Intrinsic Instability Research Articles

Experimental study of foam stability and interfacial behaviour of cellulose nanocrystals-enhanced C22-tailed zwitterionic betaine surfactant

The intrinsic thermodynamic instability of foam systems significantly constrains their effectiveness in enhancing oil and gas recovery from unconventional reservoirs. This study investigated the foam properties and interfacial rheological characteristics of the EDAB/CNC/APG system, analyzing the influence of various factors including temperature, pH, and inorganic salts. The results indicated that the optimal concentration ratio for CNC-surfactant system consists of 0.3 % EDAB, 1.5 % CNC and 0.5 % APG by mass fraction. In this system, the addition of CNC forms a three-dimensional network structure at the gas–liquid continuous interface, significantly extending the drainage half-life of the system. At elevated temperatures, the intense molecular thermal motion disrupts the interactions between CNC and EDAB. This disruption leads to a decrease in surface tension and the viscoelastic modulus of interfacial expansion, resulting in an increase of foam volume but a decline in foam drainage half-life. Foam performance and interfacial rheological characteristics are optimal under neutral pH conditions and manifest higher stability in alkaline conditions compared to acidic conditions. In highly mineralized reservoirs (≥5.0 % salt concentration), inorganic salt ions shield the attraction between CNC and oppositely charged surfactants. This shielding weakens the cross-linking within CNC-surfactant systems, altering the structure of the liquid film interface and causing a sharp decrease in foam half-life. The C22-tailed zwitterionic betaine surfactant EDAB, enhanced by CNC, provides a novel, environmentally friendly, efficient, and safe approach to the exploitation of complex, low-permeability oil and gas reservoirs.

Protein Microarrays for High Throughput Hydrogen/Deuterium Exchange Monitored by FTIR Imaging.

Proteins form the fastest-growing therapeutic class. Due to their intrinsic instability, loss of native structure is common. Structure alteration must be carefully evaluated as structural changes may jeopardize the efficiency and safety of the protein-based drugs. Hydrogen deuterium exchange (HDX) has long been used to evaluate protein structure and dynamics. The rate of exchange constitutes a sensitive marker of the conformational state of the protein and of its stability. It is often monitored by mass spectrometry. Fourier transform infrared (FTIR) spectroscopy is another method with very promising capabilities. Combining protein microarrays with FTIR imaging resulted in high throughput HDX FTIR measurements. BaF2 slides bearing the protein microarrays were covered by another slide separated by a spacer, allowing us to flush the cell continuously with a flow of N2 gas saturated with 2H2O. Exchange occurred simultaneously for all proteins and single images covering ca. 96 spots of proteins that could be recorded on-line at selected time points. Each protein spot contained ca. 5 ng protein, and the entire array covered 2.5 × 2.5 mm2. Furthermore, HDX could be monitored in real time, and the experiment was therefore not subject to back-exchange problems. Analysis of HDX curves by inverse Laplace transform and by fitting exponential curves indicated that quantitative comparison of the samples is feasible. The paper also demonstrates how the whole process of analysis can be automatized to yield fast analyses.

Identifying the β-to-α phase transition during the long cycling process in Na2FePO4F cathode

Na2FePO4F has emerged as a promising cathode for large-scale electrochemical energy storage, primarily due to its abundance of raw materials and distinctive two-dimensional ion channels. Counterintuitively, pristine Na2FePO4F lacks the long-term stability typically seen in polyanionic cathodes, which severely impedes its practical application. Traditionally, the origin of this problem has been only phenomenologically attributed to the poor intrinsic electronic conductivity and structural instability of Na2FePO4F. Here, we identify that rapid capacity fading of Na2FePO4F is closely related to the β-to-α phase transition during the long cycling process. Furthermore, we develop a practical high-entropy doping strategy and the corresponding microstructure engineering to mitigate the impact of the phase transition on the crystal structure, thereby increasing the capacity retention from 56 % to 94 % over 400 cycles at 0.5C in coin cell, and attain almost 100 % capacity retention after 300 cycles at 0.1C in pouch cell. Overall, this work unveils the mechanism of rapid capacity decay in Na2FePO4F and lays the groundwork for the rational design of durable polyanionic electrodes.

