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Chemical doping is verified to be a promising strategy to regulate local electron distribution and further promote the poor intrinsic catalytic activity of graphdiyne. However, the current doping approach still faces problems such as precise doping for creating active sites and the destruction of graphdiyne skeleton calling for high temperature. Here, we achieved charge redistribution on graphdiyne surface through molecule functionalization. A p-type molecule–F4TCNQ (2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane) was introduced and the site-defined functionalization was accomplished. Theoretical calculations showed that the charge transfer ability is improved and graphdiyne becomes positively charged. The oxygen reduction electrocatalysis was conducted as a proof of principle, where the electronic states of sp hybridized C active site was tuned toward favorable reaction intermediates’ adsorption. Such work from both theoretical prediction and experimental validation, found that molecule functionalization is effective to promote the electrocatalytic oxygen reduction, which creates new possibilities for graphdiyne’s applications in different electrochemical reactions.

Understanding the interactions between metallic lithium (Li) and the anchoring sites/groups is essential for the design of stable host materials and artificial interphases in lithium metal batteries (LMBs). Here, we investigate the interactions of lithium with the polar organic functional groups in copper(II) hexadecafluorophthalocyanine (F16CuPc) and copper(II) phthalocyanine (CuPc) through the combination of in-situ X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), synchrotron-based near-edge X-ray absorption fine structures (NEXAFS), and density functional theory (DFT) calculations. It is revealed that the highly polar C-F bonds can anchor the Li atom via ionic Li-F interaction around the outer aza bridge N atoms in F16CuPc, while Li tends to interact with the inner pyrrolic N atoms around the central Cu in CuPc. The central Cu(II) ions in both molecules are reduced to Cu(I) upon interaction with Li. Electrons are transferred from Li to the lowest unoccupied molecular orbitals (LUMO) of both F16CuPc and CuPc molecules, as revealed by the UPS and NEXAFS measurements. Our systematic study can shed light on the design of anode materials by adding polar functional groups for applications in lithium metal batteries (LMBs). Ministry of Education (MOE) The authors acknowledge the financial support from the Natural Science Foundation of China (U2032147), Singapore MOE Tier II grant R143-000-A29-112, and Academic Research Fund Tie I grant RG104/18.

Summary Aqueous electrochemical CO2 reduction (CO2R) on Cu can generate a variety of valuable fuels, yet challenges remain in the improvement of electrosynthesis pathways for highly selective fuel production. Mechanistically, understanding CO2R on Cu, particularly identifying the product-specific active sites, is crucial. Herein, we rationally designed and fabricated nine large-area single-crystal Cu foils with various surface orientations as electrocatalysts and identified the voltage- and facet-dependent CO2R selectivities. Operando grazing incidence X-ray diffraction (GIXRD) and electron back-scattered diffraction (EBSD) were applied to track the top-surface reconstructions of Cu, and we correlate the structural evolution with the change of product selectivities. We extracted three distinct structural descriptors, including crystal facet, atomic coordination number, and step-terrace angle, to reveal the intrinsic structure-function relationships and uniquely identify the specific product-producing sites for CO2R. Our work guides the rational design of Cu-based CO2R electrocatalysts and, more importantly, establishes a paradigm to understand the structure-function correlation in catalysis.

Electrocatalytic dinitrogen reduction reaction (N2RR) is an emerging route for ammonia synthesis at ambient conditions. Albeit the “π back-donation” process enables N2RR activity on transition metals with empty d-orbitals, given its dilemma in overcoming hydrogen evolution reaction (HER) competition, exploring p-block-element-based catalysts with relatively inferior HER activity is achievable for high selectivity. The challenge lies in designing rational structure to improve N2RR activity. Here, we synergistically integrate oxygen vacancy (VO) with hydroxyl on Bi4O5I2 (VO-Bi4O5I2-OH), which render this p-block-element-based material active to mimic “π back-donation” behavior because of sufficient vacant orbitals. In neutral media, the electrocatalytic N2RR performance of VO-Bi4O5I2-OH in terms of splendid faradic efficiency (32.4%) is superior to most of the prior reports using p-block-element-based catalysts. Our findings show a new strategy toward standout N2RR activity, which holds great potential in exploiting other p-block-element-based electrocatalysts. Ministry of Education (MOE) Accepted version Q.Y. acknowledges the funding support from Singapore MOE AcRF Tier 1 Grant Nos. RG113/15 and 2016-T1-002-065, and Tier 2 under Grant Nos. 2017-T2-2-069 and 2018-T2-01-010. The authors greatly thank the Facility for Analysis, Characterization, Testing and Simulation (FACTS) of Nanyang Technological University, Singapore, for using their TEM, SEM, and XRD equipment.

Organic anode materials have attracted considerable interest owing to their high tunability by adopting various active functional groups. However, the interaction mechanisms between the alkali metals and the active functional groups in host materials have been rarely studied systematically. Here, a widely used organic semiconductor of perylene-3,4,9,10-tetracarboxylic diimide (PTCDI) was selected as a model system to investigate how alkali metals interact with imide functional groups and induce changes in chemical and electronic structures of PTCDI. The interaction at the alkali/PTCDI interface was probed by in-situ X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), synchrotron-based near edge X-ray absorption fine structure (NEXAFS), and corroborated by density functional theory (DFT) calculations. Our results indicate that the alkali metal replaces the hydrogen atoms in the imide group and interact with the imide nitrogen of PTCDI. Electron transfer induced gap states and downward band-bending like effects are identified on the alkali-deposited PTCDI surface. It was found that Na shows a stronger electron transfer effect than Li. Such a model study of alkali insertion/intercalation in PTCDI gives insights for the exploration of the potential host materials for alkali storage applications.

