Spin-polarized p-block antimony/bismuth single-atom catalysts on defect-free rutile TiO2(110) substrate for highly efficient CO oxidation.

Developing high-loading spin-polarized p-block-element-based single-atom catalysts (p-SACs) upon defect-free substrates for various chemical reactions wherein spin selection matters is generally considered a formidable challenge because of the difficulty of creating high densities of underpinning stable defects and the delocalized electronic features of p-block elements. Here our first-principles calculations establish that the defect-free rutile TiO2(110) wide-bandgap semiconducting anchoring support can stabilize and localize the wavefunctions of p-block metal elements (Sb and Bi) via strong ionic bonding, forming spin-polarized p-SACs. Cooperated by the underlying d-block Ti atoms via a delicate spin donation-back-donation mechanism, the p-block single-atom reactive center Sb(Bi) exhibits excellent catalysis for spin-triplet O2 activation and CO oxidation in alignment with Wigner's spin selection rule, with a low rate-limiting reaction barrier of ∼0.6 eV. This work is crucial in establishing high-loading reactive centers of high-performance p-SACs for various important physical processes and chemical reactions, especially wherein the spin degree of freedom matters, i.e., spin catalysis.

Silicon Vacancies Diamond/Silk/PVA Hierarchical Physical Unclonable Functions for Multi-Level Encryption.

Physical unclonable functions (PUFs) have emerged as a promising encryption technology, utilizing intrinsic physical identifiers that offer enhanced security and tamper resistance. Multi-level PUFs boost system complexity, thereby improving system reliability and fault tolerance. However, crosstalk-free multi-level PUFs remain a persistent challenge. In this study, a hierarchical PUF system that harnesses the spontaneous phase separation of silk fibroin /PVA blend and the random distribution of silicon-vacancy diamonds within the blend is presented. The thermodynamic instability of phase separation and inherent unpredictability of diamond dispersion gives rise to intricate random patterns at two distinct scales, enabling time-efficient hierarchical authentication for cryptographic keys. These patterns are complementary yet independent, inherently resistant to replication and damage thus affording robust security and reliability to the proposed system. Furthermore, customized authentication algorithms are constructed: visual PUFs authentication utilizes neural network combined structural similarity index measure, while spectral PUFs authentication employs Hamming distance and cross-correlation bit operation. This hierarchical PUF system attains a high recognition rate without interscale crosstalk. Additionally, the coding capacity is exponentially enhanced using M-ary encoding to reinforce multi-level encryption. Hierarchical PUFs hold significant potential for immediate application, offering unprecedented data protection and cryptographic key authentication capabilities.

Interface Modulation for the Heterointegration of Diamond on Si.

Along with the increasing integration density and decreased feature size of current semiconductor technology, heterointegration of the Si-based devices with diamond has acted as a promising strategy to relieve the existing heat dissipation problem. As one of the heterointegration methods, the microwave plasma chemical vapor deposition (MPCVD) method is utilized to synthesize large-scale diamond films on a Si substrate, while distinct structures appear at the Si-diamond interface. Investigation of the formation mechanisms and modulation strategies of the interface is crucial to optimize the heat dissipation behaviors. By taking advantage of electron microscopy, the formation of the epitaxial ß-SiC interlayer is found to be caused by the interaction between the anisotropically sputtered Si and the deposited amorphous carbon. Compared with the randomly oriented ß-SiC interlayer, larger diamond grain sizes can be obtained on the epitaxial ß-SiC interlayer under the same synthesis condition. Moreover, due to the competitive interfacial reactions, the epitaxial ß-SiC interlayer thickness can be reduced by increasing the CH4/H2 ratio (from 3% to 10%), while further increase in the ratio (to 20%) can lead to the broken of the epitaxial relationship. The above findings are expected to provide interfacial design strategies for multiple large-scale diamond applications.

Centimeter-sized diamond composites with high electrical conductivity and hardness.

