Understanding the Role of Spin State in Cobalt Oxyhydroxides for Water Oxidation.

Although the electronic state of catalysts is strongly corrected with their oxygen evolution reaction (OER) performances, understanding the role of spin state in dynamic electronic structure evolution during OER process is still challenging. Herein, we developed a spin state regulation strategy to boost the OER performance of CoOOH through elemental doping (CoMOOH, M=V, Cr, Mn, Co and Cu). Experimental results including magnetic characterization, in situ X-ray absorption spectroscopy, in situ Raman and density functional theory calculations unveil that Mn doping could successfully increase the Co sites from low spin state to intermediate spin state, leading to the largest lattice distortion and smallest energy gap between dxy and dz 2 orbitals among the obtained CoMOOH electrocatalysts. Benefiting from the promoted electron transfer from dxy to dz 2 orbital, facilitated formation of active high-valent *O-Co(IV) species at applied potential, and reduced energy barrier of rate-determining step, the CoMnOOH exhibits the highest OER performance. Our work provides significant insight into the correction between dynamic electronic structure evolution and OER performance by understanding the role of spin state regulation in metal oxyhydroxides, paving a new avenue for rational design of high-activity electrocatalysts.

Boosting Benzene Oxidation with a Spin-State-Controlled Nuclearity Effect on Iron Sub-Nanocatalysts.

A fundamental understanding of the nature of nuclearity effects is important for the rational design of superior sub-nanocatalysts with low nuclearity, but remains a long-standing challenge. Using atomic layer deposition, we precisely synthesized Fe sub-nanocatalysts with tunable nuclearity (Fe1 -Fe4 ) anchored on N,O-co-doped carbon nanorods (NOC). The electronic properties and spin configuration of the Fe sub-nanocatalysts were nuclearity dependent and dominated the H2 O2 activation modes and adsorption strength of active O species on Fe sites toward C-H oxidation. The Fe1 -NOC single atom catalyst exhibits state-of-the-art activity for benzene oxidation to phenol, which is ascribed to its unique coordination environment (Fe1 N2 O3 ) and medium spin state (t2g 4 eg 1 ); turnover frequencies of 407 h-1 at 25 °C and 1869 h-1 at 60 °C were obtained, which is 3.4, 5.7, and 13.6 times higher than those of Fe dimer, trimer, and tetramer catalysts, respectively.

Creating Ferroic Micropatterns through Geometrical Transformation.

The functionality of a ferroic device is intimately coupled to the configuration of domains, domain boundaries, and the possibility for tailoring them. Exemplified with a ferromagnetic system, we present a novel approach which allows the creation of new, metastable multidomain patterns with tailored wall configurations through a self-assembled geometrical transformation. By preparing a magnetic layer system on a polymeric platform including swelling layer, a repeated self-assembled rolling into a multiwinding tubular structure and unrolling of the functional membrane is obtained. When polarizing the rolled-up 3D structure in a simple homogeneous magnetic field, the imprinted configuration translates into a regularly arranged multidomain configuration once the tubular structure is unwound. The process is linked to the employed magnetic anisotropy with respect to the surface normal, and the geometrical transformation connects the angular with the lateral degrees of freedom. This combination offers unparalleled possibilities for designing new magnetic or other ferroic micropatterns.

Spin Regulation on 2D Pd-Fe-Pt Nanomeshes Promotes Fuel Electrooxidations.

Spin engineering provides a powerful strategy for manipulating the interaction between electrons in the d orbital and oxygen-containing adsorbates, while a little endeavor was performed to understand whether such a strategy can make a prosperous enhancement for fuel electrooxidations. Herein, we demonstrate that spin engineering of trimetallic Pd-Fe-Pt nanomeshes (NMs) can achieve superior enhancement for fuel electrooxidations. Magnetization characterizations reveal that Pd59Fe27Pt14 NMs own the highest number of polarized spins (µb = 0.85 µB/f.u.), playing an important role on facilitating the adsorption of OHads to promote the oxidation of COads, as confirmed by theoretical results. Consequently, the optimized Pd59Fe27Pt14 NMs exhibit excellent methanol oxidation reaction activity and stability with a mass activity of 1.61 A mgPt-1, 2.6-fold and 7.3-fold larger than those of PtRu/C and Pt/C. Such catalysts also present exceptional performances in ethanol oxidation and formic acid oxidation reactions. Our work highlights a new strategy for designing efficient electrocatalysts for fuel electrooxidations and beyond.

