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Understandingthe nucleation of hydrate is the key to developingeffective strategies for controlling methane hydrate formation. Herewe present a computational study of methane hydrate nucleation, bycombining the forward flux sampling (FFS) method and the coarse-grainedwater model mW. To facilitate the application of FFS in studying theformation of methane hydrate, we developed an effective order parameterλ on the basis of the topological analysis of the tetrahedralnetwork. The order parameter capitalizes the signature of hydratestructure, i.e., polyhedral cages, and is capable of efficiently distinguishinghydrate from ice and liquid water while allowing the formation ofdifferent hydrate phases, i.e., sI, sII, and amorphous. Integrationof the order parameter λ with FFS allows explicitly computinghydrate nucleation rates and obtaining an ensemble of nucleation trajectoriesunder conditions where spontaneous hydrate nucleation becomes tooslow to occur in direct simulation. The convergence of the obtainedhydrate nucleation rate was found to depend crucially on the convergenceof the spatial distribution for the spontaneously formed hydrate seedsobtained from the initial sampling of FFS. The validity of the approachis also verified by the agreement between the calculated nucleationrate and that inferred from the direct simulation. Analyzing the obtainedlarge ensemble of hydrate nucleation trajectories, we show hydrateformation at 220 K and 500 bar is initiated by the nucleation eventsoccurring in the vicinity of water–methane interface, and facilitatedby a gradual transition from amorphous to crystalline structure. Thelatter provides the direct support to the proposed two-step nucleationmechanism of methane hydrate. [ABSTRACT FROM AUTHOR]

Membrane desalination that enables the harvesting of purified water from unconventional sources such as seawater, brackish groundwater, and wastewater has become indispensable to ensure sustainable freshwater supply in the context of a changing climate. However, the efficiency of membrane desalination is greatly constrained by organic fouling and mineral scaling. Although extensive studies have focused on understanding membrane fouling or scaling separately, organic foulants commonly coexist with inorganic scalants in the feedwaters of membrane desalination. Compared to individual fouling or scaling, combined fouling and scaling often exhibits different behaviors and is governed by foulant-scalant interactions, resembling more complex but practical scenarios than using feedwaters containing only organic foulants or inorganic scalants. In this critical review, we first summarize the performance of membrane desalination under combined fouling and scaling, involving mineral scales formed via both crystallization and polymerization. We then provide the state-of-the-art knowledge and characterization techniques pertaining to the molecular interactions between organic foulants and inorganic scalants, which alter the kinetics and thermodynamics of mineral nucleation as well as the deposition of mineral scales onto membrane surfaces. We further review the current efforts of mitigating combined fouling and scaling via membrane materials development and pretreatment. Finally, we provide prospects for future research needs that guide the design of more effective control strategies for combined fouling and scaling to improve the efficiency and resilience of membrane desalination for the treatment of feedwaters with complex compositions.

Integrating different two-dimensional (2D) crystals is highly demanded for advancing their application in next-generation electronics. 2D transition metal carbides, nitrides, and carbonitrides (MXenes), as new members in the 2D family, are promising candidates for 2D electrodes because of their high conductivity and stability. However, integrating MXenes with other 2D semiconductors has been underdeveloped due to the limitation of top-down etching synthesis of MXenes. Our recent development of atomic substitution synthesis achieved ultrathin non-van der Waals (non-vdW) transition metal nitrides (TMNs) through the conversion of vdW transition metal dichalcogenides (TMDs), opening opportunities of combining TMDs with TMNs via controllable partial conversion. Here, we perform an in-depth study of the atomic substitution process from semiconducting MoS 2 to metallic MoN and realize both lateral and vertical MoN-MoS 2 heterostructures via edge and surface epitaxial conversion, respectively. The structural evolution investigation from MoS 2 to MoN using high-resolution transmission electron microscopy suggests atomically bonded interface for lateral heterostructures and moiré pattern in vertical heterostructures. Moreover, mask-assisted atomic substitution is applied to create patterned MoN-MoS 2 -MoN lateral heterostructures. Electrical measurements reveal a Schottky barrier height of meV for a three-layer MoS 2 -MoN interface, showcasing the potential of atomically bonded lateral heterostructures for MoS 2 electronics with MoN as contact electrodes.