Ideal electromagnetic (EM) wave absorption materials should exhibit strong absorption peaks and broad effective absorption bandwidths, which are important for EM protection and the stealth technology. Despite considerable advancements in this field in recent years, EM absorption materials have not reached their full potential to meet all the above-mentioned requirements, especially the broad absorption bandwidth at low frequencies. Herein, we synthesized a Co-doped NiZn ferrite (CNZFO)/polyaniline (PANI) on Ti3C2TX MXene composite with a hierarchical structure via three facile steps: exfoliation, hydrothermal process, and modified interfacial polymerization. The CNZFO particles and PANI chains as well as the small number of TiO2 particles uniformly grafted between the Ti3C2TX layers formed a unique sandwich-like structure. The multiple-layer composite showed excellent EM wave absorption with a maximum reflection loss (RL) of −37.1 dB at only 2.2 mm. It showed an effective bandwidth (RL

Graphene oxide/silica (GO/SiO2) multilayers could be successfully deposited onto a carbon fiber (CF) surface via a convenient and efficient layer-by-layer (LbL) self-assembly approach. It is possib...

Ion adsorption inside electrified carbon micropores is pivotal for the operation of supercapacitors. Depending on the electrolyte, two main mechanisms have been identified so far, the desolvation of ions in solvents and the formation of superionic states in ionic liquids. Here, it is shown that upon confinement inside negatively charged micropores, transition-metal cations dissolved in water associate to form oligomer species. They are identified using in situ X-ray absorption spectroscopy. The cations associate one with each other via hydroxo bridging, forming ionic oligomers under the synergic effect of spatial confinement and Coulombic screening. The oligomers display sluggish dissociation kinetics and accumulate upon cycling, which leads to supercapacitor capacitance fading. They may be dissolved by applying a positive potential, so an intermittent reverse cycling strategy is proposed to periodically evacuate micropores and revivify the capacitance. These results reveal new insights into ion adsorption and structural evolution with their effects on the electrochemical performance, providing guidelines for designing advanced supercapacitors. Ministry of Education (MOE) National Research Foundation (NRF) Submitted/Accepted version This work was supported by Singapore Ministry of Education Academic Research Fund Tier 2 (Grant No. MOE-T2EP10220-0005), Academic Research Fund Tier 1 (Grant No. RG104/18), Singapore National Research Foundation (Nanomaterials for Energy and Water Management CREATE Programme), Energy Innovation Research Programme (EIRP) (Grant No. NRF2015EWT-EIRP002-008), and French National Research Agency (Labex STORE-EX, Grant No. ANR-10-LABX-0076).

Free-standing metallic nanohole arrays (NAs) exhibit extraordinary benefits in combining nanofluidics and plasmonics in a single platform for flow-through plasmofluidic sensing. However, the sensing performance of NAs is usually limited by the low quality factor of the transmission peak, resulting from strong radiative damping. Here, we demonstrate a concept for high-performance plasmofluidic sensing based on the subradiant mode in free-standing metallic NAs. We show that the subradiant mode exhibits a good spectral resolution only when the dielectric media at the upper and lower metal surfaces are symmetric; otherwise, it easily emerges into other features present in the same spectral region. Therefore, free-standing NAs are particularly suitable for highly sensitive microfluidic sensing based on the subradiant mode. In addition, the subradiant mode exhibits a highly tunable frequency and refractive index sensitivity (RIS), depending strongly on the film thickness and periodicity and weakly on the hole r...

Surface defects in semiconductors have a significant role to tune the photocatalytic reactions. However, the dominant studied defect type is oxygen vacancy, and metal cation vacancies are seldom ex...

The charge-transport properties of charge-transfer complexes (CTCs) play a key role in the potential applications toward novel optoelectronic devices. We have systematically studied the charge-transport properties of perylene-F4TCNQ CTCs with different stoichiometric ratios by first-principles calculations. Our calculated results showed that 1P1F4 (perylene-F4TCNQ 1:1) exhibits a higher charge-carrier mobility than 3P2F4 (perylene-F4TCNQ 3:2) due to the strong interlayer interactions in 3P2F4. Compared with the perylene-TCNQ CTC, the higher charge-carrier mobility in perylene-F4TCNQ CTC indicates that introducing fluorine atoms can enhance the charge-carrier mobility due to stronger intermolecular interactions. More importantly, the experimental measurements carried out with 1P1F4- and 3P2F4-based field-effect transistors are consistent with the theoretical predictions. Our study reveals that tuning the charge-transport properties in CTCs by controlling the stoichiometry between the donor and acceptor is a promising strategy in accelerating the development of high-performance organic electronic materials.

The design of efficient and stable photocatalysts for robust CO2 reduction without sacrifice reagent or extra photosensitizer is still challenging. Herein, a single-atom catalyst of isolated single atom cobalt incorporated into Bi3O4Br atomic layers is successfully prepared. The cobalt single atoms in the Bi3O4Br favors the charge transition, carrier separation, CO2 adsorption and activation. It can lower the CO2 activation energy barrier through stabilizing the COOH* intermediates and tune the rate-limiting step from the formation of adsorbed intermediate COOH* to be CO* desorption. Taking advantage of cobalt single atoms and two-dimensional ultrathin Bi3O4Br atomic layers, the optimized catalyst can perform light-driven CO2 reduction with a selective CO formation rate of 107.1 µmol g−1 h−1, roughly 4 and 32 times higher than that of atomic layer Bi3O4Br and bulk Bi3O4Br, respectively.

