Dynamic Structural Evolution Research Articles

Regulating electronic states of nitride/hydroxide to accelerate kinetics for oxygen evolution at large current density

Rational design efficient transition metal-based electrocatalysts for oxygen evolution reaction (OER) is critical for water splitting. However, industrial water-alkali electrolysis requires large current densities at low overpotentials, always limited by intrinsic activity. Herein, we report hierarchical bimetal nitride/hydroxide (NiMoN/NiFe LDH) array as model catalyst, regulating the electronic states and tracking the relationship of structure-activity. As-activated NiMoN/NiFe LDH exhibits the industrially required current density of 1000 mA cm−2 at overpotential of 266 mV with 250 h stability for OER. Especially, in-situ electrochemical spectroscopic reveals that heterointerface facilitates dynamic structure evolution to optimize electronic structure. Operando electrochemical impedance spectroscopy implies accelerated OER kinetics and intermediate evolution due to fast charge transport. The OER mechanism is revealed by the combination of theoretical and experimental studies, indicating as-activated NiMoN/NiFe LDH follows lattice oxygen oxidation mechanism with accelerated kinetics. This work paves an avenue to develop efficient catalysts for industrial water electrolysis via tuning electronic states.

Mechanistic Insight into Dual-Metal-Site Catalysts for the Oxygen Reduction Reaction

Incorporating a second transition metal to iron–nitrogen–carbon single-atom catalysts (Fe–N–C SACs) to design dual-metal-site catalysts (DMSCs) was demonstrated to offer a promising opportunity to enhance the oxygen reduction reaction (ORR). However, due to the many possible structural configurations and the dynamic structure evolution of metal centers under reaction conditions, it is challenging to clearly elucidate the structure–property relationship at the atomic level. Here, we develop a computational workflow integrating configuration generations, phase diagram constructions, and reaction free energy calculations to provide an insightful understanding of the active site structures and catalytic mechanisms of ORR on DMSCs. Using Fe–Cu as an example, we generate 31 configurations by tiling the hexagonal lattice of graphene and investigate their atomic structures under reaction conditions. We find that for a wide range of electrode potentials, the Fe site is covered by an *OH intermediate, while the Cu site is not covered by any intermediate. With the OH-ligated structures, we identify the configurations which possess higher catalytic activity than Fe–N–C and Pt(111). We demonstrate that ORR on Fe–Cu DMSCs proceeds via the associative pathway, and the desorption of *OH is the rate-determining step. Further analysis reveals a linear correlation between the limiting potential and the magnetic moment on Fe and suggests a closer distance between the two metal sites benefits the catalytic activity. These mechanistic insights pave the way for the rational design of efficient platinum group metal-free DMSCs for ORR.

Achieving Thermodynamic Stability of Single‐Crystal Co‐Free Ni‐Rich Cathode Material for High Voltage Lithium‐Ion Batteries

AbstractNi‐rich layered cathode materials are progressively considered as the standard configuration of high‐energy electric vehicles by virtues of their high capacity and eliminated “range anxiety.” However, the poor cyclic stability and severe cobalt supply crisis would restrain their wide commercial applicability. Here, a cost‐effective single‐crystal Co‐free Ni‐rich cathode material LiNi0.8Mn0.18Fe0.02O2 (NMF), which outperforms widely commercial polycrystalline LiNi0.83Co0.11Mn0.06O2 (MNCM) and single‐crystal LiNi0.83Co0.11Mn0.06O2 (SNCM) is reported. Surprisingly, NMF can compensate for the reversible capacity loss under the designed conditions of high‐temperature and elevated‐voltage, achieving a competitive energy density compared with conventional MNCM or SNCM. Combining operando characterizations and density functional theory calculation, it is revealed that NMF cathode with improved dynamic structure evolution largely alleviates the mechanical strain issue commonly found in Ni‐rich cathode, which can reduce the formation of intragranular cracks and improve the safety performance. Consequently, this new Co‐free NMF cathode can achieve a perfect equilibrium between material cost and electrochemical performance, which not only reduces the production cost by >15%, but also demonstrates excellent thermal stability and cycling performance..