Phase compatible surface engineering to boost the cycling stability of single-crystalline Ni-rich cathode for high energy density lithium-ion batteries

Nickel-rich layered oxide is a promising cathode material for the next generation lithium-ion batteries (LIBs) because of its high energy density and cost efficiency. Unfortunately, it suffers from unsatisfying electrochemical performance owing to intrinsic interfacial and structural instability, which limits its application at scale. In this work, a phase compatible TiBO3 coating layer on single crystalline LiNi0.83Co0.11Mn0.06O2 (TBO-SC-NCM) is constructed via modified solid-state chemical reaction. The coating layer serves as a protective screen to mitigate the erosion of organic electrolyte towards TBO-SC-NCM. Furthermore, both titanium ions and boron ions successfully diffuse into the TBO-SC-NCM bulk phase during the annealing process, with titanium ions being uniformly distributed while boron ions accumulating close to the surface. The formation of strong Ti-O bond effectively inhibits the bulk phase structure degradation of TBO-SC-NCM. The near-surface enriched B-O bond greatly stabilizes the surface lattice oxygen at the deeply delithiated state. Additionally, the spread of layer spacing due to the doping of heterogeneous ions ensures the rapid diffusion of Li+, thus improving the rate performance of TBO-SC-NCM. As a h cathode materials.

Cation-inspired polyhedral distortion boosting moisture/electrolyte stability of iron sulfate cathode for durable high-temperature sodium-ion storage

Alluaudite-type iron-based sulfates are prospective positive-electrode active materials for sodium-ion batteries given their low-cost and high operation voltage, yet suffer from poor intrinsic ionic conductivity and (electro)chemical instability at high temperatures. Herein, a cation-modified Na2.466Fe1.724Mg0.043(SO4)3 with micron-sized spherical structure was reported. The substitutive MgO6 octahedron featured stronger covalent bonding interactions and enriched the ion transfer pathways within the crystals, facilitating the ionic kinetics in bulk. Using in situ mass spectrometry and quartz crystal microbalance techniques, Mg cations were demonstrated to lower the electron density around O atoms and surficial nucleophilicity of materials, which effectively suppressed their side reactions with H2O in air and active ester molecule in electrolyte. This interaction enables an inorganic-rich and uniform interphase to stabilize the cathode/electrolyte interface at high voltage (4.5 V vs. Na+/Na). The as-prepared cathode exhibits a high discharge capacity of 102.2 mAh g−1 (voltage platform at 3.74 V), remarkable reaction reversibility (average Coulomb efficiency of 99.3% over 300 cycles) at high loading (9.0 − 9.6 mg cm−2) and temperature (60 °C), as well as long-lasting cyclability (70.8%, 5000 cycles). Its application was verified in assembled sodium-ion full cells with a hard carbon negative electrode, showing a long cycling lifetime over 190 cycles.

