Large Energy Barrier Research Articles

Roles of ESIPT and TICT in the Photophysical Process of a Ratiometric Fluorescence Sensor for Al3.

Precise detection of Al3+ with the aid of a fluorescence sensor is of fundamental importance in the fields of water pollution control and food safety. A comprehensive understanding of the photophysical process of the sensor as well as its underlying detection mechanism is a precondition for the design of highly efficient sensors. This contribution performs a thorough investigation of the ratiometric fluorescence sensing mechanism of an Al3+ sensor with the aid of density functional theory and time-dependent density functional theory. Two excited-state intramolecular proton transfer (ESIPT) processes are observed on the S1 state potential energy surface, which leads to emission around 565 nm. A twisted intramolecular charge transfer state is observed after one of the ESIPT processes via cis-trans isomerization of the C═N bond. However, the large energy barrier hinders its occurrence, which is quite unusual. Al3+ is found to form three strong coordination bonds with the sensor, which eliminates ESIPT processes and induces a significant blue shift of the emission spectrum to 480 nm. The origination of the sensor's selectivity is also uncovered by investigating the interaction between the sensor and interfering metal ions.

Twist along Central C-C Bonds in a Series of Fully π-Fused Propellanes.

Without stereogenic carbon centers, organic molecules can be chiral when they have large energy barriers for conformational inversion. In this work, conformational behaviors are investigated for a series of tricyclic propellane skeletons with increasing 6-membered-ring peripheral moieties fused with aromatic rings. According to theoretical calculations, trinaphtho[3.3.3]propellane has three vertical naphthalene rings like triptycene shape without torsion along the central C-C single bond. On the other hand, hexabenzo[4.4.4]propellane shows hexaphenylethane-like ca. 60° twist along the bond with large activation energy of 64 kcal mol-1 for twist inversion because of the high congestion caused by three 6-membered-ring loops. Indeed, the [4.4.4]propellane gives a stable pair of chiroptical enantiomers toward heating at 146 °C. By contrast, a hybrid [4.3.3]propellane exhibits fast interconversion between two twisted conformations even at -80 °C.

Functionalized porphyrin as a carrier bridge and a passivator for perovskite solar cells

Interfacial modification becomes one of the most emerging strategies in the state-of-the-art perovskite solar cells (PSCs). Here, two porphyrin derivatives (p-MeOTPP, m-DMeOTPP) with different methoxy groups are employed as the modifiers between perovskite and the hole transporting layer (HTL). The interaction at both of perovskite/modifier and modifier/HTL interfaces, and the hole-transfer ability of the modifier molecule are comprehensively studied, which are jointly responsible for the significant improvement in the optoelectronic properties of the device. More importantly, discussion on a molecular level reveals the distinct roles of modifiers with highly similar structures. A highest power conversion efficiency (PCE) of 24.56% is achieved for m-DMeOTPP modified PSCs, which is attributed to a synergy of efficient passivation effect at perovskite/modifier interface, sufficient built-in potential at modifier/HTL interface and minimal reorganization energy of hole hopping process. p-MeOTPP has a stronger passivation ability, but causes unfavorable interfacial dipole at modifier/HTL interface and a large energy barrier when hole’s hopping, only resulting in a smaller enhancement. Additionally, both modifers improve the device stability by strongly suppress the immigration of iodine species and moisture penetration. This work presents a synergy mechanism for interfacial engineering to pursue PSCs with high efficiency and stability, and provides practical guidelines at a molecular level to design a modifier not only as an efficient passivator but also as a high-speed carrier bridge.

Dual Active Sites with Charge‐asymmetry in Organic Semiconductors Promoting C‐C Coupling for Highly Efficient CO2 Photoreduction to Ethanol

Selective CO2 photoreduction into high‐energy‐density and high‐value‐added C2 products is an ideal strategy to achieve carbon neutrality and energy shortage, but it is still highly challenging due to the large energy barrier of the C‐C coupling step and severe exciton annihilation in photocatalysts. Herein, strong and localized charge polarization is successfully induced on the surface of melon‐based organic semiconductors by creating dual active sites with a large charge asymmetry. Confirmed by multiscale characterization and theoretical simulations, such asymmetric charge distribution, originated from the oxygen dopants and nitrogen vacancies over melon‐based organic semiconductors, reduces exciton binding energy and boosts exciton dissociation. The as‐formed charge polarization sites not only donate electrons to CO2 molecules but also accelerate the coupling of asymmetric *CO*CO intermediates for CO2 photoreduction into ethanol by lowering the energy barrier of this process. Consequently, an exceptionally high selectivity of up to 97% for C2H5OH and C2H5OH yield of 0.80 mmol g‐1 h‐1 have been achieved on this dual active sites organic semiconductor. This work, with its potential applicability to a variety of non‐metal multi‐site catalysts, represents a versatile strategy for the development of advanced catalysts tailored for CO2 photoreduction reactions.

