RESUMEN
Catalytic conversion of lithium polysulfides (LiPSs) is a crucial approach to enhance the redox kinetics and suppress the shuttle effect in lithium-sulfur (Li-S) batteries. However, the roles of a typical heterogenous catalyst cannot be easily identified due to its structural complexity. Compared with the distinct sites of single atom catalysts (SACs), each active site of single site catalysts (SSCs) is identical and uniform in their spatial energy, binding mode, and coordination sphere, etc. Benefiting from the well-defined structure, iron phthalocyanine (FePc) is covalently clicked onto CuO nanosheet to prepare low spin-state Fe SSCs as the model catalyst for Li-S electrochemistry. The periodic polarizability evolution of Fe-N bonding is probed during sulfur redox reaction by in situ Raman spectra. Theoretical analysis shows the decreased d-band center gap of Fe (Δd) and delocalization of dxz/dyz after the axial click confinement. Consequently, Li-S batteries with Fe SSCs exhibit a capacity decay rate of 0.029% per cycle at 2 C. The universality of this methodological approach is demonstrated by a series of M SSCs (M = Mn, Co, and Ni) with similar variation of electronic configuration. This work provides guidance for the design of efficient electrocatalysis in Li-S batteries.
RESUMEN
Strain engineering is an effective strategy to improve the activity of catalysts, especially for flexible carbon-based materials. Nitrogen-coordinated single atomic metals on a carbon skeleton (M-Nx/C) are of interest in catalytic electroreduction reactions due to their high activity and atomic utilization. However, the effect of strain on the structure-activity relationship between the electrochemical activity and the electronic and geometric structures of Ni-Nx/C remains unclear. Here, we found that by applying tensile strain on the Ni-N4/C, the spin state of the single atom can be changed from a low-spin to a high-spin state. Moreover, the energy gap between the highest occupied d orbital of Ni and the lowest unoccupied molecular orbital of the adsorbed species narrowed. With an increasing strain rate, the catalytic activity of O2 and CO2 electroreduction can be improved. Especially for the 2e- O2 reduction, the implicit solvent model, constant-potential method, and microkinetic model were used to verify the positive effect of suitable stretching on the catalytic activity from thermodynamic and kinetic viewpoints. This work can reveal the relationship between strain, spin state, and the catalytic activity of Ni-Nx/C.
RESUMEN
The water pollution caused by the abuse of antibiotics has significant harmful effects on the environment and human health. The photo-Fenton process is currently the most effective method for removing antibiotics from water, but it encounters challenges such as inadequate response to visible light, low yield and utilization of photogenerated electrons, and slow electron transport. In this study, spin state regulation was introduced into the photo-Fenton process, and the spin state of Co3+ was regulated through Ce displacement doping. The intermediate-spin state Ce-LaCoO3 could degrade 91.6 % of tetracycline within 120 min in the photo-Fenton system, which is 15.2 % higher than that of low-spin state LaCoO3. The improved degradation effect is attributed to the reasons that Ce-LaCoO3 in the intermediate-spin state have lower band gap, better charge transfer ability, and stronger adsorption capacity of H2O2, which can accelerate the redox cycle of Co2+/Co3+ and promote the generation of ·OH. This study presents a unique strategy for synthesizing efficient photo-Fenton materials to treat antibiotic wastewater effectively.
RESUMEN
The vast extensional planes of two-dimensional (2D) nanomaterials are recognized as desirable ground for electrocatalytic reactions. However, they tend to exhibit catalytic inertia due to their surface-ordered coordination configurations. Herein, an in situ autoxidation strategy enables high-density grafting of ultrafine CeO2 nanoclusters on 2D Co(OH)2. Affluent active units were activated at the inert interface of Co(OH)2 via the formation of Co-O-Ce units. The optimized catalyst exhibits oxygen evolution reaction activity with an overpotential of 83 mV lower than that of Co(OH)2 at 10 mA cm-2. The cascade orbital coupling between Co (3d) and Ce (4f) in Co-O-Ce units drives electron transfer by unlocking a "d-f electron ladder". Meanwhile, the bond-order theorem analyses and the d-band center show that the occupancy of Co-3d-eg is optimized to balance the adsorption-desorption process of active sites to the key reaction intermediate *OOH, thereby making it easier to release oxygen. This work will drive the development of wider area electron modulation methods and provide guidance for the surface engineering of 2D nanomaterials.