Parametric instability analysis of rotors under anisotropic boundary conditions

Ensuring rotor stability is a major concern in engineering, as instabilities can lead to catastrophic failures. Existing literature shows that anisotropic boundary conditions significantly affect the parametric instability characteristics of rotors under periodical axial loads. However, there is little literature systematically analyzing the formation mechanism of parametric resonance under these boundary conditions or providing a detailed classification of the parametric instability regions. Therefore, this paper presents a comprehensive parametric instability analysis of a rotor subjected to periodic axial loads under anisotropic boundary conditions. A novel approach based on the multiple scales method is proposed to address anisotropy in the boundary conditions. Using this approach, the analytical boundaries of the parametric instability regions are derived, and a proof regarding the absence of certain parametric resonances is presented. These analytical solutions are validated by numerical results obtained from the discrete transition matrix method, which form the basis for systematically investigating the effects of anisotropy in direct or cross-coupling stiffness/damping coefficients on the rotor instability. The key scientific contributions of this work include: Deriving analytical instability boundaries, providing a more efficient alternative to purely numerical methods while maintaining high accuracy; Demonstrating the absence of parametric resonance of difference type under both isotropic or anisotropic boundary conditions; Discovering that anisotropy in stiffness coefficients can induce self-interaction within a given forward or backward whirl mode, as well as interaction between two forward or two backward whirl modes, leading to additional instability regions; Reducing anisotropy in direct damping coefficients may increase critical dynamic load coefficients, potentially enhancing rotor safety; If the cross-coupling stiffness coefficients exceed the threshold for triggering intrinsic instability, the rotor may become unstable in all operating conditions. All these findings offer insights into the stability management of rotors under various operating conditions and provide valuable guidance for designing and operating safer, more efficient rotor systems.

Intrinsic instabilities in Fermi glasses

Intrinsic instabilities in Fermi glasses

Stabilizing Pure Water-Fed Anion Exchange Membrane Water Electrolyzers through Membrane-Electrode Interface Engineering.

Nickel-iron (oxy)hydroxide (NiFeOxHy) stands as a cutting-edge nonprecious electrocatalyst for the oxygen evolution reaction (OER). However, the intrinsic thermodynamic instability of nickel and iron as anode materials in pure water-fed electrolyzers poses a significant durability challenge. In this study, an anion exchange ionomer coating was applied to NiFeOxHy to modify the local pH between a membrane and an electrode. This effectively extended the diffusion length of hydroxide anions toward the electrode, establishing an alkaline local pH environment. Stability tests with the ionomer coating showed reduced Ni dissolution. Moreover, locally resolved current density measurements were used to demonstrate a notably lower degradation rate during stability testing, revealing a 6-fold increase in stability with the ionomer on NiFeOxHy. In situ Raman spectroscopy in a neutral pH electrolyte confirmed inhibited Ni oxidation with the ionomer, mitigating Ni dissolution and enhancing stability of state-of-the-art NiFeOxHy catalysts in pure water-fed water electrolyzers.

High-topological-number skyrmions with tunable diameters in two-dimensional frustrated J1−J2 magnets

Skyrmions are intriguing quasiparticles in the field of condensed matter due to their unique physics and promising applications in spintronic devices. However, despite abundant studies on skyrmions with a topological charge of Q = 1, there have been only few on those with higher Q (≥2) due to their intrinsic instability in Dzyaloshinskii–Moriya interaction (DMI) systems. In this work, applying the frustrated J1−J2 Heisenberg spin model, we investigate the stability of high-Q skyrmions and the manipulation of their diameters in a hexagonal close-packed lattice through atomistic simulations and first-principles calculations. First, three spin textures, called spiral, skyrmion, and ferromagnetic, are identified by varying (J1, J2), and it is shown that skyrmions with higher Q can occupy a wider range of (J1, J2) values. The diameter of the skyrmions can then be finely tuned using the frustration strength (|J2/J1|), the single-ion anisotropy (K), and an external magnetic field (B). As B increases, the high-Q skyrmions split into skyrmions with smaller Q and can be annihilated by a larger B. Furthermore, we find that the CoCl2 monolayer satisfies the criteria for a frustrated J1−J2 magnet, and its magnetic behaviors align with the aforementioned conclusions. In addition, high-Q skyrmions are identified in the CoCl2 monolayer, and the corresponding energy barriers for skyrmion collapse are investigated. Our findings pave the way for prospective spintronic applications based on high-Q and nanoscale skyrmionic textures.

Is There an Adduct of Pyridine N-Oxide and Boron Trifluoride in the Gaseous State? Gas Electron Diffraction vs Mass Spectrometry.

