Defect Engineering Centrosymmetric 2D Material Flexocatalysts.

In this study, the flexoelectric characteristics of 2D TiO2 nanosheets are examined. The theoretical calculations and experimental results reveal an excellent strain-induced flexoelectric potential (flexopotential) by an effective defect engineering strategy, which suppresses the recombination of electron-hole pairs, thus substantially improving the catalytic activity of the TiO2 nanosheets in the degradation of Rhodamine B dye and the hydrogen evolution reaction in a dark environment. The results indicate that strain-induced bandgap reduction enhances the catalytic activity of the TiO2 nanosheets. In addition, the TiO2 nanosheets degraded Rhodamine B, with kobs being ≈1.5 × 10-2 min-1 in dark, while TiO2 nanoparticles show only an adsorption effect. 2D TiO2 nanosheets achieve a hydrogen production rate of 137.9 µmol g-1 h-1 under a dark environment, 197% higher than those of TiO2 nanoparticles (70.1 µmol g-1 h-1 ). The flexopotential of the TiO2 nanosheets is enhanced by increasing the bending moment, with excellent flexopotential along the y-axis. Density functional theory is used to identify the stress-induced bandgap reduction and oxygen vacancy formation, which results in the self-dissociation of H2 O on the surface of the TiO in the dark. The present findings provide novel insights into the role of TiO2 flexocatalysis in electrochemical reactions.

Enhancing Zinc Electrode Stability Through Pre-Desolvation and Accelerated Charge Transfer via a Polyimide Interface for Zinc-Ion Batteries.

Aqueous zinc-based energy storage devices possess superior safety, cost-effectiveness, and high energy density; however, dendritic growth and side reactions on the zinc electrode curtail their widespread applications. In this study, these issues are mitigated by introducing a polyimide (PI) nanofabric interfacial layer onto the zinc substrate. Simulations reveal that the PI nanofabric promotes a pre-desolvation process, effectively desolvating hydrated zinc ions from Zn(H2O)6 2+ to Zn(H2O)4 2+ before approaching the zinc surface. The exposed zinc ion in Zn(H2O)4 2+ provides an accelerated charge transfer process and reduces the activation energy for zinc deposition from 40 to 21 kJ mol-1. The PI nanofabric also acts as a protective barrier, reducing side reactions at the electrode. As a result, the PI-Zn symmetric cell exhibits remarkable cycling stability over 1200 h, maintaining a dendrite-free morphology and minimal byproduct formation. Moreover, the cell exhibits high stability and low voltage hysteresis even under high current densities (20 mA cm-2, 10 mAh cm-2) thanks to the 3D porous structure of PI nanofabric. When integrated into full cells, the PI-Zn||AC hybrid zinc-ion capacitor and PI-Zn||MnVOH@SWCNT zinc-ion battery achieve impressive lifespans of 15000 and 600 cycles with outstanding capacitance retention. This approach paves a novel avenue for high-performance zinc metal electrodes.

Single Atom Ag Bonding Between PF3T Nanocluster and TiO2 Leads the Ultra-Stable Visible-Light-Driven Photocatalytic H2 Production.

Atomic Ag cluster bonding is employed to reinforce the interface between PF3T nano-cluster and TiO2 nanoparticle. With an optimized Ag loading (Ag/TiO2 = 0.5 wt%), the Ag atoms will uniformly disperse on TiO2 thus generating a high density of intermediate states in the band gap to form the electron channel between the terthiophene group of PF3T and the TiO2 in the hybrid composite (denoted as T@Ag05-P). The former expands the photon absorption band width and the latter facilitates the core-hole splitting by injecting the photon excited electron (from the excitons in PF3T) into the conduction band (CB) of TiO2. These characteristics enable the high efficiency of H2 production to 16 580 µmol h-1 g-1 and photocatalysis stability without degradation under visible light exposure for 96 h. Compared to that of hybrid material without Ag bonding (TiO2@PF3T), the H2 production yield and stability are improved by 4.1 and 18.2-fold which shows the best performance among existing materials in similar component combination and interfacial reinforcement. The unique bonding method offers a new prospect to accelerate the development of photocatalytic hydrogen production technologies.

Electron Injection via Interfacial Atomic Au Clusters Substantially Enhance the Visible-Light-Driven Photocatalytic H2 Production of the PF3T Enclosed TiO2 Nanocomposite.