Achieving high-performance materials with superior mechanical properties and electrical conductivity, especially in large-sized bulk forms, has always been the goal. However, it remains a grand challenge due to the inherent trade-off between these properties. Herein, by employing nanodiamonds as precursors, centimeter-sized diamond/graphene composites were synthesized under moderate pressure and temperature conditions (12 GPa and 1,300 to 1,500 °C), and the composites consisted of ultrafine diamond grains and few-layer graphene domains interconnected through covalently bonded interfaces. The composites exhibit a remarkable electrical conductivity of 2.0 × 104 S m-1 at room temperature, a Vickers hardness of up to ~55.8 GPa, and a toughness of 10.8 to 19.8 MPa m1/2. Theoretical calculations indicate that the transformation energy barrier for the graphitization of diamond surface is lower than that for diamond growth directly from conventional sp2 carbon materials, allowing the synthesis of such diamond composites under mild conditions. The above results pave the way for realizing large-sized diamond-based materials with ultrahigh electrical conductivity and superior mechanical properties simultaneously under moderate synthesis conditions, which will facilitate their large-scale applications in a variety of fields.

Synergetic Role of Thermal Catalysis and Photocatalysis in CO2 Reduction on Cu2/MoS2.

Effective activation of CO2 is a primarily challenging issue in CO2 reduction to value-added hydrocarbon chemicals, due to the large energy gap between the highest-occupied and lowest-unoccupied molecular orbitals (HOMO-LUMO). Here, we employ state-of-the-art first-principles calculations to explore the synergetic role of thermal catalysis and photocatalysis in CO2 reduction, on typical single-atom scale catalyst, i.e., Cu2 magic cluster on a semiconducting two-dimensional MoS2 substrate. It is identified that only about 1% of the hot electrons excited from the MoS2 substrate by at least 6.3 eV photons may be trapped by the inert CO2 molecule at the expense of 400 fs. Moreover, the physisorption-to-chemisorption transition of CO2 can be observed within 500 fs upon overcoming an about 0.05 eV energy barrier. Contrastingly, upon chemisorption, the activated CO2δ- species may trap about 7% of the hot electron excited from the MoS2 substrate by about 2.5 eV visible photons, with a cost of 140 fs.

A Path Planning Method with a Bidirectional Potential Field Probabilistic Step Size RRT for a Dual Manipulator.

The search efficiency of a rapidly exploring random tree (RRT) can be improved by introducing a high-probability goal bias strategy. In the case of multiple complex obstacles, the high-probability goal bias strategy with a fixed step size will fall into a local optimum, which reduces search efficiency. Herein, a bidirectional potential field probabilistic step size rapidly exploring random tree (BPFPS-RRT) was proposed for the path planning of a dual manipulator by introducing a search strategy of a step size with a target angle and random value. The artificial potential field method was introduced, combining the search features with the bidirectional goal bias and the concept of greedy path optimization. According to simulations, taking the main manipulator as an example, compared with goal bias RRT, variable step size RRT, and goal bias bidirectional RRT, the proposed algorithm reduces the search time by 23.53%, 15.45%, and 43.78% and decreases the path length by 19.35%, 18.83%, and 21.38%, respectively. Moreover, taking the slave manipulator as another example, the proposed algorithm reduces the search time by 6.71%, 1.49%, and 46.88% and decreases the path length by 19.88%, 19.39%, and 20.83%, respectively. The proposed algorithm can be adopted to effectively achieve path planning for the dual manipulator.

Why Does Single-Atom Photocatalysis Work Better Than Conventional Photocatalysis? A Study on Ultrafast Excited Carrier and Structure Dynamics.

With the introduction of single atoms in photocatalysis, a small change in the electronic and geometric structure of the substrate can result in higher energy conversion efficiency, whereas the underlying microscopic dynamics are rarely illustrated. Here, employing real-time time-dependent density functional theory, we explore the ultrafast electronic and structural dynamics of single-atom photocatalysts (SAPCs) in water splitting at the microscopic scale. The results demonstrate that a single-atom Pt loaded on graphitic carbon nitride greatly promotes photogenerated carriers compared to traditional photocatalysts, and effectively separates the excited electrons from holes, prolonging the lifetime of the excited carriers. The flexible oxidation state (Pt2+, Pt0, or Pt3+) renders the single atom as an active site to adsorb the reactant and to catalyze the reactions as a charge transfer bridge at different stages during the photoreaction process. Our results offer deep insights into the single-atom photocatalytic reactions and benefit the design of high-efficiency SAPCs.