Dual Active Sites with Charge-asymmetry in Organic Semiconductors Promoting C-C Coupling for Highly Efficient CO2 Photoreduction to Ethanol.

Selective CO2 photoreduction into high-energy-density and high-value-added C2 products is an ideal strategy to achieve carbon neutrality and energy shortage, but it is still highly challenging due to the large energy barrier of the C-C coupling step and severe exciton annihilation in photocatalysts. Herein, strong and localized charge polarization is successfully induced on the surface of melon-based organic semiconductors by creating dual active sites with a large charge asymmetry. Confirmed by multiscale characterization and theoretical simulations, such asymmetric charge distribution, originated from the oxygen dopants and nitrogen vacancies over melon-based organic semiconductors, reduces exciton binding energy and boosts exciton dissociation. The as-formed charge polarization sites not only donate electrons to CO2 molecules but also accelerate the coupling of asymmetric *CO*CO intermediates for CO2 photoreduction into ethanol by lowering the energy barrier of this process. Consequently, an exceptionally high selectivity of up to 97% for C2H5OH and C2H5OH yield of 0.80 mmol g-1 h-1 have been achieved on this dual active sites organic semiconductor. This work, with its potential applicability to a variety of non-metal multi-site catalysts, represents a versatile strategy for the development of advanced catalysts tailored for CO2 photoreduction reactions.

Metal nitrides as electrocatalysts in green ammonia synthesis

Green ammonia is assumed to be an important part of the European hydrogen economy and one of the most important substrates of chemical industry. The future development of its manufacturing processes can be related to the electrocatalytic studies yielding in the development of the catalytic materials that would effectively break the nitrogen-nitrogen bond to successfully drive the N2RR—a process of molecular nitrogen electroreduction to ammonia. Molecular nitrogen is characterized with strong triple bond energies (942 kJ/mol) which leading into large dissociation energy of N2 (9,76 eV) and also large energy barrier of the first step of triple bond dissociation 410 kJ/mol (4,25 eV). Those large energies makes reduction to ammonia an extremely difficult task. Metal nitrides of d and f block became in interest due to their activity in ammonia production from molecular nitrogen and hydrogen. Practically all the transition elements occurs in one of the four types of crystalline structures: regular, regular face cantered, hexagonal and hexagonal close packed. The reactions of these metals with nitrogen (or ammonia) typically yields in nitride compounds of an identical type of crystalline structure as the initial metal. Dealing with single metal systems, their ternary counterparts and metal–metal nitride heterostructures, the presented review shows that nitrides are promising groups of electrocatalytic materials. Being property-prone to their internal structural features such as non-stoichiometry and correlated concentration of nitrogen vacancies, metal nitrides are a good candidate for joined investigations spanned between electrochemistry, inorganic chemistry and material engineering.

The effect of perfluoroalkyl chain length and the type of acid group on PFAS adsorption from water

Widespread use of per- and polyfluoroalkyl substances (PFAS) poses significant ecological and health risks due to their non-degradability in the environment and consequent bioaccumulation in humans. In this work, we carried out a systematic computational study to unravel the effect of perfluorinated carbon chain length and the type of acid head group on the adsorption mechanism of PFAS from water. We considered the adsorption of perfluoroalkyl carboxylic acids (PFCA) and perfluoroalkyl sulfonic acids (PFSA) with chain lengths of three to eight perfluorinated carbons in hydrophobic all-silica zeolite Beta. Molecular dynamics (MD) simulations coupled with enhanced sampling calculations showed that adsorption free energies of both PFCA and PFSA decreased with increasing number of perfluorinated carbons. Calculated free energies further showed that PFCA and PFSA, which are anions in water, must overcome substantially large interfacial energy barriers to be adsorbed in hydrophobic pores. Subsequent ab initio MD simulations revealed that PFCA and PFSA gain a proton at the water–zeolite interface and are eventually adsorbed in neutral form. Breakdown of guest–host interaction energies into hydrophobic and polar components showed that hydrophobic interactions dominate PFCA adsorption whereas polar interactions are dominant in PFSA adsorption. This is due to sulfonic acid giving rise to stronger electrostatic interactions and the rearrangement of the electron density distribution in the perfluorinated carbon chain, which render the hydrophobic interactions relatively weaker. Our study reveals that a combination of adsorbents that provide optimized hydrophobic and polar interactions should be used for the capture of diverse PFAS from water.