Exploring new hybridized catalysts for synergistically promoting the photocatalytic efficiency hold great challenges in solar-to-chemical energy conversion and environmental remediation. Hierarchical Zn2In2S5/Ti3C2(O, OH)x hybrids have been rationally constructed using Ti3C2(O, OH)x as a two-dimensional platform for in situ growth of flower-like Zn2In2S5 microsphere under anaerobically hydrothermal conditions. Upon exposure to visible light, the Zn2In2S5/Ti3C2(O, OH)x hybrids with the Ti3C2(O, OH)x content of 1.5% (by mass) had hydrogen generation yields of 12,983.8 μmol g−1, which was significantly better than that of pure Zn2In2S5. The apparent quantum efficiency reached 8.96% at 420 nm. Furthermore, the photocatalytic tetracycline removal rate was ˜1.25 times higher than that of pure Zn2In2S5, and can be further improved with the increase of temperature in the range of 35–55 °C. Excellent photocatalytic activity originated from the synergistic effects between visible-light-active Zn2In2S5 and conductive Ti3C2(O, OH)x for spatial electrical promotion. The photogenerated-electrons transfer efficiency from Zn2In2S5 to Ti3C2(O, OH)x was 33.0%. In accordance with spectroscopic, electrochemical, and density functional theory studies, we proposed that the interfacial-built-in quasi-alloying effect between ZIS and Ti3C2(O, OH)x culminated in notable charge redistribution, which thereby facilitated the spatial separation and transfer of photogenerated electron-hole pairs. This work revealed the underlying photo-excited charge transfer between metallic compound and semiconductor. Economic Development Board (EDB) Enterprise Singapore Ministry of Education (MOE) The authors gratefully acknowledge the financial support provided by the Singapore Ministry of Education Academic Research Funds Tier 2 (MOE2014-T2-2-074; ARC16/15) and Tier 1 (2015-T1-001-023; RG7/15), the GSK (GlaxoSmithKline) – EDB (Economic Development Board) Trust Fund, and the Joint Singapore-Germany Research Project Fund (SGP-PROG3-019). We also acknowledge funding from the Projects of the National Nature Science Foundation of China (No. 21776066, 51708195). Hou Wang, Yuanmiao Sun and Yan Wu contributed equally to this work.

Crystal phase engineering is a promising strategy to tune the catalytic performance of metal nanomaterials. Generally, the crystal phase effect on catalysis is ascribed to distinct surface atomic arrangements of catalysts with different crystal phases. Here we show that even for similar surfaces, such as the close-packed surfaces, different crystal phases have considerably different surface reactivities due to their distinct intrinsic surface strains. Using first-principles calculations, we find that the close-packed surfaces of hexagonal close-packed (HCP) and double HCP (4H) gold have significantly smaller intrinsic strains (∼1.3%) than those of face-centered cubic (FCC) gold (∼2.3%). These distinct intrinsic surface strains result in various oxygen adsorption energies and O2 dissociation barriers on these close-packed gold surfaces, and the dissociation of O2 on different crystal phases and surfaces follows the Bronsted–Evans–Polanyi principle.

The electrochemical conversion of CO2 to valuable fuels is a plausible solution to meet the soaring need for renewable energy sources. However, the practical application of this process is limited by its poor selectivity due to scaling relations. Here we introduce the rational design of the monolayer hexagonal boron nitride/copper (h-BN/Cu) interface to circumvent scaling relations and improve the electrosynthesis of CH4. This catalyst possesses a selectivity of >60% toward CH4 with a production rate of 15 μmol·cm-2·h-1 at -1.00 V vs RHE, along with a much smaller decaying production rate than that of pristine Cu. Both experimental and theoretical calculations disclosed that h-BN/Cu interfacial perimeters provide specific chelating sites to immobilize the intermediates, which accelerates the conversion of *CO to *CHO. Our work reports a novel Cu catalyst engineering strategy and demonstrates the prospect of monolayer h-BN contributing to the design of heterostructured CO2 reduction electrocatalysts for sustainable energy conversion.

The description of surface-enhanced Raman scattering (SERS) as a molecular optomechanical process has provided new insights into the vibrational dynamics and nonlinearities of this inelastic scattering process. In earlier studies, molecular vibrations have typically been assumed to couple with a single plasmonic mode of a metallic nanostructure, ignoring the complexity of the plasmonic response in many configurations of practical interest such as in metallic nanojunctions. By describing the plasmonic fields as a continuum, we demonstrate here the importance of considering the full plasmonic response to properly address the molecule-cavity optomechanical interaction. We apply the continuum-field model to calculate the Raman signal from a single molecule in a plasmonic nanocavity formed by a nanoparticle-on-a-mirror configuration, and compare the results of optomechanical parameters, vibrational populations, and Stokes and anti-Stokes signals of the continuum-field model with those obtained from the single-mode model. Our results reveal that high-order non-radiative plasmonic modes significantly modify the optomechanical behavior under strong laser illumination. Moreover, Raman linewidths, lineshifts, vibrational populations, and parametric instabilities are found to be sensitive to the energy of the molecular vibrational modes. The implications of adopting the continuum-field model to describe the plasmonic cavity response in molecular optomechanics are relevant in many other nanoantenna and nanocavity configurations commonly used to enhance SERS., We acknowledge project Nr. 12004344 from the National Science Foundation of China, joint project Nr. 21961132023 from the NSFC-DPG, project PID2019-107432GB-I00 from the Spanish Ministry of Science and Innovation, project KK-2019/00101 from Eusko Jaurlaritza, project H2020-FET Open “THOR” Nr. 829067 from the European Commission, UK EPSRC EP/L027151/1, and grant IT1164-19 for consolidated groups of the Basque University, through the Department of Education, Research and Universities of the Basque Government.