Spectroscopically unraveling high-valence Ni-Fe catalytic synergism in NiSe2/FeSe2 heterostructure

Heterostructured compounds with rationally engineered interfaces are widely reported as efficient oxygen evolution reaction (OER) electrocatalysts, but the mechanism of the intrinsic activities still unclear. Herein, a typical model catalyst of NiSe2/FeSe2 heterostructure with a low overpotential of 230 mV at 10 mA cm−2 and long-term durability is fabricated by selenizing Ni-Fe Prussian-blue analog (PBA) templates. In-situ/operando Raman spectroscopy and synchrotron-based X-ray absorption spectroscopy (XAS) are employed to reveal the real catalytic process. It is attested that the dynamic surface reconstruction into Ni-O-Fe configurations, and the high-valence NiIII-O-FeIII moieties in Ni–FeOOH is responsible for the high oxygen evolution. Density functional theory (DFT) simulations further confirm that the electron transfer driven by strong Ni-Fe synergistic effect in NiSe2/FeSe2 heterostructure not only improves the density of Ni/Fe active sites, but also modulates the nature active sites. This works may deepen our understanding of intrinsic activities of metal compound heterostructures and the correlation between dynamic surface structural evolution and catalytic activity.

Direct Imaging of the Kinetic Crystallization Pathway: Simulation and Liquid-Phase Transmission Electron Microscopy Observations.

The crystallization of materials from a suspension determines the structure and function of the final product, and numerous pieces of evidence have pointed out that the classical crystallization pathway may not capture the whole picture of the crystallization pathways. However, visualizing the initial nucleation and further growth of a crystal at the nanoscale has been challenging due to the difficulties of imaging individual atoms or nanoparticles during the crystallization process in solution. Recent progress in nanoscale microscopy had tackled this problem by monitoring the dynamic structural evolution of crystallization in a liquid environment. In this review, we summarized several crystallization pathways captured by the liquid-phase transmission electron microscopy technique and compared the observations with computer simulation. Apart from the classical nucleation pathway, we highlight three nonclassical pathways that are both observed in experiments and computer simulations: formation of an amorphous cluster below the critical nucleus size, nucleation of the crystalline phase from an amorphous intermediate, and transition between multiple crystalline structures before achieving the final product. Among these pathways, we also highlight the similarities and differences between the experimental results of the crystallization of single nanocrystals from atoms and the assembly of a colloidal superlattice from a large number of colloidal nanoparticles. By comparing the experimental results with computer simulations, we point out the importance of theory and simulation in developing a mechanistic approach to facilitate the understanding of the crystallization pathway in experimental systems. We also discuss the challenges and future perspectives for investigating the crystallization pathways at the nanoscale with the development of in situ nanoscale imaging techniques and potential applications to the understanding of biomineralization and protein self-assembly.

Operando Electrochemical Liquid-Cell Scanning Transmission Electron Microscopy (EC-STEM) Studies of Evolving Cu Nanocatalysts for CO2 Electroreduction

The design and synthesis of nanocatalysts with well-defined sizes, compositions, and structures have revolutionized our accessibility to tunable catalyst activity and selectivity for a variety of energy-related electrochemical reactions. Nonetheless, establishing structure-(re)activity correlations requires the understanding of the dynamic evolution of pristine nanocatalysts and the identification of their active states under operating conditions. We previously communicated the operando observation of Cu nanocatalysts evolving into active metallic Cu nanograins for CO2 electroreduction (Yang et al. Nature 2023, 614, 262−269). Here, we expand our discussion to the technical capabilities and further research applications of operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM), which enables quantitative electrochemistry while tracking dynamic structural evolution of sub-10 nm Cu nanocatalysts. The coexistent H2 bubbles, often disruptive to operando spectroscopy, are an effective approach to create a thin-liquid layer that significantly improves spatial resolution while remaining electrochemically accessible to Cu nanocatalysts. Operando four-dimensional (4D) STEM in liquids provides insights into the complex structure of active polycrystalline metallic Cu nanograins. With continuous technical developments, we anticipate that operando EC-STEM will evolve into a powerful electroanalytical method to advance our understanding of a variety of nanoscale electrocatalysts at solid/liquid interfaces.

Dynamic Structure Evolution of Extensively Delithiated High Voltage Spinel Li1+xNi0.5Mn1.5O4 x < 1.5.