Hydrofluoric Acid-Free Broadband Near-Infrared Phosphors K2LiMF6:Cr3+ with Zero-Thermal Quenching: Structure, Luminescence, and Application.

Near-infrared (NIR) phosphor-converted light-emitting diodes (pc-LEDs) are considered promising light sources for night vision, food analysis, biomedicine, and plant growth. Yet, the application potential of this technology is vulnerable to the function degradation of the phosphors used, such as thermal quenching, which needs to be addressed urgently. Herein, the NIR phosphors K2LiMF6:Cr3+ (M = Al, Ga, In) with a cubic double-perovskite structure synthesized by a green hydrofluoric acid-free hydrothermal method exhibit outstanding thermal stability. Under 450 nm excitation, the as-synthesized K2LiMF6:Cr3+ phosphors all exhibited broadband NIR emission covering 650-1000 nm peaking at 755-780 nm. The prepared K2LiAlF6:Cr3+ phosphor shows a unique zero-thermal quenching performance (I423K/I298K = 102%). The comprehensive effects of a wide band gap, large thermal energy barrier, weak electron-phonon coupling effect, and high structural rigidity are responsible for the suppression of thermal quenching in this material. The output power of the NIR pc-LED device reached 285 mW at 100 mA. This series of phosphors has promise in night vision and bioimaging applications.

A Self‐Assembling Molecule for Improving the Mobility in PEDOT:PSS Hole Transport Layer for Efficient Perovskite Light‐Emitting Diodes

AbstractPoly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS), the most widely used hole injection layer (HIL) for perovskite light‐emitting diodes (PeLEDs), has a large hole injection energy barrier and easy charge separation at PEDOT:PSS/perovskite layer. Here, a self‐assembling molecule (SAM) called (2‐(3,6‐dimethoxy‐9H‐carbazol‐9‐yl)ethyl) phosphonic acid (MeO‐2PACz) is introduced as an interlayer between PEDOT:PSS and perovskite to overcome the limitations of PEDOT:PSS HIL. The MeO‐2PACz interlayer facilitated hole injection due to the reduced hole injection energy barrier and the improved hole mobility, enhanced photoluminescence (PL) due to the prevented charge transfer from perovskite into PEDOT:PSS, and reduced interface trap density due to the passivation of methoxy and carbazole group toward perovskite. As a result, PeLEDs with MeO‐2PACz interlayer has greatly enhanced maximum luminance (Lmax = 17,310 cd m−2) and reduced leakage current, resulting in higher maximum external quantum efficiency (EQEmax = 21.50%) compared to pristine Control device (EQEmax of 4.82%).

M/BiOCl-(M=Pt, Pd, and Au) Boosted Selective Photocatalytic CO2 Reduction to C2 Hydrocarbons via *CHO Intermediate Manipulation.

Selective CO2 photoreduction to C2 hydrocarbons is significant but limited by the inadequate adsorption strength of the reaction intermediates and low efficiency of proton transfer. Herein, an ameliorative *CO adsorption and H2O activation strategy is realized via decorating bismuth oxychloride (BiOCl) nanostructures with different metal (Pt, Pd, and Au) species. Experimental and theoretical calculation results reveal that distinct *CO binding energies and *H acquisition abilities of the metal cocatalysts mediate the CO2 reduction activity and hydrocarbon selectivity. The relatively moderate *CO adsorption and *H supply over Pd/BiOCl endows it with the lowest free energy to generate *CHO, leading to its highest activity of hydrocarbon production. Specifically, the Pt cocatalyst can efficiently participate in H2O dissociation to deliver more *H for facilitating the protonation of the *CHO and *CHOH, thereby favoring CH4 production with 76.51% selectivity. A lower *H supply over Pd/BiOCl and Au/BiOCl results in a large energy barrier for *CHO or *CHOH protonation and thus a more thermodynamically favored OC─CHO coupling pathway, which endows them with vastly increased C2 hydrocarbon selectivity of 81.21% and 92.81%, respectively. The understanding of efficient C2 hydrocarbon production in this study sheds light on how materials can be engineered for photocatalytic CO2 reduction.