MoS2/NiSe2/rGO Multiple-Interfaced Sandwich-like Nanostructures as Efficient Electrocatalysts for Overall Water Splitting.

Constructing a heterogeneous interface using different components is one of the effective measures to achieve the bifunctionality of nanocatalysts, while synergistic interactions between multiple interfaces can further optimize the performance of single-interface nanocatalysts. The non-precious metal nanocatalysts MoS2/NiSe2/reduced graphene oxide (rGO) bilayer sandwich-like nanostructure with multiple well-defined interfaces is prepared by a simple hydrothermal method. MoS2 and rGO are layered nanostructures with clear boundaries, and the NiSe2 nanoparticles with uniform size are sandwiched between both layered nanostructures. This multiple-interfaced sandwich-like nanostructure is prominent in catalytic water splitting with low overpotential for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) and almost no degradation in performance after a 20 h long-term reaction. In order to simulate the actual overall water splitting process, the prepared nanostructures are assembled into MoS2/NiSe2/rGO||MoS2/NiSe2/rGO modified two-electrode system, whose overpotential is only 1.52 mV, even exceeded that of noble metal nanocatalyst (Pt/C||RuO2~1.63 mV). This work provides a feasible idea for constructing multi-interface bifunctional electrocatalysts using nanoparticle-doped bilayer-like nanostructures.

Mixed-Dimensional Pt-Ni Alloy Polyhedral Nanochains as Bifunctional Electrocatalysts for Direct Methanol Fuel Cells.

Pt nanocatalysts play a critical role in direct methanol fuel cells (DMFCs) due to their appropriate adsorption/desorption energy, yet suffer from an unbalanced relationship between size-dependent activity and stability. Herein, mixed-dimensional Pt-Ni alloy polyhedral nanochains (Pt-Ni PNCs) with an ordered assembly of a nanopolyhedra-nanowire-nanopolyhedra architecture are fabricated as bifunctional electrocatalysts for DMFCs, effectively alleviating the size effect. The Pt-Ni PNCs exhibit 7.23 times higher mass activity for the anodic methanol oxidation reaction (MOR) than that of commercial Pt/C. In situ Fourier transform infrared spectroscopy and CO stripping measurements demonstrate the prominent stability of the Pt-Ni PNCs to resist CO poisoning. For the cathodic oxygen reduction reaction (ORR), a positive half-wave potential exceeding Pt/C is achieved by the Pt-Ni PNCs, and it can be well maintained for 10 000 cycles with negligible activity decay. The designed nanostructure can alleviate the agglomeration and dissolution problems of 0D small-sized Pt-Ni alloy nanocrystals and enrich surface atom steps and active facets of 1D chain-like nanostructures. This work provides a proposed strategy to improve the catalytic performance of Pt-based nanocatalysts by constructing novel interfacial relationships in mixed dimensions to alleviate the imbalance between catalytic activity and catalytic stability caused by size effects.

Electrocatalytic activity of a ß-Sb two-dimensional surface for the hydrogen evolution reaction.

Hydrogen energy is considered to be one of the most promising clean energy sources. The development of highly active, low-cost catalysts, and good stability is essential for hydrogen production. Herein, the catalytic activity of a two-dimensional ß-Sb surface doped with main-group elements (N, P, As, O, S, Se, and Te) for the hydrogen evolution reaction (HER) was investigated by density functional theory, and the catalytic activity of the ß-Sb monolayer can be improved by doping group VIA atoms. The catalytic activity of Se@Sb and O@Sb structures at the doping concentration of 2.78% and the S@Sb structure at the doping concentration of 5.56% may be as good as the Pt(111) surface, while keeping energetically stable. In addition, the catalytic performance could be optimized under biaxial strain. Further analysis suggests that the activity is caused by hole states in the lone pair electrons, which are created by the group VIA atom dopants. And our work also reveals that the density of states at the Fermi level could be an appropriate descriptor of the hydrogenation Gibbs free energy. This work not only proposes a novel non-platinum HER catalyst but also provides physical foundations for further application on antimonene-based catalysts.