A hybrid composite of organic-inorganic semiconductor nanomaterials with atomic Au clusters at the interface decoration (denoted as PF3T@Au-TiO2 ) is developed for visible-light-driven H2 production via direct water splitting. With a strong electron coupling between the terthiophene groups, Au atoms and the oxygen atoms at the heterogeneous interface, significant electron injection from the PF3T to TiO2 occurs leading to a quantum leap in the H2 production yield (18 578 µmol g-1 h-1 ) by ≈39% as compared to that of the composite without Au decoration (PF3T@TiO2 , 11 321 µmol g-1 h-1 ). Compared to the pure PF3T, such a result is 43-fold improved and is the best performance among all the existing hybrid materials in similar configurations. With robust process control via industrially applicable methods, it is anticipated that the findings and proposed methodologies can accelerate the development of high-performance eco-friendly photocatalytic hydrogen production technologies.

Experimental Revelation of Surface and Bulk Lattices in Faceted Cu2 O Crystals.

Semiconductor crystals have generally shown facet-dependent electrical, photocatalytic, and optical properties. These phenomena have been proposed to result from the presence of a surface layer with bond-level deviations. To provide experimental evidence of this structural feature, synchrotron X-ray sources are used to obtain X-ray diffraction (XRD) patterns of polyhedral cuprous oxide crystals. Cu2 O rhombic dodecahedra display two distinct cell constants from peak splitting. Peak disappearance during slow Cu2 O reduction to Cu with ammonia borane differentiates bulk and surface layer lattices. Cubes and octahedra also show two peak components, while diffraction peaks of cuboctahedra are comprised of three components. Temperature-varying lattice changes in the bulk and surface regions also show shape dependence. From transmission electron microscopy (TEM) images, slight plane spacing deviations in surface and inner crystal regions are measured. Image processing provides visualization of the surface layer with depths of about 1.5-4 nm giving dashed lattice points instead of dots from atomic position deviations. Close TEM examination reveals considerable variation in lattice spot size and shape for different particle morphologies, explaining why facet-dependent properties are emerged. Raman spectrum reflects the large bulk and surface lattice difference in rhombic dodecahedra. Surface lattice difference can change the particle bandgap.

Rubbing-free liquid crystal electro-optic device based on organic single-crystal rubrene.

Liquid crystals (LCs) have been a vital component of modern communication and photonic technologies. However, traditional LC alignment on polyimide (PI) requires mechanically rubbing treatment to control LC orientation, suffering from dust particles, surface damage, and electrostatic charges. In this paper, LC alignment on organic single-crystal rubrene (SCR) has been studied and used to fabricate rubbing-free LC devices. A rubrene/toluene solution is spin-coated on the indium-tin-oxide (ITO) substrate and transformed thereafter to the orthorhombic SCR after annealing. Experimental result reveals that SCR-based LC cell has a homogeneous alignment geometry, the pretilt angle of LCs is low and the orientation of LCs is determined with capillary filling action of LCs. LC alignment on SCR performs a wider thermal tolerance than that on PI by virtue of the strong anchoring nature of LCs on SCR due to van der Waals and π-π electron stacking interactions between the rubrene and LCs. SCR-based LC cell performs a lower operation voltage, faster response time, and higher voltage holding ratio than the traditional PI-based LC cell. Organic SCR enables to play a role as weakly conductive alignment layer without rubbing treatment and offers versatile function to develop novel LC devices.

Collaboration between a Pt-dimer and neighboring Co-Pd atoms triggers efficient pathways for oxygen reduction reaction.

The development of electrocatalysts with reconcilable balance between the cost and performance in oxygen reduction reaction (ORR) is an imperative task for the widespread adoption of fuel cell technology. In this study, we proposed a unique model of diatomic Pt-cluster (Pt-dimer) in the topmost layer of the Co/Pd bimetallic slab (Co@Pd-Pt2) for mimicking the Cocore@Pdshell nanocatalysts (NCs) surface and systematically investigating its local-regional collaboration pathways in ORR by density functional theory (DFT). The results demonstrate that the Pt-dimer produces local differentiation from both ligand and geometric effects on the Co@Pd surface, which forms adsorption energy (Eads) gradients for relocating the ORR-adsorbates. Our calculations for Eads-variations of ORR-species, reaction coordinates, and intraparticle charge injection propose and confirm a novel local synergetic collaboration around the Pt-dimer in the Co@Pd-Pt2 system with the best-performing ORR behavior compared with all reference models. With proper selection of the composition in intraparticle components, the proposed DFT assessments could be adopted for developing economical and high-performance catalysts in various heterogeneous reactions.

Tri-atomic Pt clusters induce effective pathways in a Cocore-Pdshell nanocatalyst surface for a high-performance oxygen reduction reaction.