Long-term memory induced correction to Arrhenius law

The Kramers escape problem is a paradigmatic model for the kinetics of rare events, which are usually characterized by Arrhenius law. So far, analytical approaches have failed to capture the kinetics of rare events in the important case of non-Markovian processes with long-term memory, as occurs in the context of reactions involving proteins, long polymers, or strongly viscoelastic fluids. Here, based on a minimal model of non-Markovian Gaussian process with long-term memory, we determine quantitatively the mean FPT to a rare configuration and provide its asymptotics in the limit of a large energy barrier E. Our analysis unveils a correction to Arrhenius law, induced by long-term memory, which we determine analytically. This correction, which we show can be quantitatively significant, takes the form of a second effective energy barrier E′<E\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$E^{\\prime} \\, < \\, E$$\\end{document} and captures the dependence of rare event kinetics on initial conditions, which is a hallmark of long-term memory. Altogether, our results quantify the impact of long-term memory on rare event kinetics, beyond Arrhenius law.

Record Quantum Tunneling Time in an Air-Stable Exchange-Bias Dysprosium Macrocycle.

In recent years, dysprosium macrocycle single-molecule magnets (SMMs) have received increasing attention due to their excellent air/thermal stability, strong magnetic anisotropy, and rigid molecular skeleton. However, they usually display fast zero-field quantum tunneling of the magnetization (QTM) rate, severely hindering their data storage applications. Herein, we report the design, synthesis, and characterization of an air-stable monodecker didysprosium macrocycle integrating strong single-ion anisotropy, near-perfect local crystal field (CF) symmetry, and efficient exchange bias. These indispensable features enable clear-cut elucidation of the crucial role of very weak antiferromagnetic coupling on magnetization dynamics, creating a prominent SMM with a large effective energy barrier (Ueff) of 670 cm-1, open hysteresis loops at zero field up to 14.9 K, and a record relaxation time of QTM (τQTM), 24281 s, for all known nonradical-bridged lanthanide SMMs.

Bistable Insect-Scale Jumpers with Tunable Energy Barriers for Multimodal Locomotion.

Drawing inspiration from the jumping mechanisms of insects (e.g., click beetles), bistable structures can convert slow deformations of soft actuating material into fast jumping motions (i.e., power amplification). However, bistable jumpers often encounter large energy barriers for energy release/re-storage, posing a challenge in achieving multimodal (i.e., height/distance) and continuous jumps at the insect scale (body length under 20mm). Here, a new offset-buckling bistable design is introduced that features antisymmetric equilibrium states and tunable energy barriers. Leveraging this design, a Boundary Actuation Tunable Energy-barrier (BATE) jumper (body length down to 15mm) is developed, and transform BATE jumper from height-jump mode (up to 12.7 body lengths) to distance-jump mode (up to 20 body lengths). BATE jumpers can perform agile continuous jumping (within 300ms for energy release/re-storage times) and real-time status detection is further demonstrated. This insect-level performance of the proposed BATE jumper showcases its potential toward future applications in exploration, search, and rescue.

Automated collective variable discovery for MFSD2A transporter from molecular dynamics simulations

Biomolecules often exhibit complex free energy landscapes in which long-lived metastable states are separated by large energy barriers. Overcoming these barriers to robustly sample transitions between the metastable states with classical molecular dynamics (MD) simulations presents a challenge. To circumvent this issue, collective variable (CV)-based enhanced sampling MD approaches are often employed. Traditional CV selection relies on intuition and prior knowledge of the system. This approach introduces bias, which can lead to incomplete mechanistic insights. Thus, automated CV detection is desired to gain a deeper understanding of the system/process. Analysis of MD data with various machine-learning algorithms, such as principal component analysis (PCA), support vector machine, and linear discriminant analysis (LDA) based approaches have been implemented for automated CV detection. However, their performance has not been systematically evaluated on structurally and mechanistically complex biological systems. Here, we applied these methods to MD simulations of the MFSD2A (Major Facilitator Superfamily Domain 2A) lysolipid transporter in multiple functionally relevant metastable states with the goal of identifying optimal CVs that would structurally discriminate these states. Specific emphasis was on the automated detection and interpretive power of LDA-based CVs. We found that LDA methods, which included a novel gradient descent-based multiclass harmonic variant, termed GDHLDA, we developed here, outperform PCA in class separation, exhibiting remarkable consistency in extracting CVs critical for distinguishing metastable states. Furthermore, the identified CVs included features previously associated with conformational transitions in MFSD2A. Specifically, conformational shifts in transmembrane helix 7 and in residue Y294 on this helix emerged as critical features discriminating the metastable states in MFSD2A. This highlights the effectiveness of LDA-based approaches in automatically extracting from MD trajectories CVs of functional relevance that can be used to drive biased MD simulations to efficiently sample conformational transitions in the molecular system.