Synergetic Charge Transfer and Spin Selection in CO Oxidation at Neighboring Magnetic Single-Atom Catalyst Sites.

Deciphering the precise physical mechanism of interaction between an adsorbed species and a reactive site in heterogeneous catalysis is crucial for predictive design of highly efficient catalysts. Here, using first-principles calculations we identify that the two-dimensional ferromagnetic metal organic framework of Mn2C18H12 can serve as a highly efficient single-atom catalyst for spin-triplet O2 activation and CO oxidation. The underlying mechanism is via "concerted charge-spin catalysis", involving a delicate synergetic process of charge transfer, provided by the hosting Mn atom, and spin selection, preserved through active participation of its nearest neighboring Mn atoms for the crucial step of O2 activation. The synergetic mechanism is further found to be broadly applicable in O2 adsorption on magnetic X2C18H12 (X = Mn, Fe, Co, and Ni) with a well-defined linear scaling dependence between the chemical activity and spin excitation energy. The present findings provide new insights into chemical reactions wherein spin selection plays a vital role.

Indirect to Direct Charge Transfer Transition in Plasmon-Enabled CO2 Photoreduction.

Understanding hot carrier dynamics between plasmonic nanomaterials and its adsorbate is of great importance for plasmon-enhanced photoelectronic processes such as photocatalysis, optical sensing and spectroscopic analysis. However, it is often challenging to identify specific dominant mechanisms for a given process because of the complex pathways and ultrafast interactive dynamics of the photoelectrons. Here, using CO2 reduction as an example, the underlying mechanisms of plasmon-driven catalysis at the single-molecule level using time-dependent density functional theory calculations is clearly probed. The CO2 molecule adsorbed on two typical nanoclusters, Ag20 and Ag147 , is photoreduced by optically excited plasmon, accompanied by the excitation of asymmetric stretching and bending modes of CO2 . A nonlinear relationship has been identified between laser intensity and reaction rate, demonstrating a synergic interplay and transition from indirect hot-electron transfer to direct charge transfer, enacted by strong localized surface plasmons. These findings offer new insights for CO2 photoreduction and for the design of effective pathways toward highly efficient plasmon-mediated photocatalysis.

Negative Differential Friction Predicted in 2D Ferroelectric In2 Se3 Commensurate Contacts.

At the macroscopic scale, the friction force (f) is found to increase with the normal load (N), according to the classic law of Da Vinci-Amontons, namely, f = µN, with a positive definite friction coefficient (µ). Here, first-principles calculations are employed to predict that, the static force f, measured by the corrugation in the sliding potential energy barrier, is lowered upon increasing the normal load applied on one layer of the recently discovered ferroelectric In2 Se3 over another commensurate layer of In2 Se3 . That is, a negative differential friction coefficient µ can be realized, which thus simultaneously breaking the classic Da Vinci-Amontons law. Such a striking and counterintuitive observation can be rationalized by the delicate interplay of the interfacial van der Waals repulsive interactions and the electrostatic energy reduction due to the enhancement of the intralayer SeIn ionic bonding via charge redistribution under load. The present findings are expected to play an instrumental role in design of high-performance solid lubricants and mechanical-electronic nanodevices.

Plasmon-Induced Water Splitting on Ag-Alloyed Pt Single-Atom Catalysts.