The crux of the hot topic concerning the widespread replacement of fuel cells (FCs) with traditional petrochemical energy is to balance improving the oxygen reduction reaction (ORR) and reducing the cost. The present study employs density functional theory (DFT) to investigate the effect of Pt ensemble size regulation from a single atom to full coverage on the physio-chemical properties, oxygen adsorption energies and overall ORR efficiency of bimetallic nanocatalysts (NCs) with a Cocore-Pdshell structure. Our results reveal that the electronegativity difference and lattice strain between neighboring heteroatoms are enhanced to trigger a synergetic effect in local domains, with the Pt cluster size reduced from nanometers to subnanometers. They induce a directed and tunable charge relocation mechanism from deep Co to topmost Pt to optimize the adsorption energies of O2/O* and achieve excellent ORR kinetics performance with minimum Pt usage but maximum Pt atom utilization (i.e., Pt1 to Pt3) compared with benchmark Pt(111). Such a dependency between the cluster size and corresponding ORR performance for the established Co@Pd-Ptn system can be applied to accurately guide the experimental synthesis of ordered heterogeneous catalysts (e.g., other core@shell-clusters structures) toward low Pt, high efficiency and green economy.

Nanoisozymes: The Origin behind Pristine CeO2 as Enzyme Mimetics.

It is known that the interplay between molecules and active sites on the topmost surface of a solid catalyst determines its activity in heterogeneous catalysis. The electron density of the active site is believed to affect both adsorption and activation of reactant molecules at the surface. Unfortunately, commercial X-ray photoelectron spectroscopy, which is often adopted for such characterization, is not sensitive enough to analyze the topmost surface of a catalyst. Most researchers fail to acknowledge this point during their catalytic correlation, leading to different interpretations in the literature in recent decades. Recent studies on pristine Cu2 O [Nat. Catal. 2019, 2, 889; Nat. Energy 2019, 4, 957] have clearly suggested that the electron density of surface Cu is facet dependent and plays a key role in CO2 reduction. Herein, it is shown that pristine CeO2 can reach 2506/1133 % increase in phosphatase-/peroxidase-like activity if the exposed surface is wisely selected. By using NMR spectroscopy with a surface probe, the electron density of the surface Ce (i.e., the active site) is found to be facet dependent and the key factor dictating their enzyme-mimicking activities. Most importantly, the surface area of the CeO2 morphologies is demonstrated to become a factor only if surface Ce can activate the adsorbed reactant molecules.

Transition-metal dichalcogenides/Mg(OH)2 van der Waals heterostructures as promising water-splitting photocatalysts: a first-principles study.

We performed first-principles calculations of the structural, electronic, and optical properties of heterostructures which consist of transition metal dichalcogenides MX2 (M = Mo, W; X = S) stacked with Mg(OH)2. All the heterostructures are formed by van der Waals forces. The MoS2/Mg(OH)2 and WS2/Mg(OH)2 vdW heterostructures were found to be semiconductors with indirect bandgaps and possess intrinsic type-II band alignment. In particular, a comparison of the band edge positions with the redox potential of water indicates that the heterostructures are potential photocatalysts for water splitting, enabling water reduction on the MX2 layer and water oxidation on the Mg(OH)2 layer. Moreover, the photogenerated charges will be effectively separated in the presence of a large built-in electric field across the interface. In addition, all of the MX2/Mg(OH)2 heterostructures show strong optical absorption in the visible and infrared regions, indicating their promise for application in photocatalytic water splitting.

Two-Dimensional In-Sb Compound on Silicon as a Quantum Spin Hall Insulator.

Two-dimensional (2D) topological insulator is a promising quantum phase for achieving dissipationless transport due to the robustness of the gapless edge states resided in the insulating gap providing realization of the quantum spin Hall effect. Searching for two-dimensional realistic materials that are able to provide the quantum spin Hall effect and possessing the feasibility of their experimental preparation is a growing field. Here we report on the two-dimensional (In, Sb)2[Formula: see text]2[Formula: see text] compound synthesized on Si(111) substrate and its comprehensive experimental and theoretical investigations based on an atomic-scale characterization by using scanning tunneling microscopy and angle-resolved photoelectron spectroscopy as well as ab initio density functional theory calculations identifying the synthesized 2D compound as a suitable system for realization of the quantum spin Hall effect without additional functionalization like chemical adsorption, applying strain, or gating.

First-Principles Study of Charge Diffusion between Proximate Solid-State Qubits and Its Implications on Sensor Applications.