High voltage spinel is one of the most promising next-generation cobalt-free cathode materials for lithium ion battery applications. Besides the typically utilized compositional range of LixNi0.5Mn1.5O4 0 < x < 1 in the voltage window of 4.90-3.00 V, additional 1.5 mol of Li per formula unit can be introduced into the structure, in an extended voltage range to 1.50 V. Theoretically, this leads to significant increase of the specific energy from 690 to 1190 Wh/kg. However, utilization of the extended potential window leads to rapid capacity fading and voltage polarization that lack a comprehensive explanation. In this work, we conducted potentiostatic entropymetry, operando XRD and neutron diffraction on the ordered stoichiometric spinel LixNi0.5Mn1.5O4 within 0 < x < 2.5 in order to understand the dynamic structure evolution and correlate it with the voltage profile. During the two-phase reaction from cubic (x < 1) to tetragonal (x > 1) phase at ∼2.8 V, we identified the evolution of a second tetragonal phase with x > 2. The structural evaluation during the delithiation indicates the formation of an intermediate phase with cubic symmetry at a lithium content of x = 1.5. Evaluation of neutron diffraction data, with maximum entropy method, of the highly lithiated phase LixNi0.5Mn1.5O4 with 2 < x < 2.5 strongly suggests that lithium ions are located on octahedral 8a and tetrahedral 4a positions of the distorted tetragonal phase I41amd. Consequently, we were able to provide a conclusive explanation for the additional voltage step at 2.10 V, the sloping voltage profile below 1.80 V, and the additional voltage step at ∼3.80 V.

Dynamic structural evolution of lignin macromolecules and hemicelluloses during Chinese pine growth

To comprehend the biosynthesis processes of conifers, it is essential to investigate the disparity between the cell wall shape and the interior chemical structures of polymers throughout the development of Chinese pine. In this study, branches of mature Chinese pine were separated according to their growth time (2, 4, 6, 8 and 10 years). The variation of cell wall morphology and lignin distribution was comprehensively monitored by scanning electron microscopy (SEM) and confocal Raman microscopy (CRM), respectively. Moreover, the chemical structures of lignin and alkali-extracted hemicelluloses were extensively characterized by nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The thickness of latewood cell walls increased steadily from 1.29 μm to 3.38 μm, and the structure of the cell wall components became more complicated as the growth time increased. Based on the structural analysis, it was found that the content of β-O-4 (39.88–45.44/100 Ar), β-β (3.20–10.02/100 Ar) and β-5 (8.09–15.35/100 Ar) linkages as well as the degree of polymerization of lignin increased with the growth time. The complication propensity increased significantly over 6 years before slowing to a trickle over 8 and 10 years. Furthermore, alkali-extracted hemicelluloses of Chinese pine mainly consist of galactoglucomannans and arabinoglucuronxylan, in which the relative content of galactoglucomannans increased with the growth of the pine, especially from 6 to 10 years.

Dynamic Construction and Maintenance of Confined Nanoregions via Hydrogen-Bond Networks between Acetylene Reactants and a Polyoxometalate-Based Metal-Organic Framework.

The nanoconfinement effect in catalysis has attracted much attention because it provides a novel means of regulating the molecular properties and related reactions. Confined nanoregions composed of both reactants and catalysts through weak interactions are expected to improve the catalytic performance and promote the mass transport of relevant molecules simultaneously. However, at reaction temperatures, the structural variation of such confined spaces constructed via weak interactions remains unclear. Herein, through density functional theory calculations combined with ab initio molecular dynamics simulations, we have systematically investigated the dynamic structural evolution of the confined space constructed by acetylene reactants and a polyoxometalate-based metal-organic framework (POMOF) via hydrogen-bond networks. It is found that, at the reaction temperature of acetylene semihydrogenation, the hydrogen-bond networks and generated confined nanoregions are not rigid but are constantly changing and dynamically maintained. The steering role played by the O atoms at the surfaces of the polyoxometalate clusters is essential for generation of the hydrogen-bond networks and maintenance of the nanoregions. Upon confinement, the acetylene reactants can be better activated than those in an unconstrained atmosphere, which is reflected by the different dynamic distributions of the ∠CHC bending magnitude. Moreover, from a comparison of the distinct interaction characteristics between acetylene/ethylene and POMOF, the different manifestations in the adsorption energy variations of the confined molecules can be interpreted. This work helps to elucidate the underlying mechanisms of confined catalysis and may promote its application in practical catalytic processes.

Single Platinum Atom Catalysts with HighDensity.