Decentralized electrosynthesis of hydrogen peroxide (H2 O2 ) via oxygen reduction reaction (ORR) can enable applications in disinfection control, pulping and textile bleaching, wastewater treatment, and renewable energy storage. Transition metal oxides are usually not efficient catalysts because they are more selective to produce H2 O. Here, it is shown that divalent 3d transition metal cations (Mn, Fe, Co, Ni, and Cu) can control the catalytic activity and selectivity of columbite nanoparticles. They are synthesized using polyoxoniobate (K7 HNb6 O19 ·13H2 O) and divalent metal cations by a hydrothermal method. The optimal NiNb2 O6 holds an H2 O2 selectivity of 96% with the corresponding H2 O2 Faradaic efficiency of 92% in a wide potential window from 0.2 to 0.6 V in alkaline electrolyte, superior to other transition metal oxide catalysts. Ex situ X-ray photoelectron and operando Fourier-transformed infrared spectroscopic studies, together with density functional theory calculations, reveal that 3d transition metals shift the d-band center of catalytically active surface Nb atoms and change their interactions with ORR intermediates. In an application demonstration, NiNb2 O6 delivers H2 O2 productivity up to 1 molH2O2 gcat -1 h-1 in an H-shaped electrolyzer and can yield catholytes containing 300 × 10-3 m H2 O2 to efficiently decomposing several organic dyes. The low-cost 3d transition-metal-mediated columbite catalysts show excellent application potentials.

The thermal expansion coefficient (TEC) and thermal conductivity (k) of thermal fillers are key factors for designing thermal management and thermal protection composite materials. Due to its unique advantages, hexagonal boron nitride (h-BN) is one of the most commonly used thermal fillers. However, its TEC and k values are still unclear due to the inconsistency of characterization techniques and sample preparations. In this work, these disputes were addressed using the quasi-harmonic approximation (QHA) method and phonon Boltzmann transport equation (BTE) theory based on the density functional theory (DFT), respectively. The accuracy of our calculated TEC and k values was confirmed by previously reported experimental results, and the underlying physical principles were analyzed from the phonon behaviors. Our TEC results show that the h-BN has small in-plane negative value and large cross-plane positive value, which are −2.4×10−6 and 36.4×10−6 K−1 at 300 K, respectively. And the anisotropic TEC is mainly determined by the anisotropic isothermal bulk modulus and the low-frequency out-of-plane longitudinal phonon modes. We found that the convergence of cutoff radius and q-grid size have significant effect on the accuracy of k of h-BN. Our results show that the in-plane k is much higher than the cross-plane k, and the values at 300 K are 286.6 and 2.7 W m−1 K−1, respectively. The anisotropic phonon group velocity arising from the vibration behaviors of acoustic phonon modes should be primarily responsible for the anisotropic k. Our calculated TEC and k values will provide important references for the design of h-BN composite materials. This work was supported by the National Natural Science Foundation of China (51621091, 51225203, and 51672060), and the National Key Research and Development Program of China (2017YFB0310400).

Due to mechanical flexibility and low cost, heterojunctions consisting of graphene and small organic molecules are regarded as promising candidate materials for vertical organic field-effect transistors (VOFETs), where the charge carrier mobility perpendicular to the graphene plane is crucial to their performance. Herein, through density functional simulations, we find that the vertical charge carrier mobility of the heterojunctions can be greatly adjusted by tuning their π-π stacking distances. For the 6,13-dichloropentacene (DCP)/graphene heterojunctions, with the distance between the first DCP layer and graphene decreasing to below 2.4 A, the vertical electron mobility between DCP layers is improved dramatically while the vertical hole mobility is greatly reduced. The strong dependence of vertical charge carrier mobility on the distance between the first molecular layer and substrate for smaller values than the typical π-π stacking distance (3.3-3.8 A) was also observed in the perylenetetracarboxylic dianhydride (PTCDA)/graphene and DCP/hexagonal-BN heterojunctions, where the tendency is very different to that of the DCP/graphene heterojunction. Our simulation results enabled us to develop a new strategy to tune the vertical charge transport properties in molecule/graphene heterojunctions, which provides insights into developing efficient VOFETs.

