FRACTALS OF HYBRID ORBITALS AND THEIR APPLICATIONS IN THE ENZYME MODELS

An enzyme is a kind of protein with catalytic activity and long chain,and its structure and shape are determined by the hybridized state of atomic orbital.The fractal dimension(D_f)is closely related to the hybridization,e.g.D_f=2ln2/ln[2(1+α/(1-α))]for the spa type, where a denotes the fraction of the s orbital in the hybridized molecular orbital.This relationship and the five fractal theorems introduced by the present paper play an important role in the investigations of the model of imitative enzyme.

p-d Orbital Hybridization Engineered Single-Atom Catalyst for Electrocatalytic Ammonia Synthesis

The rational design of metal single-atom catalysts(SACs)for electrochemical nitrogen reduction reaction(NRR)is challenging.Two-dimensional metal-organic frameworks(2DMOFs)is a unique class of promising SACs.Up to now,the roles of individual metals,coordination atoms,and their synergy effect on the electroanalytic performance remain unclear.Therefore,in this work,a series of 2DMOFs with different metals and coordinating atoms are systematically investigated as electrocatalysts for ammonia synthesis using density functional theory calculations.For a specific metal,a proper metal-intermediate atoms p-d orbital hybridization interaction strength is found to be a key indicator for their NRR catalytic activities.The hybridization interaction strength can be quantitatively described with the p-/d-band center energy difference(Δd-p),which is found to be a sufficient descriptor for both the p-d hybridization strength and the NRR performance.The maximum free energy change(ΔG_(max))andΔd-p have a volcanic relationship with OsC_(4)(Se)_(4)located at the apex of the volcanic curve,showing the best NRR performance.The asymmetrical coordination environment could regulate the band structure subtly in terms of band overlap and positions.This work may shed new light on the application of orbital engineering in electrocatalytic NRR activity and especially promotes the rational design for SACs.

Manipulating d-d orbital hybridization induced by Mo-doped Co_(9)S_(8) nanorod arrays for high-efficiency water electrolysis

Precisely refining the electronic structure of electrocatalysts represents a powerful approach to further optimize the electrocatalytic performance.Herein,we demonstrate an ingenious d-d orbital hybridization concept to construct Mo-doped Co_(9)S_(8) nanorod arrays aligned on carbon cloth(CC)substrate(abbreviated as Mo-Co_(9)S_(8)@CC hereafter)as a high-efficiency bifunctional electrocatalyst toward water electrolysis.It has experimentally and theoretically validated that the 4d-3d orbital coupling between Mo dopant and Co site can effectively optimize the H_(2)O activation energy and lower H^(*)adsorption energy barrier,thereby leading to enhanced hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)activities.Thanks to the unique electronic and geometrical advantages,the optimized Mo-Co_(9)S_(8)@CC with appropriate Mo content exhibits outstanding bifunctional performance in alkaline solution,with the overpotentials of 75 and 234 mV for the delivery of a current density of 10 mA cm^(-2),small Tafel slopes of 53.8 and 39.9 mV dec~(-1)and long-term stabilities for at least 32 and 30 h for HER and OER,respectively.More impressively,a water splitting electrolylzer assembled by the self-supported Mo-Co_(9)S_(8)@CC electrode requires a low cell voltage of 1.53 V at 10 mA cm^(-2)and shows excellent stability and splendid reversibility,demonstrating a huge potential for affordable and scalable electrochemical H_(2) production.The innovational orbital hybridization strategy for electronic regulation herein provides an inspirable avenue for developing progressive electrocatalysts toward new energy systems.

Enhanced Redox Electrocatalysis in High‑Entropy Perovskite Fluorides by Tailoring d–p Hybridization

High-entropy catalysts featuring exceptional properties are,in no doubt,playing an increasingly significant role in aprotic lithium-oxygen batteries.Despite extensive effort devoted to tracing the origin of their unparalleled performance,the relationships between multiple active sites and reaction intermediates are still obscure.Here,enlightened by theoretical screening,we tailor a high-entropy perovskite fluoride(KCoMnNiMgZnF_(3)-HEC)with various active sites to overcome the limitations of conventional catalysts in redox process.The entropy effect modulates the d-band center and d orbital occupancy of active centers,which optimizes the d–p hybridization between catalytic sites and key intermediates,enabling a moderate adsorption of LiO_(2)and thus reinforcing the reaction kinetics.As a result,the Li–O2 battery with KCoMnNiMgZnF_(3)-HEC catalyst delivers a minimal discharge/charge polarization and long-term cycle stability,preceding majority of traditional catalysts reported.These encouraging results provide inspiring insights into the electron manipulation and d orbital structure optimization for advanced electrocatalyst.