A study of saturated vapor over the pyridine N-oxide-boron trifluoride (PyO-BF3) adduct was carried out at T = 448(5) K by a synchronous gas electron diffraction/mass spectrometry (GED/MS) experiment. Due to the absence of ions in the mass spectrum, indicating the presence of a structure with an O-B dative bond, several models of vapor composition were tested by the GED method. It was found that the dominant molecular form (up to 100%) in vapor is the PyO-BF3 adduct. Using the DFT/M06-2X/aug-cc-pVTZ method, geometric optimization of the molecular ion [PyO-BF3]+ was carried out, which showed its intrinsic instability and dissociation into a [PyO]+ cation and a BF3 molecule. This study certainly demonstrates the significant advantage of the GED method to determine the qualitative and quantitative gas-phase composition of dative-bonded adducts and other noncovalent complexes as well, whereas the interpretation of mass spectra may be ambiguous due to the possible intrinsic instability of ions containing a dative bond. The nature of the O-B bond is discussed in terms of the natural bond orbitals (NBOs) and the quantum theory of atoms in molecules (QTAIM). A comparison of structural and energetic parameters for PyO-BF3 and the previously studied BF3 adducts allows the theoretical comprehension of the nature of the O-B bond to be extended and to explain the different thermal stabilities of these compounds.

Conducting polymer functionalization in search of advanced materials in ionometry: ion-selective electrodes and optodes.

Functionalized conducting polymers (FCPs) have recently garnered attention as ion-selective sensor materials, surpassing their intrinsic counterparts due to synergistic effects that lead to enhanced electrochemical and analytical parameters. Following a brief introduction of the fundamental concepts, this article provides a comprehensive review of the recent developments in the application of FCPs in ion-selective electrodes (ISEs) and ion-selective optodes (ISOs), particularly as ion-to-electron transducers, optical transducers, and ion-selective membranes. Utilizing FCPs in these devices offers a promising avenue for detecting and measuring ions in various applications, regardless of the sample nature and composition. Research has focused on functionalizing different conducting polymers, such as polyaniline and polypyrrole, through strategies such as doping and derivatization to alter their hydrophobicity, conductance, redox capacitance, surface area, pH sensitivity, gas and light sensitivity, etc. These modifications aim to enhance performance outcomes, including potential stability/emission signal stability, reproducibility and low detection limits. The advancements have led to the transition of ISEs from conventional zero-current potentiometric ion sensing to innovative current-triggered sensing approaches, enabling calibration-free applications and emerging concepts such as opto-electro dual sensing systems. The intrinsic pH cross-response and instability of the optical signal of ISOs have been overcome through the novel optical signal transduction mechanisms facilitated by FCPs. In this review, the characteristics of materials, functionalization approaches, particular implementation strategies, specific performance outcomes and challenges faced are discussed. Consolidating dispersed information in the field, the in-depth analysis presented here is poised to drive further innovations by broadening the scope of ion-selective sensors in real-world scenarios.

Enhanced Local Ion Transport in High-Performance Anion Exchange Membrane Water Electrolyzers Via Quaternary Ammonium-Functionalized Metal-Organic Framework Electrocatalysts