Zwitterionic peptides are great candidates as antifouling coating materials in many biomedical applications. We investigated the structure and antifouling properties of surface-tethered zwitterionic peptide monolayers with different peptide chain lengths and charge distributions using a combination of surface plasma resonance, atomic force microscopy, and all atomistic molecular dynamics (MD) simulation techniques. Our results demonstrate that zwitterionic peptides with more zwitterionic lysine (K) and glutamic acid (E) repeating units exhibit better antifouling performance. The block charge distributions of the positive and negative charges in the peptides (having multiple positive charges next to the same amount of negative charges), although affecting the structure of the peptide molecules, do not significantly change the antifouling properties of the peptide monolayers in the solutions containing monovalent ions. However, divalent cations, Ca2+ and Mg2+, in solution can significantly alter the structure and lower the antifouling performance of the zwitterionic peptide monolayers, especially with the sequences of block charges. All atomistic MD simulations quantitatively reveal that the divalent cations in solution lead to more interchain electrostatic cross-links between peptide chains, especially for peptides with block charges, which causes dehydration of the zwitterionic peptides and diminishes their antifouling performances. NRF (Natl Research Foundation, S’pore) MOE (Min. of Education, S’pore) Accepted version

Bacterial infections remain a leading threat to global health because of the misuse of antibiotics and the rise in drug-resistant pathogens. Although several strategies such as photothermal therapy and magneto-thermal therapy can suppress bacterial infections, excessive heat often damages host cells and lengthens the healing time. Here, a localized thermal managing strategy, thermal-disrupting interface induced mitigation (TRIM), is reported, to minimize intercellular cohesion loss for accurate antibacterial therapy. The TRIM dressing film is composed of alternative microscale arrangement of heat-responsive hydrogel regions and mechanical support regions, which enables the surface microtopography to have a significant effect on disrupting bacterial colonization upon infrared irradiation. The regulation of the interfacial contact to the attached skin confines the produced heat and minimizes the risk of skin damage during thermoablation. Quantitative mechanobiology studies demonstrate the TRIM dressing film with a critical dimension for surface features plays a critical role in maintaining intercellular cohesion of the epidermis during photothermal therapy. Finally, endowing wound dressing with the TRIM effect via in vivo studies in S. aureus infected mice demonstrates a promising strategy for mitigating the side effects of photothermal therapy against a wide spectrum of bacterial infections, promoting future biointerface design for antibacterial therapy. National Research Foundation (NRF) Accepted version This work was financially supported by the NTU-Northwestern Institute for Nanomedicine and the National Research Foundation, Prime Minister’s Office, Singapore, under the NRF Investigatorship (NRF-NRFI2017-07).

The rational design of previously unidentified materials that could realize excellent electrochemical‐controlled optical and charge storage properties simultaneously, are especially desirable and useful for fabricating smart multifunctional devices. Here, a facile synthesis of a 1D π–d conjugated coordination polymer (Ni‐BTA) is reported, consisting of metal (Ni)‐containing nodes and organic linkers (1,2,4,5‐benzenetetramine), which could be easily grown on various substrates via a scalable chemical bath deposition method. The resulting Ni‐BTA film exhibits superior performances for both electrochromic and energy storage functions, such as large optical modulation (61.3%), high coloration efficiency (223.6 cm2 C−1), and high gravimetric capacity (168.1 mAh g−1). In particular, the Ni‐BTA film can maintain its electrochemical recharge‐ability and electrochromic properties even after 10 000 electrochemical cycles demonstrating excellent durability. Moreover, a smart energy storage indicator is demonstrated in which the energy storage states can be visually recognized in real time. The excellent electrochromic and charge storage performances of Ni‐BTA films present a great promise for Ni‐BTA nanowires to be used as practical electrode materials in various applications such as electrochromic devices, energy storage cells, and multifunctional smart windows., A 1D π–d conjugated coordination polymer (CCP) is successfully fabricated in which specific organic linker and metal ions are selected with the aim of increasing the density of redox active centers and enabling conductive paths for charge transport. Moreover, this CCP enables dual electrochromic and energy storage functionalities in an integrated smart device.

van der Waals heterojunctions (vdWHs) formed between 2D materials have attracted tremendous attention recently due to their extraordinary properties, which cannot be offered by their individual components or other heterojunctions. Intriguing electronic coupling, lowered energy barrier, intimate charge transfer, and efficient exciton separation occurring at the atomically sharp interface promise their applications in catalysis, which, however, are largely unexplored. Herein, we demonstrate a 0D/2D vdWH between 0D graphene quantum dots (GQDs) and 2D pristine graphene sheets, simply prepared by ultrasonication of graphite powder using GQDs as intercalation surfactant. Such an all-carbon Schottky-diode-like 0D/2D vdWH is employed for the emerging photoelectrochemical catalysis (water splitting) with high performance. The demonstrated low-cost and scalable bottom-up growth of heteroatom-doped GQDs will greatly promote their widespread applications. Moreover, the mechanisms underlying GQD growth and heterojunction-mediated catalysis are revealed both experimentally and theoretically. Accepted version

Active site number, water dissociation, and hydrogen adsorption free energy are the three main parameters for regulating the activity of electrocatalysts for hydrogen evolution reaction (HER) in alkaline media. However, at present, simultaneous modulations of these three parameters for alkaline HER still remain challenging. In this work, we take CoP as the model material and demonstrate that a metal and nonmetal dual-doping strategy can achieve simultaneous modulation of these three parameters by inducing lattice irregularity and optimizing the electronic configuration in CoP nanomaterials. Benefiting from the oxygen and copper dual-doping collective effect, the optimized O,Cu–CoP nanowire array electrode shows nearly 10-fold enhancement in catalytic activity for alkaline HER compared to a pure CoP nanowire electrode. Our work may provide a new concept to boost performance of nonprecious metal electrocatalysts for alkaline HER.