Solid-state qubits from paramagnetic point defects in solids are promising platforms to realize quantum networks and novel nanoscale sensors. Recent advances in materials engineering make it possible to create proximate qubits in solids that might interact with each other, leading to electron spin or charge fluctuation. Here we develop a method to calculate the tunneling-mediated charge diffusion between point defects from first principles and apply it to nitrogen-vacancy (NV) qubits in diamond. The calculated tunneling rates are in quantitative agreement with previous experimental data. Our results suggest that proximate neutral and negatively charged NV defect pairs can form a NV-NV molecule. A tunneling-mediated model for the source of decoherence of the near-surface NV qubits is developed based on our findings on the interacting qubits in diamond.

First-principles calculations of the electronic properties of SiC-based bilayer and trilayer heterostructures.

Recently, van der Waals (vdW) two-dimensional heterostructures have attracted great attention. The combination structures demonstrate unique properties that individual layers do not possess, which foretell promising future applications. Here, we investigate the structural and electronic properties of SiC/graphene, SiC/MoS2, and graphene/SiC/MoS2 vdW heterostructures using first-principles calculations. The SiC/graphene interface forms a p-type Schottky contact, which can be turned into an n-type Schottky contact by applying an external electric field. Moreover, a transition from a Schottky to an Ohmic contact at the interface can be triggered by varying the interlayer distance or applying an external electric field. The SiC/MoS2 interface forms a type-II heterostructure, in which the recombination of photoexcited charges will be greatly suppressed. The transition from type-II to type-III band alignment can be realized in the SiC/MoS2 heterostructure by applying a biaxial strain. This heterostructure also shows excellent optical absorption abilities in the visible and far-infrared range, which merits its application as a photocatalyst. The trilayer heterostructure exhibits a tunable Schottky barrier with different stacking patterns and the assembled graphene could act as a protective encapsulating layer on SiC/MoS2. The results show that graphene and MoS2 can tune and improve the electronic performance of SiC and demonstrate the promising application of SiC-based heterostructures for nanoelectronics and nanophotonics.

Nitrogen-Terminated Diamond (111) Surface for Room-Temperature Quantum Sensing and Simulation.

The nitrogen-vacancy (NV) center in diamond has shown great promise of nanoscale sensing applications, however, near-surface NV suffer from relatively short spin coherence time that limits its sensitivity. This is presumably caused by improper surface termination. Using first-principles calculations, we propose that nitrogen-terminated (111) diamond provides electrical inactivity and surface spin noise free properties. We anticipate that the nitrogen-terminated (111) surface can be fabricated by nitrogen plasma treatment. Our findings pave the way toward an improved NV-based quantum sensing and quantum simulation operating at room temperature.

Weak C-HF-C hydrogen bonds make a big difference in graphane/fluorographane and fluorographene/fluorographane bilayers.

Using density functional theory computations with van der Waals (vdW) corrections, we reveal that C-HF-C hydrogen bonding exists in graphane/fluorographene and fluorographane/fluorographane bilayers. The significant C-HF-C hydrogen bonding is strong enough to combine two separate monolayers to form the bilayer. Interestingly, both the graphane/fluorographene and fluorographane/fluorographane bilayers are metallic in the most stable stacking configuration. Applying a perpendicular electric field can effectively open a bandgap for both bilayers, and we found that the field-induced gap opening for both graphane/fluorographene and fluorographane/fluorographane bilayers can be enhanced by biaxial tensile strain. These results are expected to aid in the design of novel electronic and optoelectronic devices based on graphene materials, and they highlight the use of weak interactions for modulating band structures in two-dimensional materials.

Electronic properties of blue phosphorene/graphene and blue phosphorene/graphene-like gallium nitride heterostructures.

Blue phosphorene (BlueP) is a graphene-like phosphorus nanosheet which was synthesized very recently for the first time [Nano Lett., 2016, 16, 4903-4908]. The combination of electronic properties of two different two-dimensional materials in an ultrathin van der Waals (vdW) vertical heterostructure has been proved to be an effective approach to the design of novel electronic and optoelectronic devices. Therefore, we used density functional theory to investigate the structural and electronic properties of two BlueP-based heterostructures - BlueP/graphene (BlueP/G) and BlueP/graphene-like gallium nitride (BlueP/g-GaN). Our results showed that the semiconducting nature of BlueP and the Dirac cone of G are well preserved in the BlueP/G vdW heterostructure. Moreover, by applying a perpendicular electric field, it is possible to tune the position of the Dirac cone of G with respect to the band edge of BlueP, resulting in the ability to control the Schottky barrier height. For the BlueP/g-GaN vdW heterostructure, BlueP forms an interface with g-GaN with a type-II band alignment, which is a promising feature for unipolar electronic device applications. Furthermore, we discovered that both G and g-GaN can be used as an active layer for BlueP to facilitate charge injection and enhance the device performance.