As a new frontier, the rapid development of single-atom catalysts (SACs) in heterogeneous catalysis has attracted extensive attention. However, a fundamental understanding of the dynamic formation process of active metal atom sites is lacking. The rational design of high-performance SACs now becomes possible byexplicitly addressing the conundrum of constructing high-density SACs and elucidating the evolution of SACs during the synthesis.

In Situ Surface Reconstruction of Catalysts for Enhanced Hydrogen Evolution

The in situ surface reconstitution of a catalyst for hydrogen evolution refers to its structure evolution induced by strong interactions with reaction intermediates during the hydrogen evolution reaction (HER), which eventually leads to the self-optimization of active sites. In consideration of the superior performance that can be achieved by in situ surface reconstitution, more and more attention has been paid to the relationship between active site structure evolution and the self-optimization of HER activity. More and more in situ and/or operando techniques have been explored to track the dynamic structural evolution of HER catalysts in order to clarify the underlying mechanism. This review summarizes recent advances in various types of reconstruction such as the reconfiguration of crystallinity, morphological evolution, chemical composition evolution, phase transition refactoring, surface defects, and interface refactoring in the HER process. Finally, different perspectives and outlooks are offered to guide future investigations. This review is expected to provide some new clues for a deeper understanding of in situ surface reconfiguration in hydrogen evolution reactions and the targeted design of catalysts with desirable structures.

Long lifespan thermal barrier coatings overview: Materials, manufacturing, failure mechanisms, and multiscale structural design

A long lifespan is a basic support for the thermal protection of thermal barrier coatings (TBCs). Plasma-sprayed TBCs provide high thermal insulation and cost-effective advantages; thus, they are used in cutting-edge areas, such as land-based gas turbines. However, following thermal exposure, sintering causes structural changes and significant degradation in thermal insulation and strain tolerance. Thus, plasma-sprayed TBCs often show poor performance in thermal cycling tests. Therefore, extending the lifespan of plasma-sprayed TBCs is crucial. This study reviews the structural design of TBCs for a long lifespan. The main contents reviewed include the following aspects: (1) the basic structural features of plasma-sprayed TBCs with high thermal insulation and strain tolerance in an as-deposited state; (2) the dynamic structural evolution during thermal exposure to reveal the degradation mechanism in thermal and mechanical properties; and (3) multiscale structural design of TBCs to achieve a long lifespan. This review aims to contribute to the development of advanced gas turbines.

Prospect for application of radial distribution function in coal carbonisation research

ABSTRACT Carbonisation is an important way of comprehensive utilisation of coal. In this short contribution, the application of wide angle X-ray scattering (WAXD) and radial distribution function (RDF) in coal carbonisation research is briefly reviewed and prospected. General WAXD analysis can only provide basic geometrical structural parameters of crystals in the sample; while RDF derived from WAXD by Fourier transform can give further detailed structural parameters of coordination of atoms in sample. The application of RDF in coal science has been reported in offline static studies, but not in-situ studies. Here, a new ideal to perform in-situ RDF study on coal carbonisation is presented, which is based on a powerful synchrotron radiation platform with a proper detector and a high-temperature furnace. Thus, it is expected to obtain the fine dynamic structural evolution characteristics of coal during carbonisation.

Absolute molecular structure of the polystyrene at the buried polystyrene/silica interface and its relationship to dewetting during annealing

Dewetting is a common phenomenon observed from polymer thin films under stimuli, such as annealing, which directly affects the applications of polymer thin films. A key to understanding such dewetting behavior is to precisely probe the molecular structure evolution at the buried polymer/substrate interface during annealing. However, non-destructively probing the buried interface is very difficult at the molecular level and in situ. In this study, the specific surface- and phase-sensitive sum frequency generation (SFG) vibrational spectroscopy was used to investigate PS thin films on silica substrates during annealing. The results showed that the absolute orientation/conformation of PS at the film surface was significantly different from that of the flattened PS nanolayer formed near the substrate by dewetting. The dynamic molecular structure evolution of the PS nanolayer (the formation process of the flattened PS nanolayer) at the buried PS/silica interface was directly observed in situ. The dewetting occurred at the non-adsorbed (bulk, free) PS/the flattened PS nanolayer interface due to the autophobic effect. Furthermore, the effects of end groups and solvents on the PS dewetting rate were also elucidated. This study provides a molecular-level understanding of the PS structure at the buried PS/silica interface and its relationship to dewetting behavior.