Anion-exchange membrane water electrolyzers (AEMWEs) present a multitude of advantages, particularly in the utilization of non-platinum group (non-PGM) catalysts. While diverse catalysts have demonstrated notable electrocatalytic activity in alkaline conditions, the integration of the ionomer with the electrocatalyst at the active catalyst layer is crucial for enhancing overall AEMWE performance in practical device demonstrations by improving mass transport. However, the intrinsic instability of polymeric ionomers, leading to physical detachments or alkaline (chemical) degradation, poses a challenge that can potentially diminish performance. In this study, drawing inspiration from the aforementioned ionomer chemistry, we introduce non-PGM NiFe-based metal-organic frameworks (MOFs) incorporating quaternary ammonium (QA) cation moieties covalently functionalized to benzenedicarboxylic acid (BDC) ligands as promising electrocatalysts for the oxygen evolution reaction (OER) in alkaline environments. Three specifically designed functional groups with varying ion exchange capacities (IEC) and alkaline stability—trimethylamine (TMA), N-methylpyrrolidine (C4N), and N-methylpiperidine (C5N)—were directly tethered to BDC ligands. The alkaline OER activity of Ni2Fe1-QA-MOF was meticulously assessed using rotating disk electrodes and AEMWE devices. These directly tethered QA groups markedly facilitated improved ionic transport of OH- ions at the catalyst/electrolyte interfaces compared to BDC ligands, ultimately leading to a significant enhancement in half-cell activity and AEMWE performance. In-situ IR/RAMAN spectroscopy revealed that QA moieties highly promoted local ionic transport at the interfaces, as evidenced by characteristic peaks indicating a robust interaction between QA and OH- ions. Unexpectedly, QA moieties not only contributed to ionic transport in local environments but also induced oxidation states of Ni metal sites, while Fe sites exhibited no changes during the applied potential in the OER region, as comprehensively revealed by synchrotron X-ray absorption spectroscopy (XAS). In comparison with conventional NiFe layered double hydroxide (LDH) structures, we posit that the substantial structural transformation of Ni moieties can be attributed to an increased degree of M-O bond interaction, enhanced by the local interaction between QA and OH- ions. Density functional theory (DFT) calculations also validate the balanced adsorption of OER intermediates on QA-MOFs. Finally, QA-NiFe-MOF was directly synthesized on a porous transport layer (PTL), and its AEMWE performance was evaluated without the use of any ionomer. At 1.0 M KOH, C4N, C5N, and TMA-based NiFe MOFs exhibited current densities of 9.35 A/cm2, 9.11 A/cm2, and 7.6 A/cm2, respectively. These current densities surpassed those of bare BDC-NiFe MOF and commercial IrO2 anode catalysts, which exhibited only 7.39 A/cm2 and 6.4 A/cm2, respectively. Consequently, we emphasize that the facilitation of local ionic transport could yield remarkable AEMWE performance, even in the absence of conventional polymeric ionomers.

Mixed-Layered Lead Halide Frameworks with High Stability and Efficient Room-Temperature Phosphorescence.

Room-temperature phosphorescent (RTP) materials play a crucial role in optical anticounterfeiting science and information security technologies. Ionically bonded organic metal halides have emerged as promising RTP material systems due to their excellent self-assembly and unique photophysical property, but their intrinsic instability largely hinders their advanced practical applications. Herein, we employ a coordination-driven synthetic strategy utilizing organocarboxylates for the synthesis of two isostructural layered lead halide frameworks. The frameworks adopt a new mixed-layered topology, consisting of alternating [Pb10X9]11+ (X = Cl-/Br-) layers and [Pb6XO3]11+ (X = Cl-/Br-) layers that are coordinatively sandwiched by organocarboxylate layers. The frameworks exhibit long-lived green afterglow emission with the long lifetime of up to 45.89 ms and the photoluminescence quantum yield (PLQY) of up to 43.13%. The Pb2+-carboxylate coordination accelerates the metal-to-ligand charge transfer from the light-harvesting lead halide layers to the phosphorescent organic component, promoting efficient spin-orbit coupling and intersystem crossing. Moreover, the coordination networks exhibit good structural robustness under ambient conditions for at least 12 months, as well as stability in boiling water, acidic and basic aqueous environments. The highly efficient afterglow and high structural integrity enable multiple anticounterfeiting applications across diverse chemical environments.