Recognition of structure prototypes from tremendous known inorganic crystal structures has been an important subject beneficial for materials science research and new materials design. The existing databases of inorganic crystal structure prototypes were mostly constructed by classifying materials in terms of the crystallographic space group information. Herein, we employed a distinct strategy to construct the inorganic crystal structure prototype database, relying on the classification of materials in terms of local atomic environments (LAEs) accompanied by unsupervised machine learning method. Specifically, we adopted a hierarchical clustering approach onto all experimentally known inorganic crystal structure data to identify structure prototypes. The criterion for hierarchical clustering is the LAE represented by the state-of-the-art structure fingerprints of the improved bond-orientational order parameters and the smooth overlap of atomic positions. This allows us to build up a LAE-based Inorganic Crystal Structure Prototype Database (LAE-ICSPD) containing 15,613 structure prototypes with defined stoichiometries. In addition, we have developed a Structure Prototype Generator Infrastructure (SPGI) package, which is a useful toolkit for structure prototype generation. Our developed SPGI toolkit and LAE-ICSPD are beneficial for investigating inorganic materials in a global way as well as accelerating the materials discovery process in the data-driven mode.

In recent decades, metal halide semiconductors represented by lead-based halide perovskites have shown broad potential in optoelectronic applications. This family of semiconductors differs from traditional tetrahedral semiconductors in crystalline structure, chemical bonding, electronic-structure features, optoelectronic properties, as well as material fabrication method. At present, difficulties arising from both intrinsic material properties (including Pb toxicity and long-term stability) and technological aspects hinder their large-scale commercialization. In this Perspective, we focus on up-and-coming lead-free metal halide semiconductors toward high-performance optoelectronic applications. We start by outlining the advantages of metal halide semiconductors and their physical and chemical underpinnings. We then review composition and structure, electronic structure, optoelectronic properties, and device applications according to classification into three material categories, i.e., three-dimensional halide perovskites, low-dimensional perovskites and perovskite-like materials, and materials beyond perovskites. We conclude with an outlook on the challenges and opportunities of metal halide semiconductors and the future development of the field.

The freezing of water mostly proceeds via heterogeneous ice nucleation, a process in which an effective nucleation medium not only expedites ice crystallization but also may effectively direct the polymorph selection of ice. Here, we show that water confined within a hydrophobic slit nanopore exhibits a freezing behavior strongly distinguished from its bulk counterpart. Such a difference is reflected by a strong, non-monotonic pore-size dependence of freezing temperature but, more surprisingly, by an unexpected stacking ordering of crystallized two-dimensional ice containing just a few ice layers. In particular, confined trilayer ice is found to exclusively crystallize into a well-ordered, hexagonal stacking sequence despite the fact that nanopore exerts no explicit constraint on stacking order. The absence of cubic stacking sequence is found to be originated from the intrinsically lower thermodynamic stability of cubic ice over hexagonal ice at the interface, which contrasts sharply the nearly degenerated stability of bulk hexagonal and cubic ices. Detailed examination clearly reveals that the divergence is attributed to the inherent difference between the two ice polymorphs in their surface phonon modes, which is further found to generically occur at both hydrophobic and hydrophilic surfaces.

We alloyed Zn 2+ into CsPbI 3 perovskite nanocrystals by partial substitution of Pb 2+ with Zn 2+ , which does not change their crystalline phase. The resulting alloyed CsPb 0.64 Zn 0.36 I 3 nanocrystals exhibited an improved, close-to-unity photoluminescence quantum yield of 98.5% due to the increased radiative decay rate and the decreased non-radiative decay rate. They also showed an enhanced stability, which correlated with improved effective Goldschmidt tolerance factors, by the incorporation of Zn 2+ ions with a smaller radius than the Pb 2+ ions. Simultaneously, the nanocrystals switched from n-type (for CsPbI 3 ) to nearly ambipolar for the alloyed nanoparticles. The hole injection barrier of electroluminescent LEDs was effectively eliminated by using alloyed CsPb 0.64 Zn 0.36 I 3 nanocrystals, and a high peak external quantum efficiency of 15.1% has been achieved.