RESUMEN
Designing robust catalysts for increasing the sluggish kinetics of the urea oxidation reaction (UOR) is challenging. Herein, the regulation of spin states for metal active sites by photoexcitation to facilitate the adsorption of urea and intermediates is demonstrated. Mo-doped nickel sulfide nanoribbon arrays (Mo-Ni3S2@NMF) with excellent light-trapping capacity are successfully prepared. Under AM 1.5G illumination, the activity of the Mo-Ni3S2@NMF exhibits a 50% improvement in the UOR current. Compared with those under dark conditions, Mo-Ni3S2@NMF achieve 10 mA cm-2 at 1.315 VRHE for UOR and 1.32 Vcell for urea electrolysis, which are decreases of 15 and 80 mV, respectively. The electron spin resonance, in situ Fourier transform infrared spectroscopy analysis and density functional theory calculations reveal that illumination led to the formation of Ni3+ active sites in a high-spin state, which strengthens the d-p orbital hybridization of Ni-N, hence facilitating the adsorption of urea. CâN cleavage of the *CONN intermediate is further inhibited, which promotes the oxidation of urea molecules via the active N2 pathway, thereby accelerating the UOR rate.
RESUMEN
Iron antimonide (FeSb2) has been investigated for decades due to its puzzling electronic properties. It undergoes the temperature-controlled transition from an insulator to an ill-defined metal, with a cross-over from diamagnetism to paramagnetism. Extensive efforts have been made to uncover the underlying mechanism, but a consensus has yet to be reached. While macroscopic transport and magnetic measurements can be explained by different theoretical proposals, the essential spectroscopic evidence required to distinguish the physical origin is missing. In this paper, through the use of X-ray absorption spectroscopy and atomic multiplet simulations, we have observed the mixed spin states of 3d 6 configuration in FeSb2. Furthermore, we reveal that the enhancement of the conductivity, whether induced by temperature or doping, is characterized by populating the high-spin state from the low-spin state. Our work constitutes vital spectroscopic evidence that the electrical/magnetical transition in FeSb2 is directly associated with the spin-state excitation.
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Non-heme mononuclear iron dependent (NHM-Fe) enzymes exhibit exceedingly diverse catalytic reactivities. Despite their catalytic versatilities, the mononuclear iron centers in these enzymes show a relatively simple architecture, in which an iron atom is ligated with 2-4 amino acid residues, including histidine, aspartic or glutamic acid. In the past two decades, a common high-valent reactive iron intermediate, the S=2 oxyferryl (Fe(IV)-oxo or Fe(IV)=O) species, has been repeatedly discovered in NHM-Fe enzymes containing a 2-His-Fe or 2-His-1-carboxylate-Fe center. However, for 3-His/4-His-Fe enzymes, no common reactive intermediate has been identified. Recently, we have spectroscopically characterized the first S=1 Fe(IV) intermediate in a 3-His-Fe containing enzyme, OvoA, which catalyzes a novel oxidative carbon-sulfur bond formation. In this review, we summarize the broad reactivities demonstrated by S=2 Fe(IV)-oxo intermediates, the discovery of the first S=1 Fe(IV) intermediate in OvoA and the mechanistic implication of such a discovery, and the intrinsic reactivity differences of the S=2 and the S=1 Fe(IV)-oxo species. Finally, we postulate the possible reasons to utilize an S=1 Fe(IV) species in OvoA and their implications to other 3-His/4-His-Fe enzymes.
RESUMEN
Integrating controllable spin states into single-molecule magnets (SMMs) enables precise manipulation of magnetic interactions at a molecular level, but remains a synthetic challenge. Herein, we developed a 3d-4f metallacrown (MC) magnet [DyNi5(quinha)5(Clsal)2(py)8](ClO4) â 4H2O (H2quinha=quinaldichydroxamic acid, HClsal=5-chlorosalicylaldehyde) wherein a square planar NiII is stabilized by chemical stacking. Thioacetal modification was employed via post-synthetic ligand substitutions and yielded [DyNi5(quinha)5(Clsaldt)2(py)8](ClO4) â 3H2O (HClsaldt=4-chloro-2-(1,3-dithiolan-2-yl)phenol). Thanks to the additional ligations of thioacetal onto the NiII site, coordination-induced spin state switching (CISSS) took place with spin state altering from low-spin S=0 to high-spin S=1. The synergy of CISSS effect and magnetic interactions results in distinct energy splitting and magnetic dynamics. Magnetic studies indicate prominent enhancement of reversal barrier from 57â cm-1 to 423â cm-1, along with hysteresis opening and an over 200-fold increment in coercive field at 2â K. Ab initio calculations provide deeper insights into the exchange models and rationalize the relaxation/tunnelling pathways. These results demonstrate here provide a fire-new perspective in modulating the magnetization relaxation via the incorporation of controllable spin states and magnetic interactions facilitated by the CISSS approach.