Optimizing the hydrogen adsorption on electrodes is one of the most effective strategies to promote the hydrogen evolution reaction (HER). In recent years, cobalt phosphides (CoP) have been identified as a promising catalyst for HER in acid. However, the hydrogen adsorption on CoP is strong and a considerable overpotential has to be applied to enable HER. Here, we report a strategy to weaken the hydrogen adsorption on CoP through an electron deficiency in CoP induced by Au@CoP core/shell structure. A weakened hydrogen adsorption is confirmed by the density functional theory (DFT) calculation. Au@CoP gave an overpotential (η) of 160 mV at the current density of 1 mA cm−2CoP, which is about 50 mV less than pure CoP. It also exhibited a turn-over frequency (TOF) value of 0.68 s−1 per active site at η = 150 mV, which is more than 4 times higher than CoP. The strategy reported here holds potential to be extended to other electrodes for optimizing their hydrogen adsorption for HER. NRF (Natl Research Foundation, S’pore) MOE (Min. of Education, S’pore)

Organizing nanoparticles into supercrystals comprising multiple structures remains challenging. Here, we achieve one assembly with dual structures for Ag polyhedral building blocks, comprising truncated cubes, cuboctahedra, truncated octahedra, and octahedra. We create two micro-environments in a solvent evaporation-driven assembly system: one at the drying front and one at the air/water interface. Dynamic solvent flow concentrates the polyhedra at the drying front, generating hard particle behaviors and leading to morphology-dependent densest-packed bulk supercrystals. In addition, monolayers of nanoparticles adsorb at the air/liquid interface to minimize the air/liquid interfacial energy. Subsequent solvent evaporation gives rise to various structurally diverse dual-structure supercrystals. The topmost monolayers feature distinct open crystal structures with significantly lower packing densities than their densest-packed supercrystals. We further highlight a 3.3-fold synergistic enhancement of surface-enhanced Raman scattering efficiency arising from these dual-structure supercrystals as compared to a uniform one., Crystals with multiple structures often perform special functions in nature, inspiring the creation of synthetic analogues. Here, the authors subject polyhedral nanoparticles to two self-assembly micro-environments to realize supercrystals with dual structures, in which the order of the surface layer differs from the bulk structure.

Nitrogen-doped graphenes (NG) fabricated through thermal annealing of graphene oxide (GO) and urea was applied to activate peroxymonosulfate (PMS) for sulfacetamide (SAM) degradation. The contents of reactive functional groups (graphitic N, pyridinic N, pyrrolic N, nitric oxide and C O) and catalytic performance of NG were delicately controlled by adjusting thermal annealing temperature. Thermal annealing temperature of ≥500°C was required to produce the NG endowed with catalytic activity for SAM degradation via PMS activation. NG600 (NG prepared at 600°C) with a high N doping level (16.0 wt%) and a most optimum amount of pyridinic N (38.4%N), pyrrolic N (31.8%N), graphitic N (25.9%N) and C O groups (43.7%O) exhibited the most outstanding catalytic activity to activate PMS. NG600 with the controlled N bonding configurations possessed a higher SAM degradation efficiency than NGs prepared via other optimized synthesis methods The specific surface area (SSA) contributed less significantly than N doping to the SAM degradation performance. Increments in the PMS dosage and catalyst loading were both conducive to the catalytic performance of NG. The presence of NO3− in the NG600/PMS system had a negligible influence on SAM degradation but Cl− and humic acid decreased the SAM degradation rate. Experiments using chemical scavengers and electron paramagnetic resonance (EPR) study revealed that SAM degradation process follows predominantly the radical pathway with sulfate radical (SO4 −) as the main reactive oxygen species over the non-radical pathway. Density functional theory (DFT) calculations suggest that graphitic N can facilitate PMS adsorption on the NG and SAM degradation. This study improves the understanding on the role of different surface N functional groups of NG in the PMS activation.

The peak positions of localized surface plasmonic resonance (LSPR) are strongly dependent on the sizes of metallic nanoparticles. TDDFT calculations have shown a remarkable size effect for metallic nanoparticles smaller than 1 nm, because it could account for fully nonlocal effects. Due to the high resource consumption of TDDFT, several semiquantum approaches have been proposed to reduce the computation time while addressing nonlocal effects, and it is still desirable to introduce new ideas into this area since physical origins of related fields are not completely known yet. In this work, we took account of both spilling out of s-band electrons and the screening effect of d-band electrons in the LSPR phenomena and developed a model using pseudopermittivity to describe several quantum mechanical effects that contribute to nonlocal effects in LSPR. With incorporation of machine learning, this model is capable of calculating the optical response of large nanostructures above the nanometer scale. Besides succ...