A promising route to realize solar-to-chemical energy conversion resorts to water splitting using plasmon photocatalysis. However, the ultrafast carrier dynamics and underlying mechanism in such processes has seldom been investigated, especially when the single-atom catalyst is introduced. Here, from the perspective of quantum dynamics at the atomic length scale and femtosecond time scale, we probe the carrier and structural dynamics of plasmon-assisted water splitting on an Ag-alloyed Pt single-atom catalyst, represented by the Ag19Pt nanocluster. The substitution of an Ag atom by the Pt atom at the tip of the tetrahedron Ag20 enhances the interaction between water and the nanoparticle. The excitation of localized surface plasmons in the Ag19Pt cluster strengthens the charge separation and electron transfer upon illumination. These facts cooperatively turn on more than one charge transfer channels and give rise to enhanced charge transfer from the metal nanoparticle to the water molecule, resulting in rapid plasmon-induced water splitting. These results provide atomistic insights and guidelines for the design of efficient single-atom photocatalysts for plasmon-assisted water splitting.

Highly efficient catalytic properties of Sc and Fe single atoms stabilized on a honeycomb borophene/Al(111) heterostructure via a dual charge transfer effect.

Theoretical design and experimental fabrication of highly efficient single-atom catalysts (SACs) containing isolated metal atoms monodispersed on appropriate substrates have surged to the forefront of heterogeneous catalysis in recent years. Nevertheless, the instability of SACs, i.e., preferential clustering in chemical reaction processes, dramatically hinders their practical applications. In this paper, using first-principles calculations, we predict that a honeycomb borophene/Al(111) heterostructure can be an ideal candidate to stabilize and enhance the catalysis of many transition metal (TM) SACs via a dual charge transfer mechanism. The Al(111) substrate donates electrons to the pre-covered two-dimensional honeycomb borophene (h-B) to stabilize the latter, and the deposited TM atoms further provide electrons to the h-B, enhancing the covalent binding between the h-B and the Al(111) substrate. Intriguingly, during CO oxidation, the h-B/Al(111) heterostructure can in turn serve as an efficient electron reservoir to accept electrons from or donate electrons to the deposited TM-SACs and the reactants. Such a flexible dual charge transfer mechanism not only facilitates stabilizing the TM-SACs rather than clustering, but also effectively reduces the reaction barriers. Particularly, in contrast to expensive noble metal atoms such as Pd and Pt, low-cost Sc- and Fe-SACs are found to be the most promising SAC candidates that can be stabilized on h-B/Al(111) for O2 activation and CO oxidation, with fairly low reaction barriers (around 0.50-0.65 eV). The present findings may provide important theoretical guidance for the experimental fabrication of highly stable, efficient, and economic SACs stabilized on various heterostructure substrates.

Inter-chain double-site synergistic photocatalytic hydrogen evolution in robust cuprous coordination polymers.

Here, we evaluate photocatalytic H2 generation of three stable Cu-based coordination polymers (CPs), where each two-coordinated Cu(i) is stabilized in interchain -[Cu-imidazole(R)-Cu]- units. Importantly, a record-high H2 evolution rate of 57.64 mmol g-1 h-1 is identified for Cu-MIM. Theoretical calculations reveal that the excellent catalytic performances are due to the delicate synergies of the inter-chain double-site Cu atoms.

Pressure-Induced Structural Evolution and Bandgap Optimization of Lead-Free Halide Double Perovskite (NH4)2SeBr6.

Lead-free halide double perovskites (HDPs) are promising candidates for high-performance solar cells because of their environmentally-friendly property and chemical stability in air. The power conversion efficiency of HDPs-based solar cells needs to be further improved before their commercialization in the market. It requires a thoughtful understanding of the correlation between their specific structure and property. Here, the structural and optical properties of an important HDP-based (NH4)2SeBr6 are investigated under high pressure. A dramatic piezochromism is found with the increase in pressure. Optical absorption spectra reveal the pressure-induced red-shift in bandgap with two distinct anomalies at 6.57 and 11.18 GPa, and the energy tunability reaches 360 meV within 20.02 GPa. Combined with structural characterizations, Raman and infrared spectra, and theoretical calculations using density functional theory, results reveal that, the first anomaly is caused by the formation of a Br-Br bond among the [SeBr6]2- octahedra, and the latter is attributed to a cubic-to-tetragonal phase transition. These results provide a clear correlation between the chemical bonding and optical properties of (NH4)2SeBr6. It is believed that the proposed strategy paves the way to optimize the optoelectronic properties of HDPs and further stimulate the development of next-generation clear energy based on HDPs solar cells.