RESUMEN
Light-induced excited spin-state trapping reactions in iron pyridinic complexes allow the iron's low-to-high spin transition in a sub-picosecond timescale. Employing a recently developed model for [Fe(2,2'-bipyridine)3]2+ photochemical spin-crossover reaction in conjunction with quantum wavepacket dynamics, we explore the possibility of controlling the reaction through external electromagnetic fields, aiming at stabilizing the initial metal-to-ligand charge transfer states. We show that simple Gaussian-shaped electromagnetic fields have a minor effect on the population kinetics. However, introducing vibrationally excited initial wavepacket representations allows for maintaining the population trapped in the metal-to-ligand charge transfer states. Using optimal control theory, we propose an electromagnetic field shape that increases the lifetime of metal-to-ligand charge transfer states. These results open the route for controlling the iron photochemistry through the action of external electric fields.
RESUMEN
Photosynthetic water splitting, when synergized with hydrogen production catalyzed by hydrogenases, emerges as a promising avenue for clean and renewable energy. However, theoretical calculations have faced challenges in elucidating the low-lying spin states of iron-sulfur clusters, which are integral components of hydrogenases. To address this challenge, we employ the Extended Broken-Symmetry method for the computation of the cubane-[Fe3S4] cluster within the [FeNi] hydrogenase enzyme. This approach rectifies the error caused by spin contamination, allowing us to obtain the magnetic exchange coupling constant and the energy level of the low-lying state. We find that the Extended Broken-Symmetry method provides more accurate results for differences in bond length and the magnetic coupling constant. This accuracy assists in reconstructing the low-spin ground state force and determining the geometric structure of the ground state. By utilizing the Extended Broken-Symmetry method, we further highlight the significance of the geometric arrangement of metal centers in the cluster's properties and gain deeper insights into the magnetic properties of transition metal iron-sulfur clusters at the reaction centers of hydrogenases. This research illuminates the untapped potential of hydrogenases and their promising role in the future of photosynthesis and sustainable energy production.
RESUMEN
The catalytic activation of the Li-S reaction is fundamental to maximize the capacity and stability of Li-S batteries (LSBs). Current research on Li-S catalysts mainly focuses on optimizing the energy levels to promote adsorption and catalytic conversion, while frequently overlooking the electronic spin state influence on charge transfer and orbital interactions. Here, hollow NiS2/NiSe2 heterostructures encapsulated in a nitrogen-doped carbon matrix (NiS2/NiSe2@NC) are synthesized and used as a catalytic additive in sulfur cathodes. The NiS2/NiSe2 heterostructure promotes the spin splitting of the 3d orbital, driving the Ni3+ transformation from low to high spin. This high spin configuration raises the electronic energy level and activates the electronic state. This accelerates the charge transfer and optimizes the adsorption energy, lowering the reaction energy barrier of the polysulfides conversion. Benefiting from these characteristics, LSBs based on NiS2/NiSe2@NC/S cathodes exhibit high initial capacity (1458 mAh·gâ»1 at 0.1C), excellent rate capability (572 mAh·gâ»1 at 5C), and stable cycling with an average capacity decay rate of only 0.025% per cycle at 1C during 500 cycles. Even at high sulfur loadings (6.2 mg·cmâ»2), high initial capacities of 1173 mAh·gâ»1 (7.27 mAh·cmâ»2) are measured at 0.1C, and 1058 mAh·gâ»1 is retained after 300 cycles.
RESUMEN
The interaction between oxygen species and metal sites of various orbitals exhibits intimate correlation with the oxygen reduction reaction (ORR) kinetics. Herein, a new approach for boosting the inherent ORR activity of atomically dispersed Fe-N-C matrix is represented by implanting Fe atomic clusters nearby. The as-prepared catalyst delivers excellent ORR activity with half-wave potentials of 0.78 and 0.90 V in acidic and alkaline solutions, respectively. The decent ORR activity can also be validated from the high-performance rechargeable Zn-air battery. The experiments and density functional theory calculations reveal that the electron spin-state of monodispersed Fe active sites is transferred from the low spin (LS, t2g 6 eg 0) to the medium spin (MS, t2g 5 eg 1) due to the involvement of Fe atomic clusters, leading to the spin electron filling in σ∗ orbit, by which it favors OH- desorption and in turn boosts the reaction kinetics of the rate-determining step. This work paves a solid way for rational design of high-performance Fe-based single atom catalysts through spin manipulation.