Ultrafast dual-fluorescence dynamics of 2-(2'-hydroxyphenyl) benzimidazole by femtosecond transient absorption spectroscopy

2-(2'-Hydroxyphenyl) benzimidazole (HBI) and its derivatives are widely used in fluorescent probes, luminescent materials, and other sensing materials. In this study, the time-resolved fluorescence behaviour, and excited-state dynamics of HBI and 2-phenyl-1H-benzo[d]imidazole (BI) were studied using femtosecond transient absorption (fs-TA) spectroscopy. The stimulated emission (SE) and excited-state absorption signals of the BI molecule were located at 355 and 437 nm, respectively. For HBI, these signals were located at 475 and 384 nm, respectively. The SE signals of the BI and HBI molecules in their fs-TA spectra were consistent with the experimental short-wave fluorescence at 340 and 460 nm, respectively, in the steady-state spectra. The long-wave signal of HBI at 475 nm indicates its dual fluorescence, which may be caused by proton transfer or conformational torsion after photoexcitation. The large theoretical energy barrier of 40.97 kcal/mol in first excited (S1) state of HBI excludes the latter hypothesis. Additionally, the small energy barrier (1.88 kcal/mol) in the S1 state confirmed the excited-state intramolecular proton transfer (ESIPT). This indicates that ESIPT induces dual fluorescence behaviour of the HBI molecule, which was also demonstrated by the infrared spectra, theoretical fluorescence peaks, and molecular orbitals.

Fatigue-resistant adhesion through high energy barriers

The applications of soft materials in various fields often require interfacial adhesion to sustain prolonged static or cyclic loads, whereas most existing adhesives are susceptible to fatigue failure. Unlike in a quasistatic debonding process, which depends more on the average resistance, the key to preventing fatigue crack propagation is to build up high energy barriers locally. Herein, we invoke three types of structural designs to induce large energy barriers at the interface to achieve fatigue-resistant adhesion. By varying the local bending stiffness of the backing layer, locally altering the fracture mode through kirigami patterns, or hindering crack initiation with simple edge notches, we enhanced the fatigue thresholds of various adhesives against peeling by several orders of magnitude, reaching record-breaking values. To verify the proposed mechanism and reveal the details of these remarkable enhancements, we develop theoretical models to study the peeling processes. Based entirely on structural design, the proposed mechanism is non-material-specific and universally applicable to various intermolecular interactions under any harsh environment, such as high temperature, high humidity, and physiological environments. We envision that the strategy and methodologies presented can pave the avenue of future adhesion designs for both durability and reliability.

Theoretical prediction and regulation of interlayer stable angle in twisting bilayer graphene

Recent researches showed that interlayer rotation, as a control method, can effectively regulate the mechanical, electrical, and optical properties of two-dimensional (2D) materials. The control of the twisting angle and its stability influence the properties of rotation-tunable electronics, so it has attracted much attention. In this research, based on the Lennard-Jones (L-J) potential and energy density method, the energy landscape of twisted bilayer graphene (tBLG) is studied. The dependence of the locally stable twisting angle and the number of potential energy barriers on the size of the top layer graphene is analyzed. It is found that the size effect is related to the vertical distance between carbon atoms and the rotation axis. The large-sized top layer graphene has a larger energy barrier and higher stability under the same conditions, which is conducive to the structural stability of the rotation-tunable electronics. The vacancy defect and the shape of the top layer graphene have an effect on the energy landscape, based on which the regulation of stable twisting angle can be achieved. In addition, the effect of the position of the top layer graphene on the energy landscape is studied, and it is found that the energy landscape has a 2D periodicity with the change of the position, which is related to the lattice structure of graphene. There are two main modes of energy landscape with the variation of the position of top layer graphene, and the changing trend is similar under the same mode. Our research predicts the interlayer stable twisting angle theoretically and provides theoretical support for the design of rotation-tunable electronics.