Exploring earth-abundant electrocatalysts to realize efficient oxygen evolution reaction (OER) is highly desired for developing sustainable electrochemical energy storage and conversion technologies. Herein, ultrathin single-crystalline Fe-doped nickel thiophosphate (NiPS3) nanosheets prepared in large scale by an easy solid-state method were demonstrated to be highly efficient OER electrocatalysts. The density functional theory (DFT) calculations reveal that the Fe-doping effectively decreases the energy barrier of OER path by reducing the binding of the oxygen-containing species on the surface of NiPS3. As such, the Fe-doped NiPS3 nanosheets show a low overpotential of 256 mV to reach a current density of 30 mA cm−2 and a small Tafel slope of 46 mV dec−1. To our knowledge, this is one of the best OER electrocatalysts in alkaline medium to date. The in-depth mechanism study demonstrates that the in-situ formed Fe-doped nickel oxides/hydroxides shell, resulting from the surface oxidation during the OER process, not only may serve as favorable electrocatalytic species but also improves the chemical stability of the Fe-doped NiPS3 in alkaline electrolyte. This work provides a new perspective for designing highly efficient OER electrocatalysts based on the ternary two-dimensional layered metal thiophosphates. NRF (Natl Research Foundation, S’pore) MOE (Min. of Education, S’pore)

The coupling of the localized surface plasma resonance (LSPR) between noble metals of Au, Ag and Cu and semiconductors of Cu2 xE (E ¼ S, Se, Te) opens new regime to design photothermal (PT) agents with enhanced PT conversion efficiency. However, it is rarely explored on fabricating of engineered dual plasmonic hybrid nanosystem for combinatory therapeutic-diagnostic applications. Herein, rattle-type Au@Cu2 xS hollow mesoporous nanoparitcles with advanced PT conversion efficiency are designed for cellular vehicles and chemo-photothermal synergistic therapy platform. The LSPR coupling between the Au core and Cu2 xS shell are investigated experimentally and theoretically to generate a PT conversion efficiency high to 35.2% and enhanced by 11.3% than that of Cu2 xS. By conjugating microRNA (miRNA) gene probe on the surface, it can realize the intracellular oncogenic miRNA detection. After loading of anticancer drug doxorubicin into the cavity of the Au@Cu2 xS, the antitumor therapy efficacy is greatly enhanced in vitro and in vivo due to the NIR photoactivation chemo- and photothermal synergistic therapy. The rattle-type metal-semiconductor hollow mesoporous nanostructure with efficient LSPR coupling and high cargo loading capability will be beneficial to future design of LSPR-based photothermal agents for a broad range of biomedical application. MOE (Min. of Education, S’pore) Accepted version

Because of their intrinsic geometric structure of vertices, edges, and facets, Platonic nanoparticles are promising materials in plasmonics and biosensing. Their position and orientation often play a crucial role in determining the resultant assembly structures at a liquid/liquid interface. Here, we numerically explored all possible orientations of three Platonic nanoparticles (tetrahedron, cube, and octahedron) and found that a specific orientation (vertex-up, edge-up, or facet-up) is more preferred than random orientations. We also demonstrated their positions and orientations can be quantitatively predicted when the surface tensions dominate their total interaction energies. The line tensions may affect their positions and orientations only when total interaction energies are close to each other for more than one orientation. The molecular dynamics simulation results were in excellent agreement with our theoretical predictions. Our theory will advance our ability toward predicting the final structures of Platonic nanoparticle assemblies at a liquid/liquid interface. MOE (Min. of Education, S’pore) Accepted version

In recent years, organic-based, especially carbonyl-based, Li-ion battery electrode materials have attracted great attention due to their low-cost, environmentally friendly nature and strong Li-ion bonding abilities. However, new research is required to further increase the electron mobility and cycling performance of organic materials. The performance of a high-carbonyl C6O6 molecule-functionalized graphene electrode for Li-ion batteries is investigated using the density functional theory. The binding energy calculations indicate that the C6O6 molecule is adsorbed on graphene via physisorption. C6O6@graphene maintains excellent electronic conductivity with 1 to 6 Li ions. By our statistical method, the reduced voltage of the C6O6@graphene cathode displays a voltage between 2.6 V and 1.5 V with 2 phases from 1 to 6 Li ions with energy density of approximately 155 mA h g−1. The results obtained reveal that C6O6@graphene is a promising electrode material for renewable Li-ion batteries.

Novel nitrogen-doped porous molybdenum carbide (α-MoC1−x and β-Mo2C) architectures were prepared using Mo-based metal–organic frameworks (MOFs) as the precursor. The synthesized molybdenum carbides consist of numerous nanocrystals organized into micro-sized rods with interpenetrating mesoporous-channels and macroporous-tunnels along the axial direction. When employed as the cathode catalyst for Li-O2 batteries, this dual pore configuration offers abundant active sites for the electrochemical reaction and many nucleation sites for the discharge product of Li2O2; hence, decent performances were obtained. Among the two synthesized molybdenum carbides, the α-MoC1−x electrode stands out as being better due to its lower charge transfer resistance (395.8 Ω compared to 627.9 Ω) and better O2 adsorption (binding energy of −1.87 eV of α-(111)-Mo compared to −0.72 eV of β-(101)-Mo). It delivered a high full discharge of 20 212 mA h g−1 with a discharge voltage of 2.62 V at 200 mA g−1. A good cycling stability was also obtained: i.e. 100 stable cycles with a fixed capacity of 1000 mA h g−1 (at a current density of 200 mA g−1) with a charging voltage of 4.24 V and maintaining a respectable round-trip efficiency of ∼70%. NRF (Natl Research Foundation, S’pore) MOE (Min. of Education, S’pore)