Asymmetric orbital hybridization in Zn-doped antiperovskite Cu_(1-x)Zn_(x)NMn_(3)enables highly efficient electrocatalytic hydrogen production

Rational design of efficient and robust earth-abundant alkaline hydrogen evolution reaction(HER)catalysts is a key factor for developing energy conversion technologies.Currently,antiperovskite nitride CuNMn_(3)has garnered significant interest due to its remarkable properties such as negative/zero thermal expansion and magnetocaloric effects.However,when utilized as hydrogen evolution catalysts,it encounters large challenge resulting from excessively strong/weak interactions with adsorbed H on Mn/Cu active sites,which leads to low HER activity.In this study,we introduce an asymmetric orbital hybridization strategy in Zn-doped Cu_(1-x)Zn_(x)NMn_(3)by leveraging the localization of Zn electronic states to reconfigure the electronic structures of Cu and Mn,thereby reducing the energy barrier for water dissociation and optimizing Cu and Mn active sites for hydrogen adsorption and H_(2)production.Electrochemical evaluations reveal that Cu_(0.85)Zn_(0.15)NMn_(3)with x=0.15 demonstrates exceptional electrocatalytic activity in alkaline electrolytes.A low overpotential of 52 mV at 10 mA cm^(-2)and outstanding stability over a 150-h test period are achieved,surpassing commercial Pt/C.This research offers a novel strategy for enhancing HER performance by modulating asymmetric hybridization of electron orbitals between multiple metal atoms within a material structure.

Accelerating Oxygen Electrocatalysis Kinetics on Metal-Organic Frameworks via Bond Length Optimization

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 BiVO_(4),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.

Oscillation of Dzyaloshinskii–Moriya interaction driven by weak electric fields

Dzyaloshinskii–Moriya interaction(DMI) is under extensive investigation considering its crucial status in chiral magnetic orders, such as Néel-type domain wall(DW) and skyrmions. It has been reported that the interfacial DMI originating from Rashba spin–orbit coupling(SOC) can be linearly tuned with strong external electric fields. In this work, we experimentally demonstrate that the strength of DMI exhibits rapid fluctuations, ranging from 10% to 30% of its original value, as a function of applied electric fields in Pt/Co/MgO heterostructures within the small field regime(< 10-2V/nm). Brillouin light scattering(BLS) experiments have been performed to measure DMI, and first-principles calculations show agreement with this observation, which can be explained by the variation in orbital hybridization at the Co/MgO interface in response to the weak electric fields. Our results on voltage control of DMI(VCDMI) suggest that research related to the voltage control of magnetic anisotropy for spin–orbit torque or the motion control of skyrmions might also have to consider the role of the external electric field on DMI as small voltages are generally used for the magnetoresistance detection.

Retaining the self-released chalcogenate at reconstructed cobalt sites by self-transformed carbonate regulation for boosted oxygen evolution

The in-situ generated oxyanions at electrochemically reconstructed catalysts from metal-based nonoxide compounds have been proven to significantly accelerate oxygen evolution reaction(OER)kinetics.However,it remains a challenge to retain these self-released oxyanions at reconstructed catalysts,hindering its utilization as a tool to develop efficient OER catalysts.Here,we demonstrate a versatile selftransformed carbonate regulation strategy to efficiently retain the self-released chalcogenate at Co oxyhydroxides reconstructed from carbon-incorporated Co selenides under OER conditions.These selftransformed CO_(3)^(2-)can induce electron accumulation and narrow d bond at Co sites to facilitate the Co3d-O 2p orbital hybridization between Co sites and SeO_(x)^(2-)for enhanced SeO_(x)^(2-)retention,which can accelerate the rate-limiting step for^(*)OOH formation during OER.Relative to CoOOH-SeO_(x)^(2-)with limited SeO_(x)^(2-)residues,CoOOH-CO_(3)^(2-)/SeO_(x)^(2-)with elevated SeO_(x)^(2-)retention by CO_(3)^(2-)regulation exhibited a 5.6-fold increase in current density and a remarkable lower Tafel slope towards OER.This strategy paves a rational avenue to design efficient catalysts for electrooxidation reactions through finely regulating self-released oxyanions at reconstructed structures.