RESUMEN
Metal-organic frameworks (MOFs) have been developed as an ideal platform for exploration of the relationship between intrinsic structure and catalytic activity, but the limited catalytic activity and stability has hampered their practical use in water splitting. Herein, we develop a bond length adjustment strategy for optimizing naphthalene-based MOFs that synthesized by acid etching Co-naphthalenedicarboxylic acid-based MOFs (donated as AE-CoNDA) to serve as efficient catalyst for water splitting. AE-CoNDA exhibits a low overpotential of 260 mV to reach 10 mA cm-2 and a small Tafel slope of 62 mV dec-1 with excellent stability over 100 h. After integrated AE-CoNDA onto BiVO4, photocurrent density of 4.3 mA cm-2 is achieved at 1.23 V. Experimental investigations demonstrate that the stretched Co-O bond length was found to optimize the orbitals hybridization of Co 3d and O 2p, which accounts for the fast kinetics and high activity. Theoretical calculations reveal that the stretched Co-O bond length strengthens the adsorption of oxygen-contained intermediates at the Co active sites for highly efficient water splitting.
RESUMEN
Tracking changes in the chemical state of transition metals in alkali-ion batteries is crucial to understanding the redox chemistry during operation. X-ray absorption spectroscopy (XAS) is often used to follow the chemistry through observed changes in the chemical state and local atomic structure as a function of the state-of-charge (SoC) in batteries. In this study, we utilize an operando X-ray emission spectroscopy (XES) method to observe changes in the chemical state of active elements in batteries during operation. Operando XES and XAS were compared by using a laboratory-scale setup for four different battery systems: LiCoO2 (LCO), Li[Ni1/3Co1/3Mn1/3]O2 (NMC111), Li[Ni0.8Co0.1Mn0.1]O2 (NMC811), and LiFePO4 (LFP) under a constant current charging the battery in 10 h (C/10 charge rate). We show that XES, despite narrower chemical shifts in comparison to XAS, allows us to fingerprint the battery SOC in real time. We further demonstrate that XES can be used to track the change in net spin of the probed atoms by analyzing changes in the emission peak shape. As a test case, the connection between net spin and the local chemical and structural environment was investigated by using XES and XAS in the case of electrochemically delithiated LCO in the range of 2-10% lithium removal.
RESUMEN
Designing biomimetic nanomaterials with peroxidase (POD)-like activity at neutral pH remains a significant challenge. An S-doping strategy is developed to afford an iron single-atom nanomaterial (Fe1@CN-S) with high POD-like activity under neutral conditions. To the best of knowledge, there is the first example on the achievement of excellent POD-like activity under neutral conditions by regulating the active site structure. S-doping not only promotes the dissociation of the NâH bond in 3,3â³,5,5â³-tetramethylbenzidine (TMB), but also facilitates the desorption of OH* by the transformation of iron species' spin states from middle-spin (MS FeII) to low-spin (LS FeII). Meanwhile, LS FeII sites typically have more unfilled d orbitals, thereby exhibiting stronger interactions with H2O2 than MS FeII, which can enhance POD-like activity. Finally, a one-pot visual detection of glucose at pH 7 is performed, demonstrating the best selectivity and sensitivity than previous reports.
RESUMEN
Water-soluble metalloporphyrins, depending on the metal center, possess special spectral, coordination, and photochemical features. In nickel(II) porphyrins, the Ni(II) center can occur with low-spin or high-spin electronic configuration. In aqueous solution, the cationic nickel(II) complex (Ni(II)TMPyP4+, where H2TMPyP4+ = 5,10,15,20-tetrakis(1-methylpyridinium-4-yl)porphyrin), exists in both forms in equilibrium. In this study, an equilibrium system involving the low-spin and high-spin forms of Ni(II)TMPyP4+ was investigated via application of irradiation, temperature change, and various potential axial ligands. Soret band excitation of this aqueous system, in the absence of additional axial ligands, resulted in a shift in the equilibrium toward the low-spin species due to the removal of axial solvent ligands. The kinetics and the thermodynamics of the processes were also studied via determination of the rate and equilibrium constants, as well as the ΔS, ΔH, and ΔG values. Temperature increase had a similar effect. The equilibrium of the spin isomers was also shifted by decreasing the solvent polarity (using n-propanol) as well as by the addition of a stronger coordinating axial ligand (such as ammonia). Since triethanolamine is an efficient electron donor in Ni(II)TMPyP4+-based photocatalytic systems, its interaction with this metalloporphyin was also studied. The results promote the development of efficient photocatalytic systems based on this complex.