Insight into the biological effects of acupuncture points by X-ray absorption fine structure.

Exploration of the biological effects of transition metal ions in acupuncture points is essential to clarify the functional mechanism of acupuncture treatment. Here we show that in the SP6 acupuncture point (Sanyinjiao) the Fe ions are in a high-spin state of approximately t2g4.5eg1.5 in an Fe-N(O) octahedral crystal field. The Fe K-edge synchrotron radiation X-ray absorption fine structure results reveal that the Fe-N and Fe-O bond lengths in the SP6 acupuncture point are 2.05 and 2.13 Å, respectively, and are 0.05-0.10 Å longer than those in the surrounding tissue. The distorted atomic structure reduces the octahedral symmetry and weakens the crystal field around the Fe ions by approximately 0.3 eV, leading to the high-spin configuration of the Fe ions, which is favorable for strengthening the magnetotransport and oxygen transportation properties in the acupuncture point by the enhanced spin coherence. This finding might provide some insight into the microscopic effect of the atomic and electronic interactions of transition metal ions in the acupuncture point. Graphical Abstract ᅟ.

Spin-dependent electrocatalysis.

The shift towards sustainable energy requires efficient electrochemical conversion technologies, emphasizing the crucial need for robust electrocatalyst design. Recent findings reveal that the efficiency of some electrocatalytic reactions is spin-dependent, with spin configuration dictating performance. Consequently, understanding the spin's role and controlling it in electrocatalysts is important. This review succinctly outlines recent investigations into spin-dependent electrocatalysis, stressing its importance in energy conversion. It begins with an introduction to spin-related features, discusses characterization techniques for identifying spin configurations, and explores strategies for fine-tuning them. At the end, the article provides insights into future research directions, aiming to reveal more unknown fundamentals of spin-dependent electrocatalysis and encourage further exploration in spin-related research and applications.

Exchange Bias Between van der Waals Materials: Tilted Magnetic States and Field-Free Spin-Orbit-Torque Switching.

Magnetic van der Waals heterostructures provide a unique platform to study magnetism and spintronics device concepts in the 2D limit. Here, studies of exchange bias from the van der Waals antiferromagnet CrSBr acting on the van der Waals ferromagnet Fe3GeTe2 (FGT) are reported. The orientation of the exchange bias is along the in-plane easy axis of CrSBr, perpendicular to the out-of-plane anisotropy of the FGT, inducing a strongly tilted magnetic configuration in the FGT. Furthermore, the in-plane exchange bias provides sufficient symmetry breaking to allow deterministic spin-orbit torque switching of the FGT in CrSBr/FGT/Pt samples at zero applied magnetic field. A minimum thickness of the CrSBr of >10 nm is needed to provide a non-zero exchange bias at 30 K.

Engineering Spin Configurations of Synthetic Antiferromagnet by Controlling Long-Range Oscillatory Interlayer Coupling and Neighboring Ferrimagnetic Coupling.

Controllable manipulation of specific spin configurations of magnetic materials is the key to constructing functional spintronic devices. Here, it is demonstrated by integrating the merits of ferromagnetic, ferrimagnetic, and antiferromagnetic spin configurations into one synthetic antiferromagnetic (SAF) heterostructure by controlling both long-range oscillatory interlayer coupling and neighboring ferrimagnetic coupling. A controllable manipulation of four types of spin configurations of the Pt/[Co/Pt/Co]/Ru/CoTb SAF heterostructures composed of ferromagnetic Co/Pt/Co and ferrimagnetic CoTb layers is successfully achieved. In particular, the compensated magnetization, enhanced anomalous Hall resistance in the remanence state, wide-temperature spin-orbit torque switching of magnetization, and high immunity to the external magnetic field are simultaneously obtained in one of the SAF heterojunctions with macroscopic interlayer antiferromagnetic coupling. This design concept of engineering spin configurations may enable efficient spin manipulation for customized memory and logic applications.

Unraveling the π-interaction of NiFe-based metal-organic frameworks with enhanced oxygen evolution: Optimizing electronic structure and facilitating electron transfer modulation.