Intermediate sp-hybridization for chemical bonds in nonplanar covalent molecules of carbon

General representations for symmetrical and asymmetrical intermediate sp-hybridization are provided, with which the development of electronic structure in C3v-symmetrical C2H6 and the bonding configuration in C60 have been analyzed as an example. The spherical structure of C60 does not necessarily require the fourth hybrid, h4, to lie along the radial direction. Rather, h4 runs at an angle of 3.83° from the radius, in the plane bisecting a pentagon, to achieve maximum overlap with adjacent h4-hybrids. By virtue of these representations, a number of properties of covalent molecules and solids can be conveniently calculated. This work might be particularly helpful for the study of C-C bonding in curved structures of carbon, such as fullerenes, carbon nanotubes, and buckled graphene.

Deciphering orbital hybridization in heterogeneous catalysis

The catalytic coordinate is essentially the evolving frontier orbital interaction while feeding with catalytic materials and adsorbates under proper reaction conditions.The heterogeneous catalytic reaction mechanism involves the initial adsorption and activation of reactants,subsequent intermediate transformation,final target product desorption,and regeneration of catalytic materials.In these catalytic processes,interaction modulations in terms of orbital hybridization/coupling allow an intrinsic control on both thermodynamics and kinetics.Concerned charge transfer and redistribution,orbital splitting and rearrangement with specific orientation,and spin change and crossover pose a formidable challenge on mechanism elucidation;it is hard to precisely correlate the apparent activity and selectivity,let alone rational modulations on it.Therefore,deciphering the orbital couplings inside a catalytic round is highly desirable and the dependent descriptor further provides in-depth insights into catalyst design at the molecule orbital level.This review hopes to provide a comprehensive understanding on orbital hybridizations,modulations,and correlated descriptors in heterogeneous catalysis.

Modulating p-d orbital hybridization by CuO/Cu nanoparticles enables carbon nanofibers high cycling stability as anode for sodium storage

Carbon nanofibers(CNFs)have been extensively studied as anode materials for sodium-ion batteries due to their high conductivity,large aspect ratio and good electrochemical stability.The low specific capacity and low first cycle efficiency of CNFs,however,have hindered its practical application.Herein,we present a facile strategy to synthesize a novel CNFs decorated with Cu/CuO nanoparticles(Cu-CNFs)using magnetron sputtering method.Cu/CuO nanoparticles were uniformly distributed on the surface of CNFs.According to the density functional theory(DFT)calculation,Cu/CuO nanoparticles d-orbitals and CNFs p-orbitals present hybridization states,and the Na~+adsorption energy of the modified CNFs decreases from-2.14 to-2.97 eV.The Cu-CNFs composites exhibit excellent sodium storage properties,presenting a desirable initial Coulombic efficiency of 76%and a high specific reversible capacity of 300 mAh·g^(-1)at 0.1 A·g^(-1)after 400 cycles.Cu-CNFs anode has excellent cycling stability under high current density,maintaining a high capacity of 150 mAh·g^(-1)at 1 A·g^(-1)after 6000 cycles.Using magnetron sputtering to regulate the electronic structure provides a new thought for improving the electrochemical performance of carbon materials.

Electronic structures of vacancies in Co_(3)Sn_(2)S_(2)

Co_(3)Sn_(2)S_(2)has attracted a lot of attention for its multiple novel physical properties,including topological nontrivial surface states,anomalous Hall effect,and anomalous Nernst effect.Vacancies,which play important roles in functional materials,have attracted increasing research attention.In this paper,by using density functional theory calculations,we first obtain band structures and magnetic moments of Co_(3)Sn_(2)S_(2)with exchange–correlation functionals at different levels.It is found that the generalized gradient approximation gives the positions of Weyl points consistent with experiments in bulk Co_(3)Sn_(2)S_(2).We then investigate the electronic structures of defects on surfaces with S and Sn terminations which have been observed in experiments.The results show that the single sulfur vacancy on the S-terminated surface introduces localized bond states inside the bandgap near the Fermi level.For di-and tri-sulfur vacancies,the localized defect states hybridize with neighboring ones,forming bonding states as well as anti-bonding states.The Sn vacancy on the Sn-terminated surface also introduces localized bond states,which are merged with the valence bands.These results provide a reference for future experimental investigations of vacancies in Co_(3)Sn_(2)S_(2).