Dynamic Structural Evolution of [Rh(NO)2]+ Complex/Rh Metal Cluster in Zeolite during de-NOx via in Situ Formed NH3 under Lean/Rich Periodic Conditions

The dynamic structural evolution of Rh species in mordenite (MOR) zeolite was investigated using in situ spectroscopic techniques and density functional theory (DFT) calculations. In situ X-ray absorption spectroscopy and operando infrared (IR) revealed that metallic Rh species were oxidized to afford isolated [Rh(NO)2]+ species under NO flow at 200 °C, whereas small Rh metal clusters are formed under the subsequent H2 flow. Ab initio thermodynamics analysis shows that the plausible structures under NO and H2 at 200 °C are [Rh(NO)2]+ and Rh clusters in MOR, which is consistent with the experimental observations. A comparative study of Rh-loaded Al2O3 suggests that Al sites in MOR increase the thermodynamic stability of isolated Rh+ species and thus prevent their overoxidation to Rh2O3 under NO. NO capture in the form of [Rh(NO)2]+ and its selective reduction toward NH3 under H2 flow were observed by in situ IR measurements. The RhMOR catalyst exhibited ∼60% of NOx conversion above 200 °C under periodic lean/rich conditions. Transition-state calculations showed that the activation barrier for NO reduction to NH3 on [Rh(NO)2]+ (178 kJ/mol) is higher than that for Rh13 (156 kJ/mol), suggesting that Rh metal clusters are preferable NH3 formation sites, where the Rh13-catalyzed NO reduction into N2 and N2O was less preferable than NH3 formation, which is consistent with the experimental results. Combined with operando IR experiments under lean (NO + O2) and rich (NO + H2) conditions, we show that the reversible dynamic structural evolution of Rh species ([Rh(NO)2]+ ↔ Rh metal clusters under lean and rich conditions) is a key mechanistic feature for unsteady-state de-NOx via the capture of NO, its selective reduction to NH3, and the selective reduction of NO with NH3 formed in situ.

The Electrochemical Interface As a Reactive Environment to Re-Synthesize Electrode Surface Chemistry Using the Dissolution-Redeposition Dynamics

The electrode-electrolyte interface governs the efficiency and life time of almost all electrochemical reactions. Essentially, this interface, as a geometrically confined environment, allows many interfacial reactions occurring and provides a versatile toolbox of tailoring electrode surface chemistry under operating conditions. Here, through synchrotron spectroscopic, microscopic, and imaging characterizations, using the electrochromic tungsten trioxide (WO3) in an acidic electrolyte as the research platform, we reveal that the performance degradation is related to electrode material morphology evolution, phase transformation, and charge heterogeneity. We experimentally demonstrate that WO3 dissolution and redeposition across the electrochemical interface trigger all these evolutions. The redeposition process provokes the in situ crystal growth, inducing the evolution from the semicrystalline WO3 to the single-crystalline, nanoflake-shaped, proton-trapped tungsten trioxide di-hydrate (H x WO3·2H2O). Importantly, as a ubiquitous phenomenon, transition metal dissolution will form the diffusion layer at the interface. We have established a novel experimental design to probe and understand how the dissolved transition metal species evolve in the diffusion layer. The thickness of the diffusion layer is up to tens of micrometers, and the local electronic structure of dissolved species varies with the distance from the electrode surface. Furthermore, this dynamic dissolution and redeposition feature can be manipulated to regulate the chemical composition and crystal structure of the electrode surface as well as the overall electrochemical performance. Foreign cations (e.g., Ti4+), either added as electrolyte additives or dissolved from surface coatings, can rapidly participate in the electrode dissolution-redeposition process and facilitate the establishment of the dissolution-redeposition equilibrium, thereby alleviating W net dissolution, modulating the electrode morphology, and improving the Coulombic efficiency and cycling stability during long-term electrochemical reactions. Therefore, our systematic study demonstrates that it is feasible to exploit the intertwined dissolution-redeposition kinetics between oxide surface coatings and electrodes in aqueous electrolytes to extend control over electrochemical interfacial reactions. Electrode surface chemistry can be re-synthesized in terms of regulating the dynamic structural evolution of electrode surface and the correlatively developing speciation at the interface, which highlights the significance of more fundamental investigations at the electrode-electrolyte interfaces.