Metal-organic frameworks (MOFs) with conjugation carboxylate ligands as electrocatalysts can significantly improve oxygen evolution reaction (OER), but the role of π-interaction on the reactive sites of OER is often neglected. We intend to unravel the mechanism of how π-interaction enhances OER performance. The results of Rietveld refinement, density functional theory (DFT) calculations, and in-situ Raman spectra show that π-interaction can efficiently modulate the local spin configuration of metal centers, facilitate γ-Ni1-xFexOOH active species with high-valence Ni sites modified by high-spin Fe, accelerate electron transfer, optimize the d-band center together with the beneficial rate-determining step of OER. NiFe-BPDC MOFs/NF with 0.8559 eV π-interaction energy generated γ-Ni1-xFexOOH in only 60 s at 1.4 V, demonstrating that π-interaction promotes the rapid generation of highly active reactive sites. Furthermore, the results of in-situ Raman and electron paramagnetic resonance (EPR) spectra reveal that the deprotonation and deoxygenation steps of OER are accompanied by changes in the oxidation state of metal ions and the generation of oxygen vacancies on the surface of catalysts. In addition, NiFe-BPDC MOFs/NF rapidly completes the deprotonation and deoxygenation steps, and it requires only 288 mV overpotential to reach 100 mA/cm2 with 100 h of stability, suggesting promising industrial application.

High Oxygen Evolution Activity of Tungsten Bronze Oxides Boosted by Anchoring of Co2+ at Nb5+ Sites Accompanied by Substantial Oxygen Vacancy.

The participation of lattice oxygen in the oxygen evolution reaction (OER) process has been proved to be faster in kinetics than the mechanisms where only metal is involved, although activating the lattice oxygen in the traditional rigid structures remains a big challenge. In this work, efforts are devoted to exploring a new flexible structure that is competent in providing large amounts of oxygen vacancies as well as offering the freedom to manipulate the electronic structure of metal cations. This is demonstrated by anchoring low valence state Co at high valence state Nb sites in the tetragonal tungsten bronze (TTB)-structured Sr0.5Ba0.5Nb2- x Co x O6-δ , with different ratios of Co to Nb to optimize the Co substitution proportion. It is found that the occupation of Co in the Nb5+ sites gives rise to the generation of massive surface oxygen vacancies (Ovac), while Co itself is stabilized in Co2+ by adjacent Ovac. The coexistence of Ovac and LS Co2+ enables an oxygen intercalation mechanism in the optimal SBNC45 with specific activity at 1.7 V versus reversible hydrogen electrode that is 20 times higher than for the commercial IrO2. This work illuminates an entirely new avenue to rationally design OER electrocatalysts with ultrafast kinetics.

Quantitative Nanoscale Magnetic Study of Isolated Diameter-Modulated FeCoCu Nanowires.

The comprehension of the magnetic configuration in FeCoCu nanowires with a diameter-modulated cylindrical geometry will allow controlling the domain wall motion in this low-dimensional system under the application of magnetic fields and/or the injection of current pulses. Here we perform a quantitative magnetic characterization of isolated diameter-modulated FeCoCu nanowires by combining nanoscale magnetic characterization techniques such as electron holography, magnetic force microscopy, and micromagnetic simulations. Local reconstructions of the magnetic distribution show the diameter-modulated geometry of the wires induces the formation of vortex-like structures and magnetic charges in the regions where the diameter is varied. Vortex-like structures modify the axial alignment of the magnetization in large-diameter segments. Moreover, the magnetic charges control the demagnetizing field distribution, promoting a flux-closure stray field configuration around large-diameter segments and keeping the demagnetizing field parallel to the NW's magnetization around small diameter segments. The detailed description of the remanent state in diameter-modulated cylindrical FeCoCu nanowires allows us to provide a clear explanation of the origin of bright and dark contrast observed in magnetic force microscopy images, which have the same feature of magnetic domain walls. This work establishes the primary knowledge required for future magnetization reversal studies with the aim of searching efficient modulated geometries that allow an optimum and controlled domain wall propagation.

A novel crystal structure of {tris[4-(1H-pyrazol-3-yl-κN(2))-3-azabut-3-enyl]amine-κN}iron(II) bis(tetrafluoridoborate) methanol monosolvate featuring a low-spin configuration.

Mononuclear complexes are good model systems for evaluating the effects of different ligand systems on the magnetic properties of iron(II) centres. A novel crystal structure of the title compound, [Fe(C18H24N10)](BF4)2·CH3OH, with one molecule of methanol per formula unit exhibits a strictly sixfold coordination sphere associated with a low-spin configuration at the metal centre. The incorporated methanol solvent molecule promotes extended hydrogen-bonding networks between the tetrafluoridoborate anions and the cationic units. A less constrained crystal structure regarding close contacts between the tetrafluoridoborate anions and the cationic units allows a spin transition which is inhibited in the previously published hydrate of the title compound.