轨道杂化诱导吸附-催化效应在四电子水系锌碘电池的应用

The successive I^(–)/I^(0)/I^(+)redox couples in the four-electron zinc-iodine aqueous battery(4eZIB)is plagued by the instability of the electrophilic I~+species,which could either be hydrolyzed or be neutralized by the I_(3)~–redox intermediates.We present an adsorption-catalysis approach that effectively suppresses the hydrolysis of ICl species and also provides an enhanced reaction kinetics to surpass the formation of triiodide ions.We elucidate that the improved stability is attributed to the pronounced orbital hybridization between the d orbitals of Fe-N_4 moieties(atomic Fe supported on nitrogen doped carbon)and the p orbitals of iodine species(I_(2)and ICl).Such d-p orbital hybridization leads to enhanced adsorption for iodine species,increased energy barrier for proton detachment from the ICl.HOH intermediate during hydrolysis,and efficient catalysis of the iodine redox reactions with high conversion efficiency.The proposed 4eZIB demonstrates practical areal capacity(>3 mAh cm^(-2))with a near-unity coulombic efficiency,high energy density of 420 Wh kg^(-1)(based on cathode mass),and long-term stability(over 10,000 cycles).Even at–20℃,the battery exhibits stable performance for over 1000 cycles with high iodine utilization ratio.

NIR-II Organic Photothermal Cocrystals with Strong Charge Transfer Interaction for Flexible Wearable Heaters

The organic cocrystal strategy has provided a convenient and efficient platform for preparing organic photothermal materials.However,the rapidly directional preparation of cocrystals with desirable photothermal properties remains challenging due to a lack of suitable design ideas.Here,two new photothermal cocrystals,MTC and MFC,based on acceptor molecules(TCNQ and F4TCNQ)with different electron-withdrawing capacities were quickly prepared by the coprecipitation method,aiming to explore the effect of charge transfer(CT)interaction on photothermal properties.Compared with MTC,the stronger intermolecular CT interaction in MFC facilitates extending the absorption range(from the NIR-I to the NIR-II region)and enhancing the non-radiative transition process.Under the 808 nm laser irradiation,the photothermal conversion efficiency(PCE)of MFC is 54.6%,whereas MTC displays a mere 36.8%.The MFC cocrystal was further combined with a flexible polymer substrate(HPDMS)to prepare a flexible wearable heater(HPDMS@MFC),which exhibits excellent NIR-II photothermal performance.This work points out a research direction for the rapid assembly of efficient photothermal cocrystals and additionally provides an extensive application prospect for organic photothermal cocrystals in the field of wearable devices.

Hybridized valence electrons of 4f^(0-14)5d^(0-1)6s^2:the chemical bonding nature of rare earth elements

The chemical bonding nature of rare earth（RE） elements can be studied by a quantitative analysis of electron domain of an atom. The outer electrons of RE elements are within the valence shell 4f^（0-14）5d^（0-1）6s^2, which are involved in all chemical bonding features. We in this work found that the chemical bonding characteristics of 4f electrons are a kind of hybridizations, and classified them into three types of chemical bonding of 4f^（0-14）5d^（0-1）6s^2, furthermore, the coordination number ranging from 2 to 16 could thus be determined. We selected Y（NO_3）_3, La（NO_3）_3, Ce（NO_3）_3, YCl_3, LaCl_3, and CeCl_3 as examples to in-situ observe their IR spectra of chemical bonding behaviors of Y^（3＋）, La^（3＋） and Ce^（3＋） cations, which could show different chemical bonding modes of 4f and 5d electrons. In the present study, we obtained the direct criterion to confirm whether 4f electrons can participate in chemical bonding, that is, only when the coordination number of RE cations is larger than 9.

