health risk posed by Cr in soils.

Asunto(s)

RESUMEN

Electrochemical CO2 reduction provides a potential means for synthesizing value-added chemicals over the near equilibrium potential regime, i.e., formate production on Pd-based catalysts. However, the activity of Pd catalysts has been largely plagued by the potential-depended deactivation pathways (e.g., [Formula: see text]-PdH to [Formula: see text]-PdH phase transition, CO poisoning), limiting the formate production to a narrow potential window of 0 V to -0.25 V vs. reversible hydrogen electrode (RHE). Herein, we discovered that the Pd surface capped with polyvinylpyrrolidone (PVP) ligand exhibits effective resistance to the potential-depended deactivations and can catalyze formate production at a much extended potential window (beyond -0.7 V vs. RHE) with significantly improved activity (~14-times enhancement at -0.4 V vs. RHE) compared to that of the pristine Pd surface. Combined results from physical and electrochemical characterizations, kinetic analysis, and first-principle simulations suggest that the PVP capping ligand can effectively stabilize the high-valence-state Pd species (Pdδ+) resulted from the catalyst synthesis and pretreatments, and these Pdδ+ species are responsible for the inhibited phase transition from [Formula: see text]-PdH to [Formula: see text]-PdH, and the suppression of CO and H2 formation. The present study confers a desired catalyst design principle, introducing positive charges into Pd-based electrocatalyst to enable efficient and stable CO2 to formate conversion.

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The modification of Au nanoparticles can improve the antioxidant activity of CeO2, however, nano Au/CeO2has also met some problems such as low atomic utilization, the limit of reaction conditions, and high cost. Au single atom catalysts can well solve the above-mentioned problems, but there are some contradictory results about the activity of single atom Au1/CeO2and nano Au/CeO2. Here, we synthesized rod-like Au single atom Au/CeO2(0.4% Au1/CeO2) and nano Au/CeO2(1% Au/CeO2, 2% Au/CeO2and 4% Au/CeO2), and their antioxidant activity from strong to weak is 0.4% Au1/CeO2, 1% Au/CeO2, 2% Au/CeO2and 4% Au/CeO2, respectively. The higher antioxidant activity of 0.4% Au1/CeO2is mainly due to the high Au atomic utilization ratio and the stronger charge transfer between Au single atoms and CeO2, resulting in the higher content of Ce3+. Due to the coexistence of Au single atoms and Au NPs in 2% Au/CeO2, the antioxidant activity 2% Au/CeO2is higher than that of 4% Au/CeO2. And the enhancement effect of Au single atoms was not affected by the concentration of ·OH and material concentration. These results can promote the understanding of the antioxidant activity of 0.4% Au1/CeO2and promote its application.

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The discovery of superconductivity in the infinite-layer nickelate Nd0.8Sr0.2NiO2 has motivated tremendous efforts for its significance toward the understanding of high-temperature superconductivity. However, the synthesis of infinite-layer nickelates is instable and has become a hindrance to experimental progress. Optimizing the growth of precursor Nd0.8Sr0.2NiO3 by pulsed laser deposition is crucial for obtaining infinite-layer nickelates. By systematically investigating the growth of Nd0.8Sr0.2NiO3 with wide range of conditions, we found that the laser fluence plays a critical role in determining the stoichiometry, lattice structure, and electronic properties. A higher Ni deficiency and larger c-axis lattice constant appeared with the lower laser fluence. At 0.6 J/cm2, the Ni deficiency is as large as 25%. According to X-ray absorption spectra and X-ray linear dichroism, we further find that (i) there are no obvious changes of the Ni valence and (ii) the energy level of the dx2-y2 orbital gradually increases relative to the d3z2-r2 orbital with increasing Ni deficiency. What is more, the onset temperature and magnitude of the resistivity change at the metal-to-insulator transitions (MITs) also are found to decrease with increasing laser fluence during the growth.