High-Valence Ion Doped Compositionally Partitioned Li[Ni0.78Co0.10Mn0.12]O2 Cathode for Advanced Lithium-Ion Batteries

Numerous approaches have been employed to reduce the intrinsic instability of Ni-rich cathodes. Among them, the introduction of concentration gradient (CG), i.e., a strategy to protect the labile Ni-enriched compartment with a chemically protective Mn-rich shell, has proven successful in commercial applications.1 However, because the segmentation of transition metal (TM) constituents and the formation of unique geometric configurations are characteristics inherited from the CG hydroxide precursor; it is crucial to select the optimal calcination temperature and precisely control it.2 Excessive thermal energy input can result in concentration planarization because the CG of the hydroxide precursor is intrinsically susceptible to the interdiffusion of TM elements during lithiation. Moreover, the immoderate coarsening of the primary particles can eliminate the advantageous features of the CG design by producing equiaxed primary particles.2 In this study, we propose a strategy that can effectively ameliorate the deterioration of Ni-rich CG cathodes resulting from excessive thermal energy input and remarkably improve their electrochemical cycling performance. It was revealed that a trace amount of tungsten incorporation during the cathode calcination can effectively mitigate the high-temperature-induced cathode degeneration and maintain outstanding product quality over a wide range of temperatures. Thus, the proposed strategy opens new avenues for the facile synthesis of long-life Ni-rich CG cathodes. Reference s : [1] Y.-K. Sun, S.-T. Myung, B.-C. Park, J. Prakash, I. Belharouak, K. Amine, Nat. Mater. 8 (2009) 320-324.[2] G.-T. Park, H.-H. Ryu, T.-C. Noh, G.-C. Kang, Y.-K. Sun, Mater. Today 52 (2022) 9-18.

Enhancement of unbalanced robot performance using fuzzy sliding mode control

An unbalanced robot faces difficulties in balancing its tilt to an upright position due to its intrinsic instability. Simulation, implementation in real time and performance testing of a fuzzy sliding mode controller for an unbalanced robot are the targets of this research. PID, sliding mode control and fuzzy logic control are designed to compare the proposed controller in both real time and simulation to achieve the robot's balancing. The main development of this technology is to combine the advantages of fuzzy logic and sliding mode in one model, directly controlling the tilt angle to track the desired point and maintain good control of the motor. All controllers have been compared using computational time and integral measures. The proposed controller has been tested under the effect of an external disturbance in real time and on a MATLAB Simulink. The FSMC controller's performance has given better results in speed response and integral measures.

Strain in Halide Perovskite Solar Cells: Origins, Impacts, and Regulation

Perovskite solar cells have made significant progress in the past decade, demonstrating promising potential for next‐generation solar technology. However, the strain‐induced intrinsic instability of mixed‐halide perovskites poses a significant obstacle to their widespread commercialization. Relaxation of the perovskite lattice strain is a crucial approach for enhancing photovoltaic performance and broadening their application potential. In this study, the authors conduct an analysis of strain progression in perovskite thin films, examining its impact on the physical properties of perovskites and the performance of perovskite solar cells. Furthermore, they explore its influence on device stability from the perspectives of phase transitions, chemical decomposition, and mechanical fragility. Additionally, they provide a summary of key advancements in strain‐relaxation strategies and offer design principles and synthetic approaches to address the issue of lattice strain in perovskites. This paper is intended to lay the groundwork for the theoretical development of effective strain‐relaxation methods, moving beyond sole reliance on empirical optimization.

Role of very large-scale motions in shock wave/turbulent boundary layer interactions

The present study investigates the cause of low-frequency unsteadiness in shock wave/turbulent boundary layer (TBL) interactions. A supersonic turbulent flow over a compression ramp is studied using wall-resolved large eddy simulation (LES) with a freestream Mach number of 2.95 and a Reynolds number (based on δ0: the thickness of the incoming TBL) of 63 560. From the view of stability analysis, the effect of intrinsic instability on such low-frequency unsteadiness is excluded from the flow system by designing a ramp angle of 15°, and our attention is paid to the convective instability contributed by the incoming TBL. The LES results are analyzed by linear and nonlinear disambiguation optimization (LANDO), spectral proper orthogonal decomposition (SPOD), and resolvent analysis. The LANDO results reveal a streamwise scale-frequency relation of coherent structures in a very long (around 60δ0) TBL, which indicates that the dynamics of very large-scale motions (VLSMs) in the TBL are featured by a low frequency. The SPOD results reveal that the most energetic SPOD mode features a low frequency that is identical to the dominant low frequency of the wall-pressure spectrum. Additionally, coherent structures of the mode resemble the VLSMs in the incoming TBL. These consistencies imply that the dynamics of VLSMs contribute to the low-frequency unsteadiness of the present flow. A resolvent analysis then further suggests that the origins of low-frequency dynamics of the present flow are from the VLSMs, which can be optimally amplified by the forcing in the turbulent flow.