New insight into pyrrolic-N site effect towards the first NIR window absorption of pyrrolic-N-rich carbon dots

Controlled C-N configurations,i.e.,pyrrolic-N,pyridinic-N,and graphitic-N,are promising strategies to tailor the carbon dots’(CDs)optical properties into the first near infrared(NIR)window(650-900 nm),a responsive range for biomedical application.However,a deep understanding of the role of the C-N configuration in the CDs’properties is still challenging and thoughtprovoking owing to their complex structure.Here,an underlying pyrrolic-N concentration and position effect on the pyrrolic-N-rich CDs’absorption was comprehensively elucidated based on the integrated experimental and computational studies.The assynthesized pyrrolic-N-rich CDs exhibit a first NIR window absorption centered at 650 nm with high photothermal conversion.Pyrrolic-N concentrations from 1.4%to 11.3%and positions(edge and mid-site)were systematically investigated.A mid-site pyrrolic-N was subsequently generated after the pyrrolic-N concentration more than 10%.Edge-site pyrrolic-N induces a frontier orbital hybridization,reducing bandgap energy,while mid-site pyrrolic-N plays a critical role in inducing a first NIR window absorption owing to their high charge transfer.Also,pyrrolic-N-rich CDs inherit a bowl-like topological feature,elevating the CDs’layer thickness as much as 0.71 nm.This study shed light on the design and optimization of pyrrolic-N on CDs for the first NIR window responsive materials in any biomedical application.

Tensile Strain and Interatomic Orbital Hybridization Effects Boost the Electrocatalytic Performance of Intermetallic Pd3Pb Nanowires for Ethanol Electrooxidation

We present a strategy that effectively modulate the d-band electronic structure of the active center by strain effect and interatomic orbital hybridization.This strategy efficiently promotes the kinetic process of the ethanol oxidation reaction(EOR)in alkaline media.In the intermetallic Pd_(3)Pb nanowires,the introduction of Pb not only causes the lattice expansion of Pd but also achieves the interatomic orbital hybridization bonding with Pd.Such interatomic orbital hybridization effect and tensile strain effect can effectively achieve a co-regulation of the d-band electronic structure of Pd,which directly affects the adsorption behavior of intermediate on Pd for EOR.Hence,the intermetallic Pd_(3)Pb nanowires demonstrate enhanced EOR activity and anti-poisoning ability against CO_(ads).Theoretical calculations show that the enhanced OH^(*)adsorption ability and the low energy barrier for the oxidative dehydrogenation of ethanol are the keys to high EOR activity and stability of the intermetallic Pd_(3)Pb nanowires.

Progress in oxygen behaviors in two-dimensional thin films

With the development of spintronics,the investigation on the behavior of oxygen in two-dimensional materials has never ceased.On account of its lively nature,oxygen is hard to exist alone in the system.However,it will interact with other atoms and produce complex orbital hybridization effect,which has influenced the performance of the material.Especially for materials in nanoscale,it is inevitable to introduce the oxygen atoms,no matter what in the process of preparation or employ.Therefore,it is necessary to carry on the research about the effect of oxygen behaviors in the two-dimensional thin films.In this paper,it will mainly introduce the effect of oxygen behaviors on the magnetic properties,electrical properties,phase transition,spin-dependent properties and thermal stability,summarize several factors which influence the oxygen behaviors,and generalize the research progress of the mechanism behind the oxygen behaviors.

Establishing a theoretical insight for penta-coordinated ironnitrogen-carbon catalysts toward oxygen reaction

Developing highly active iron-nitrogen-carbon catalysts for electrocatalytic oxygen reduction reactions(ORR)is pivotal to future energy technology.The penta-coordinated Fe-N-C with an augmented activity toward the oxygen reduction has been regarded as one of the promising candidates to replace platinum-based ORR catalysts.However,the lack of pertinent fundamental understanding hinders further optimizing the catalytic activity of such catalysts.Herein,through density functional theory(DFT)calculations,we systematically investigated the catalytic activity and ligand/metal coordination effects of 17 penta-coordinated FeN-C catalysts(labeled as FeNC-Xs,X denotes axial ligand).Our results not only show the theoretical overpotential of FeNC-Xs is lower than that of conventional tetra-coordinated Fe-N-C catalysts(labeled as FeNC),verifying the preeminent performance of FeNC-Xs,but also further indicate that the axial coordination effect of X ligands can decrease the orbital hybridization of Fe active center with ORR-relevant intermediates,sequentially accelerating the ORR.More importantly,we reveal that the catalytic activity of FeNC-Xs increases with a decreased electronegativity of X ligands,which can be utilized to describe the axial coordination effect for FeNC-Xs.These findings can deeply advance the understanding of penta-coordinated iron-nitrogencarbon catalysts,which provide timely guidelines for designing optimum Fe-N-C based catalysts.