Optically induced changes in the band structure of the Weyl charge-density-wave compound

Collective modes are responsible for the emergence of novel quantum phases in topological materials. In the quasi-one dimensional (1D) Weyl semimetal , a charge density wave (CDW) opens band gaps at the Weyl points, thus turning the system into an axionic insulator. Melting the CDW would restore the Weyl phase, but 1D fluctuations extend the gapped regime far above the 3D transition temperature (T = 263 K), thus preventing the investigation of this topological phase transition with conventional spectroscopic methods.Here we use a non-equilibrium approach: we perturb the CDW phase by photoexcitation, and we monitor the dynamical evolution of the band structure by time- and angle-resolved photoelectron spectroscopy. We find that, upon optical excitation, electrons populate the linearly dispersing states at the Fermi level (E ), and fill the CDW gap. The dynamics of both the charge carrier population and the band gap renormalization (BGR) show a fast component with a characteristic time scale of a few hundreds femtoseconds. However, the BGR also exhibits a second slow component on the µs time scale. The combination of an ultrafast response and of persistent changes in the spectral weight at E , and the resulting sensitivity of the linearly dispersing states to optical excitations, may explain the high performances of as a material for broadband infrared photodetectors.

Multifunctional 1D Nanostructures toward Future Batteries: A Comprehensive Review

AbstractDue to the unique properties which are considerably different from macro‐scale or bulk materials, 1D) nanostructures have received great interests. In particular, they have greatly contributed to building next‐generation batteries by providing beneficial features such as short ion/electron pathways, structural versatility (i.e., formation of 3D current collectors, free‐standing electrodes, and separators), and excellent stress relaxation. Owing to these definite advantages, 1D nanostructure is often followed by discovery of new electrode materials. This review provides a systematic overview of the state‐of‐the‐art research progresses on 1D nanostructures, which are extensively used for rechargeable batteries. Specifically, a brief introduction of some important 1D nanostructuring methods is started and then, in situ structural characterizations using 1D nanostructures are summarized, which allow a great step forward in atomic‐scale monitoring of reaction kinetics and observing dynamic structural evolution of electrode materials. 1D nanstructuring in solid‐state electrolytes and stabilization of metal anodes are also highlighted which are not only substantially important in current research trends for future batteries but also rarely discussed in previous reviews. At the end, critical perspective and future research direction of 1D nanoengineering for future batteries are suggested.

Molecular Crowding Electrolytes for Stable Proton Batteries.

Proton electrochemistry is promising for developing post-lithium energy storage devices with high capacity and rate capability. However, some electrode materials are vulnerable because of the co-intercalation of free water molecules in traditional acid electrolytes, resulting in rapid capacity fading. Here, the authorsreport a molecular crowding electrolyte with the usage of poly(ethylene glycol) (PEG) as a crowding agent, achieving fast and stable electrochemical proton storage and expanded working potential window (3.2V). Spectroscopic characterisations reveal the formation of hydrogen bonds between water and PEG molecules, which is beneficial for confining the activity of water molecules. Molecular dynamics simulations confirm a significant decrease of free water fraction in the molecular crowding electrolyte. Dynamic structural evolution of the MoO3 anode is studied by in-situ synchrotron X-ray diffraction (XRD), revealing a reversible multi-step naked proton (de)intercalation mechanism. Surficial adsorption of PEG molecules on MoO3 anode works in synergy to alleviate the destructive effect of concurrent water desolvation, thereby achieving enhanced cycling stability. This strategy offers possibilities of practical applications of proton electrochemistry thanks to the low-cost and eco-friendly nature of PEG additives.

Atomic Imaging and Thermally Induced Dynamic Structural Evolution of Two-Dimensional Cr2S3.

In this study, facile salt-assisted chemical vapor deposition (CVD) was used to synthesize ultrathin non-van der Waals chromium sulfide (Cr2S3) with a thickness of ∼1.9 nm. The structural transformation of as-grown Cr2S3 was studied using advanced in situ heating techniques combined with transmission electron microscopy (TEM). Two-dimensional (2D) and quasi-one-dimensional (1D) samples were fabricated to investigate the connection between specific planes and the dynamic behavior of the structural variation. The rearrangement of atoms during the phase transition was driven by the loss of sulfur atoms at elevated temperatures, resulting in increased free energy. A decrease in the ratio of the (001) plane led to an overall increase in surface energy, thus lowering the critical phase transition temperature. Our study provides detailed insight into the mechanism of structural transformation and the critical factors governing transition temperature, thus paving the way for future studies on intriguing Cr-S compounds.