Elucidating the Discrepancy between the Intrinsic Structural Instability and the Apparent Catalytic Steadiness of M‐N‐C Catalysts toward Oxygen Evolution Reaction

AbstractDespite the widespread investigations on the M‐N‐C type single atom catalysts (SACs) for oxygen evolution reaction (OER), an internal conflict between its intrinsic thermodynamically structural instability and apparent catalytic steadiness has long been ignored. Clearly unfolding this contradiction is necessary and meaningful for understanding the real structure‐property relation of SACs. Herein, by using the well‐designed pH‐dependent metal leaching experiments and X‐ray absorption spectroscopy, an unconventional structure reconstruction of M‐N‐C catalyst during OER process was observed. Combining with density functional theory calculations, the initial Ni−N coordination is easily broken in the presence of adsorbed OH*, leading to favorable formation of Ni−O coordination. The formed Ni−O works stably as the real active center for OER catalysis in alkaline media but unstably in acid, which clearly explains the existing conflict. Unveiling the internal contradiction between structural instability and catalytic steadiness provides valuable insights for rational design of single atom OER catalysts.

Elucidating the Discrepancy between the Intrinsic Structural Instability and the Apparent Catalytic Steadiness of M-N-C Catalysts toward Oxygen Evolution Reaction.

Despite the widespread investigations on the M-N-C type single atom catalysts (SACs) for oxygen evolution reaction (OER), an internal conflict between its intrinsic thermodynamically structural instability and apparent catalytic steadiness has long been ignored. Clearly unfolding this contradiction is necessary and meaningful for understanding the real structure-property relation of SACs. Herein, by using the well-designed pH-dependent metal leaching experiments and X-ray absorption spectroscopy, an unconventional structure reconstruction of M-N-C catalyst during OER process was observed. Combining with density functional theory calculations, the initial Ni-N coordination is easily broken in the presence of adsorbed OH*, leading to favorable formation of Ni-O coordination. The formed Ni-O works stably as the real active center for OER catalysis in alkaline media but unstably in acid, which clearly explains the existing conflict. Unveiling the internal contradiction between structural instability and catalytic steadiness provides valuable insights for rational design of single atom OER catalysts.

Maneuvering magic-sized transition metal chalcogenides nanoclusters for Solar-to-Hydrogen conversion

Magic-sized nanoclusters (MSCs) have recently deemed as a novel and crucial sector of nanomaterials on account of their large absorption coefficient for light harvesting, peculiar quantum confinement effect, and abundant active. Nevertheless, precise control of photoinduced charge carriers over MSCs has so far not yet been reported because of the ultra-short carrier lifetime and intrinsic instability of MSCs, which renders the complexity of MSCs photosystems with photoredox mechanism remaining blank. Herein, we for the first time conceptually demonstrate the grafting of amino-containing organic molecular onto the L-cysteine (L-Cys) ligand of CdSe@L-Cys MSCs as charge transport mediator, and the amino functional group acts as an efficient electron-withdrawing trap, which markedly boosts the charge separation and prolongs the charge lifetime of CdSe@L-Cys MSCs, resulting in the significantly improved photocatalytic hydrogen generation performances under visible light irradiation along with favorable stability. Our work will provide sparking ideas for fine tuning of photoinduced charge separation and transfer over transition metal chalcogenides MSCs photosystems for solar-to-hydrogen energy conversion.