Strain Engineering of a Defect-Free, Single-Layer MoS2 Substrate for Highly Efficient Single-Atom Catalysis of CO Oxidation.

Single-atom catalysts (SACs) are of great scientific and technical importance due to their low cost, high site density, and high specificity to enhance chemical reactions. Nevertheless, a major issue that severely limits the practical exploration of SACs is their instability, i.e., the preference of sintering and clustering over a defect-free substrate during operation. Here, we employ first-principles calculations to investigate how substrate engineering can stabilize SACs by strain-tuning the electronic interactions between the metal and the substrate using two Pd adatoms on a defect-free, single-layer MoS2 as a typical example. It is identified that the Pd2 dimer is prone to dissociate and form highly efficient SACs for CO oxidation due to the enhanced charge transfer and orbital hybridization with the MoS2 substrate under a suitable tensile strain. The straining induces a semiconductive-to-metallic phase transition of the substrate. Moreover, low-cost elements, such as Ag, Ni, Cu, and Cr, can also be stabilized into high-performance SACs for CO oxidation with tunable reaction barriers by straining. The present findings offer a new avenue to inhibit the transition metal atoms from clustering into nanoclusters/particles and provide a clear guidance for the development of highly cost-efficient and stable SACs on defect-free substrates.

Porphyrinic Silver Cluster Assembled Material for Simultaneous Capture and Photocatalysis of Mustard-Gas Simulant.

Silver cluster-assembled materials (SCAMs), by virtue of their tunable structure, accessible surface area and excellent stability, hold great promise as highly efficient catalysts. Herein, we report a new SCAM [Ag12(StBu)6(CF3COO)3(TPyP)]n (denoted as Ag12TPyP) composed of a Ag12 chalcogenolate cluster core stabilized by porphyrinic ligands. Ag12TPyP showed superior sulfur mustard simulant (2-chloroethyl ethyl sulfide, CEES) degradation efficiency and achieved a half lifetime (t1/2) of 1.5 min with 100% selectivity. The experimental results demonstrated that synergistic effects between the silver cluster and photosensitizer ligand promote the efficiency of the generation of singlet oxygen (1O2), which accelerates the decontamination rate. Additionally, benefiting from strong affinity between the silver cluster and CEES, Ag12TPyP exhibits a CEES uptake of 74.2 mg g-1. This work demonstrates that SCAMs offer a new route to the rational design of novel materials for the detoxification of mustard gas.

Kinetic pathways towards mass production of single crystalline stanene on topological insulator substrates.

As a highly appealing new member of the two-dimensional (2D) materials family, stanene was first epitaxially grown on a three-dimensional topological insulator of Bi2Te3; yet, to date, a standing challenge is to drastically improve the overall quality of such stanene overlayers for a wide range of potential applications in next-generation quantum devices. Here we use state-of-the-art first-principles approaches to explore the atomistic growth mechanisms of stanene on different Bi2Te3(111)-based substrates, with intriguing discoveries. We first show that, when grown on experimentally studied Te-terminated Bi2Te3, stanene would follow an unusual partial-layer-by-partial-layer growth mode, characterized by short-range repulsive pairwise interactions of the Sn adatoms; the resultant stanene overlayer is destined to contain undesirable grain boundaries. More importantly, we find that stanene growth on Bi2Te3(111) pre-covered with a Bi bilayer follows a highly desirable nucleation-and-growth mechanism, strongly favoring single crystalline stanene. We further show that both systems exhibit pronounced Rashba spin-orbit couplings, while the latter system also provides new opportunities for the potential realization of topological superconductivity in 2D heterostructures. The novel kinetic pathways revealed here will be instrumental in achieving the mass production of high-quality stanene with emergent physical properties of technological significance.