RESUMEN
A FeCo/DA@NC catalyst with the well-defined FeCoN6 moiety is customized through a novel and ultrafast Joule heating technique. This catalyst demonstrates superior oxygen reduction reaction activity and stability in an alkaline environment. The power density and charge-discharge cycling of znic-air batteries driven by FeCo/DA@NC also surpass those of Pt/C catalyst. The source of the excellent oxygen reduction reaction activity of FeCo/DA@NC originates from the significantly changed charge environment and 3d orbital spin state. These not only improve the bonding strength between active sites and oxygen-containing intermediates, but also provide spare reaction sites for oxygen-containing intermediates. Moreover, various in situ detection techniques reveal that the rate-determining step in the four-electron oxygen reduction reaction is *O2 protonation. This work provides strong support for the precise design and rapid preparation of bimetallic catalysts and opens up new ideas for understanding orbital interactions during oxygen reduction reactions.
RESUMEN
The spin states of active sites have a significant impact on the adsorption/desorption ability of the reaction intermediates during the oxygen evolution reaction (OER). Sulfide spinel is not generally considered a highly efficient OER catalyst owing to the low spin state of Co3+ and the lack of unpaired electrons available for adsorption of reaction intermediates. Herein, it is proposed a novel Nd-evoked valence electronic adjustment strategy to engineer the spin state of Co ions. The unique f-p-d orbital electronic coupling effect stimulates the rearrangement of Co d orbital electrons and increases the eg electron filling to achieve high-spin state Co ions, which promotes charge transport by propagating a spin channel and generates a high number of active sites for intermediate adsorption. The optimized CuCo1.75 Nd0.25 S4 catalyst exhibits outstanding electrocatalytic properties with a low overpotential of 320 mV at 500 mA cm-2 and a 48 h stability at 300 mA cm-2 . In situ synchrotron radiation infrared spectra confirm the quick accumulation of key *OOH and *O intermediates. This work deepens the comprehensive understanding of the relationship between OER activity and spin configurations of Co ions and offers a new design strategy for spinel compound catalysts.
RESUMEN
As a promising strategy to improve photocatalytic efficiency, spin polarization has attracted enormous attention in recent years, which could be involved in various steps of photoreaction. The Pauli repulsion principle and the spin selection rule dictate that the behavior of two electrons in a spatial eigenstate is based on their spin states, and this fact opens up a new avenue for manipulating photocatalytic efficiency. In this review, recent advances in modulating the photocatalytic activity with spin polarization are systematically summarized. Fundamental insights into the influence of spin-polarization effects on photon absorption, carrier separation, and migration, and the behaviors of reaction-related substances from the photon uptake to reactant desorption are highlighted and discussed in detail, and various photocatalytic applications for environmental purification and energy conversion are presented. This review is expected to deliver a timely overview of the recent developments in spin-polarization-modulated photocatalysis for environmental purification and energy conversion in terms of their practical applications.
RESUMEN
Enhancing electrocatalytic performance through structural and compositional engineering attracts considerable attention. However, most materials only function as pre-catalysts and convert into "real catalysts" during electrochemical reactions. Such transition involves dramatic structural and compositional changes and disrupts their designed properties. Herein, for the first time, a laser-ironing (LI) approach capable of in-situ forming a laser-ironing capping layer (LICL) on the Co-ZIF-L flakes is developed. During the oxygen evolution reaction (OER) process, the LICL sustains the leaf-like morphology and promotes the formation of OER-active Co3 O4 nanoclusters with the highest activity and stability. In contrast, the pristine and conventional heat-treated Co-ZIF-Ls both collapse and transform to less active CoOOH. The density functional theory (DFT) calculations pinpoint the importance of the high spin (HS) states of Co ions and the narrowed band gap in Co3 O4 nanoclusters. They enhance the OER activity by promoting spin-selected electron transport, effectively lowering the energy barrier and realizing a spontaneous O2 -releasing step that is the potential determining step (pds) in CoOOH. This study presents an innovative approach for modulating both structural and compositional evolutions of electrocatalysts during the reaction, sustaining stability with high performance during dynamic electrochemical reactions, and providing new pathways for facile and high-precision surface microstructure control.