Proper surface termination for luminescent near-surface NV centers in diamond.

By accurate quantum mechanical simulations, we show that typical diamond surfaces possess image states with sub-bandgap energies, and compromise the photostability of NV centers placed within a few nm of the surface. This occurs due to the mixture of the NV-related gap states and the surface image states, which is a novel and distinct process from the well-established band bending effect. We also find that certain types of coverages on the diamond surface may lead to blinking or bleaching due to the presence of acceptor surface states. We identify a combination of surface terminators that is perfect for NV-center based nanoscale sensing.

Investigating the role of undercoordinated Pt sites at the surface of layered PtTe2 for methanol decomposition.

Transition metal dichalcogenides, by virtue of their two-dimensional structures, could provide the largest active surface for reactions with minimal materials consumed, which has long been pursued in the design of ideal catalysts. Nevertheless, their structurally perfect basal planes are typically inert; their surface defects, such as under-coordinated atoms at the surfaces or edges, can instead serve as catalytically active centers. Here we show a reaction probability > 90 % for adsorbed methanol (CH3OH) on under-coordinated Pt sites at surface Te vacancies, produced with Ar+ bombardment, on layered PtTe2 - approximately 60 % of the methanol decompose to surface intermediates CHxO (x = 2, 3) and 35 % to CHx (x = 1, 2), and an ultimate production of gaseous molecular hydrogen, methane, water and formaldehyde. The characteristic reactivity is attributed to both the triangular positioning and varied degrees of oxidation of the under-coordinated Pt at Te vacancies.

Dual-plasmonic Au@Cu7S4 yolk@shell nanocrystals for photocatalytic hydrogen production across visible to near infrared spectral region.

Near infrared energy remains untapped toward the maneuvering of entire solar spectrum harvesting for fulfilling the nuts and bolts of solar hydrogen production. We report the use of Au@Cu7S4 yolk@shell nanocrystals as dual-plasmonic photocatalysts to achieve remarkable hydrogen production under visible and near infrared illumination. Ultrafast spectroscopic data reveal the prevalence of long-lived charge separation states for Au@Cu7S4 under both visible and near infrared excitation. Combined with the advantageous features of yolk@shell nanostructures, Au@Cu7S4 achieves a peak quantum yield of 9.4% at 500 nm and a record-breaking quantum yield of 7.3% at 2200 nm for hydrogen production in the absence of additional co-catalysts. The design of a sustainable visible- and near infrared-responsive photocatalytic system is expected to inspire further widespread applications in solar fuel generation. In this work, the feasibility of exploiting the localized surface plasmon resonance property of self-doped, nonstoichiometric semiconductor nanocrystals for the realization of wide-spectrum-driven photocatalysis is highlighted.

Atomic Scaled Depth Correlation to the Oxygen Reduction Reaction Performance of Single Atom Ni Alloy to the NiO2 Supported Pd Nanocrystal.

This study demonstrates the intercalation of single-atom Ni (NiSA ) substantially reduces the reaction activity of Ni oxide supported Pd nanoparticle (NiO2 /Pd) in the oxygen reduction reaction (ORR). The results indicate the transition states kinetically consolidate the adsorption energy for the chemisorbed O and OH species on the ORR activity. Notably, the NiO2 /Ni1 /Pd performs the optimum ORR behavior with the lowest barrier of 0.49 eV and moderate second-step barrier of 0.30 eV consequently confirming its utmost ORR performance. Through the stepwise cross-level demonstrations, a structure-Eads -ΔE correspondence for the proposed NiO2 /Nin /Pd systems is established. Most importantly, such a correspondence reveals that the electronic structure of heterogeneous catalysts can be significantly differed by the segregation of atomic clusters in different dimensions and locations. Besides, the doping-depth effect exploration of the NiSA in the NiO2 /Pd structure intrinsically elucidates that the Ni atom doping in the subsurface induces the most fruitful NiSA /PdML synergy combining the electronic and strain effects to optimize the ORR, whereas this desired synergy diminishes at high Pd coverages. Overall, the results not only rationalize the variation in the redox properties but most importantly provides a precision evaluation of the process window for optimizing the configuration and composition of bimetallic catalysts in practical experiments.