Enhanced Adsorption Response of pH-Sensitive Peptides: The Role of Membrane Acidity.

pH-sensitive peptides bind and traverse lipid membranes in response to changes in pH. They can be used to target tumors and other acidic tissues. We investigate the influence of acidic lipids on the pH-driven adsorption of recently synthesized peptides. Using a statistical-thermodynamic theory that takes into account the acid-base chemistry of peptides and lipids, we find that the presence of acidic lipids amplifies changes in peptide surface concentration when transitioning from high to low pH. We study cyclic and linear peptides, containing tryptophan, glutamic acid, and arginine residues, examining their behavior in both neutral and acidic membranes. Membrane binding consistently results from the shallow insertion of tryptophan residues with hydrophilic residues facing the aqueous solution. Regardless of the pH, the peptide's geometry predominantly determines the orientation and distribution of residues. Notably, we find that not only the extent of adsorption is pH-sensitive but also the underlying adsorption mechanism: it is barrier-free at low pH but hindered by a large free energy barrier at high pH. Hence, under more acidic conditions, pH-sensitive peptides show facilitated adsorption both kinetically and thermodynamically.

On the Diffusion of Ionic Liquids in ILs@ZIF-8 Composite Materials: A Density Functional Theory Study.

Recently, composite materials consisting of ionic liquids (ILs) and metal-organic frameworks (MOFs) have attracted a great deal of attention due to their fantastic properties. Many theoretical studies have been performed on their special structures and gas separation applications. Yet, the mechanism for the diffusion of ILs inside MOF channels still remains unclear. Here, the DFT calculations (e.g., rigid and relaxed potential energy surface, PES, scan) together with frontier orbital analysis, natural charge analysis, and energy decomposition analysis were performed to investigate the diffusion behavior of a typical IL, [C4mim][PF6], into the ZIF-8 SOD cage. The PES profiles indicate that it is quite difficult for the cation [C4min]+ to diffuse into the cage of ZIF-8 through the pristine pores because of the large imidazole steric hindrance, which results in a large energy barrier of ca. 40 kcal·mol-1 at the least. Interestingly, the PES reveals that a successful diffusion could be obtained by thermal contributions, which enlarge the pore size through swing effects at higher temperatures. For example, both [C4mim]+ and [PF6]- could easily diffuse through the channel of the ZIF-8 SOD cage when the pore size was increased to 6.9 Å. Subsequently, electronic structure analyses reveal that the main interactions between [PF6]- or [C4mim]+ and ZIF-8 are the steric repulsion interactions. Finally, the effects of the amounts of [C4mim][PF6] on the ZIF-8 structures were investigated, and the results show that two pairs of [C4mim][PF6] per SOD cage are the most stable in terms of the interaction between energies and structural changes. With these findings, we propose that the high-temperature technique could be employed during the synthesis of IL@MOF membranes, to enrich their family members and their industrial applications.

Layer-by-layer phase transformation in Ti3O5 revealed by machine-learning molecular dynamics simulations

Reconstructive phase transitions involving breaking and reconstruction of primary chemical bonds are ubiquitous and important for many technological applications. In contrast to displacive phase transitions, the dynamics of reconstructive phase transitions are usually slow due to the large energy barrier. Nevertheless, the reconstructive phase transformation from β- to λ-Ti3O5 exhibits an ultrafast and reversible behavior. Despite extensive studies, the underlying microscopic mechanism remains unclear. Here, we discover a kinetically favorable in-plane nucleated layer-by-layer transformation mechanism through metadynamics and large-scale molecular dynamics simulations. This is enabled by developing an efficient machine learning potential with near first-principles accuracy through an on-the-fly active learning method and an advanced sampling technique. Our results reveal that the β−λ phase transformation initiates with the formation of two-dimensional nuclei in the ab-plane and then proceeds layer-by-layer through a multistep barrier-lowering kinetic process via intermediate metastable phases. Our work not only provides important insight into the ultrafast and reversible nature of the β−λ transition, but also presents useful strategies and methods for tackling other complex structural phase transitions.