The long-term chemical instability and the presence of toxic Pb in otherwise stellar solar absorber APbX 3 made of organic molecules on the A site and halogens for X have hindered their large-scale commercialization. Previously explored ways to achieve Pb-free halide perovskites involved replacing Pb 2+ with other similar M 2+ cations in ns 2 electron configuration, e.g., Sn 2+ or by Bi 3+ (plus Ag + ), but unfortunately this showed either poor stability (M = Sn) or weakly absorbing oversized indirect gaps (M = Bi), prompting concerns that perhaps stability and good optoelectronic properties might be contraindicated. Herein, we exploit the electronic structure underpinning of classic Cu[In,Ga]Se 2 (CIGS) chalcopyrite solar absorbers to design Pb-free halide perovskites by transmuting 2Pb to the pair [B IB + C III ] such as [Cu + Ga] or [Ag + In] and combinations thereof. The resulting group of double perovskites with formula A 2 BCX 6 (A = K, Rb, Cs; B = Cu, Ag; C = Ga, In; X = Cl, Br, I) benefits from the ionic, yet narrow-gap character of halide perovskites, and at the same time borrows the advantage of the strong Cu(d)/Se(p) → Ga/In(s/p) valence-to-conduction-band absorption spectra known from CIGS. This constitutes a new group of CuIn-based Halide Perovskite (CIHP). Our first-principles calculations guided by such design principles indicate that the CIHPs class has members with clear thermodynamic stability, showing direct band gaps, and manifesting a wide-range of tunable gap values (from zero to about 2.5 eV) and combination of light electron and heavy-light hole effective masses. Materials screening of candidate CIHPs then identifies the best-of-class Rb 2 [CuIn]Cl 6 , Rb 2 [AgIn]Br 6 , and Cs 2 [AgIn]Br 6 , having direct band gaps of 1.36, 1.46, and 1.50 eV, and theoretical spectroscopic limited maximal efficiency comparable to chalcopyrites and CH 3 NH 3 PbI 3 . Our finding offers a new routine for designing new-type Pb-free halide perovskite solar absorbers.

Most ice in nature forms because of impurities which boost the exceedingly low nucleation rate of pure supercooled water. However, the microscopic details of ice nucleation on these substances remain largely unknown. Here, we have unraveled the molecular mechanism and the kinetics of ice formation on kaolinite, a clay mineral playing a key role in climate science. We find that the formation of ice at strong supercooling in the presence of this clay is about 20 orders of magnitude faster than homogeneous freezing. The critical nucleus is substantially smaller than that found for homogeneous nucleation and, in contrast to the predictions of classical nucleation theory (CNT), it has a strong two-dimensional character. Nonetheless, we show that CNT describes correctly the formation of ice at this complex interface. Kaolinite also promotes the exclusive nucleation of hexagonal ice, as opposed to homogeneous freezing where a mixture of cubic and hexagonal polytypes is observed.

Tungsten disulfide (WS2) is a layered transition metal dichalcogenide (TMD) that differs from other two-dimensional (2D) compounds such as graphene due to its unique semiconducting, tunable-band-gap nature. Multilayered WS2 exhibits an indirect band gap Eg of ∼1.3 eV, along with a higher load-bearing ability that is promising for strain-tuning device applications, but the electronic properties of multilayered WS2 at higher strain conditions (i.e., static strain >12%) remain an open question. Here we have studied the structural, electronic, electrical, and vibrational properties of multilayered WS2 at hydrostatic pressures up to ∼35 GPa experimentally in a diamond anvil cell and theoretically using first-principles ab initio calculations. Our results show that WS2 undergoes an isostructural semiconductor-to-metallic (S-M) transition at approximately 22 GPa at 280 K, which arises from the overlap of the highest valence and lowest conduction bands. The S-M transition is caused by increased sulfur-sulfur interactions as the interlayer spacing decreases with applied hydrostatic pressure. The metalization in WS2 can be alternatively interpreted as a 2D to 3D (three-dimensional) phase transition that is associated with a substantial modulation of the charge carrier characteristics including a 6-order decrease in resistivity, a 2-order decrease in mobility, and a 4-order increase in carrier concentration. These distinct pressure-tunable characteristics of the dimensionalized WS2 differentiate it from other TMD compounds such as MoS2 and promise future developments in strain-modulated advanced devices.

The reduction of [(Cp‴Co)2(μ,η(2:2)-P2)2] (Cp‴ = 1,2,4-tBu3C5H2) with the samarocenes, [(C5Me4R)2Sm(THF)n] (R = Me or n-propyl), gives [(Cp‴Co)2P4Sm(C5Me4R)2]. This is the first example of an intramolecular P-P coupling in a polyphosphide complex upon reduction of the transition metal. The formation of the P-P bond is not a result of the direct reduction of the phosphorus atoms but is induced by a rearrangement of the positive charges between the metal atoms.

Novel physical phenomena can emerge in low-dimensional nanomaterials. Bulk MoS(2), a prototypical metal dichalcogenide, is an indirect bandgap semiconductor with negligible photoluminescence. When the MoS(2) crystal is thinned to monolayer, however, a strong photoluminescence emerges, indicating an indirect to direct bandgap transition in this d-electron system. This observation shows that quantum confinement in layered d-electron materials like MoS(2) provides new opportunities for engineering the electronic structure of matter at the nanoscale.