To control the process of cation exchange (CE) in a multielemental system, a detailed understanding of structural changes at the microscopic level is imperative. However, the synthesis of a multielemental system has so far relied on the CE phenomenon of a binary system, which does not necessarily extend to the higher-order systems. Here, direct experimental evidence supported by theoretical calculations reveals a growth model of binary Cu–S to ternary Cu–Sn–S to quaternary Cu–Zn–Sn–S, which shows that cations preferentially diffuse along a specific lattice plane with the preservation of sulfuric anionic framework. In addition, we also discover that, unlike the commonly accepted structure (P63mc), the metastable crystal structure of Cu–Zn–Sn–S phase possesses fixed Sn occupancy sites. By revealing the preferential nature of cations diffusion and growth mechanism, our work provides insight into controlling the stoichiometry and phase purity of novel multielemental materials. Ministry of Education (MOE) National Research Foundation (NRF) Accepted version We acknowledge financial support from National Research Foundation (NRF), Singapore, through the Singapore-Berkeley Research Initiative for Sustainable Energy (SinBeRISE) and Nanomaterials for Energy and Water Management (SHARE NEW) CREATE program. L.H.W. thanks the funding support from Singapore Ministry of Education, Tier 2 (2016-T2-1-030). S.L. acknowledges the funding support from Singapore Ministry of Education Tier 1 (107/15). H.Z. thanks the funding support from U.S. DOE BES Materials Sciences and Engineering Division Under Contract No. KC22ZH. X.Y.L. thanks the funding support from Singapore Ministry of Education, Tier 1 (RG21/16) and Tier 2 (MOE2016-T2-1- 043) grants.. The work at the Molecular Foundry was supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. We thank Fiona Doyle for lending us her synthetic laboratory in University of California Berkeley (UCB), Song Chengyu and Karen Bustilo for their help and assistance on TEM, and Matthew P. Sherburne for nanoparticle growth discussion.

We herein report aqueous fabrication of well-defined Au@Cu2–xE (E = S, Se) core@shell dual plasmonic supraparticles (SPs) for multimodal imaging and tumor therapy at the in vivo level. By means of a modified self-limiting self-assembly based strategy, monodisperse core@shell dual plasmonic SPs, including spherical Au@Cu2–xS SPs, Au@Cu2–xSe SPs, and rod-like Au@Cu2–xS SPs, are reliably and eco-friendly fabricated in aqueous solution. Due to plasmonic coupling from the core and shell materials, the as-prepared hybrid products possess an extremely large extinction coefficient (9.32 L g–1 cm–1 for spherical Au@Cu2–xS SPs) at 808 nm, which endows their excellent photothermal effect. Furthermore, the hybrid core@shell SPs possess the properties of good biocompatibility, low nonspecific interactions, and high photothermal stability. So, they show favorable performances for photoacoustic imaging and X-ray computed tomography imaging as well as photothermal therapy of tumors, indicating their application potential...

Shape-controlled polyhedral particles and their assembled structures have important applications in plasmonics and biosensing, but the interfacial configurations that will critically determine their resultant assembled structures are not well-understood. Hence, a reliable theory is desirable to predict the position and orientation of a polyhedron at the vicinity of a liquid/liquid interface. Here we demonstrate that the free energy change theory can quantitatively predict the position and orientation of an isolated octahedral nanoparticle at a liquid/liquid interface, whose vertices and facets can play crucial roles in biosensing. We focus on two limiting orientations of an octahedral nanoparticle, vertex up and facet up. Our proposed theory indicates that the surface wettability (hydrophilic/hydrophobic ratio) of the nanoparticle determines its most stable position and the preferred orientation at a water/oil interface. The surface wettability of an octahedron is adjusted from extremely hydrophobic to extremely hydrophilic by changing the amount of charge on the Ag surface in molecular dynamics (MD) simulations. The MD simulations results are in excellent agreement with our theoretical prediction for an Ag octahedral nanoparticle at a hexane/water interface. Our proposed theory bridges the gap between molecular-level simulations and equilibrium configurations of polyhedral nanoparticles in experiments, where insights from nanoparticle intrinsic wettability details can be used to predict macroscopic superlattice formation experimentally. This work advances our ability to precisely predict the final structures of the polyhedral nanoparticle assemblies at a liquid/liquid interface. NRF (Natl Research Foundation, S’pore) MOE (Min. of Education, S’pore) Accepted version

Photocatalytic solar energy conversion is a clean technology for producing renewable energy sources, but its efficiency is greatly hindered by the kinetically sluggish oxygen evolution reaction. Herein, confined defects in atomically-thin BiOCl nanosheets were created to serve as a remarkable platform to explore the relationship between defects and photocatalytic activity. Surface defects can be clearly observed on atomically-thin BiOCl nanosheets from scanning transmission electron microscopy images. Theoretical/experimental results suggest that defect engineering increased states of density and narrowed the band gap. With combined effects from defect induced shortened hole migratory paths and creation of coordination-unsaturated active atoms with dangling bonds, defect-rich BiOCl nanosheets displayed 3 and 8 times higher photocatalytic activity towards oxygen evolution compared with atomically-thin BiOCl nanosheets and bulk BiOCl, respectively. This successful application of defect engineering will pave a new pathway for improving photocatalytic oxygen evolution activity of other materials.

Regulating the interfacial interaction between fillers and matrices is crucial for fabricating high-performance polymer composites. In this research, a functionalized core–shell hybrid silica@graphene oxide was produced by the charge attraction method, and then added to a trans-1,4-polyisoprene matrix as a neoteric filler to obtain a brand-new silica@graphene oxide/trans-1,4-polyisoprene polymer nanocomposite. The hybrid incorporation simultaneously improved the fracture toughness, mechanical strength and heat resistance of the nanocomposites. We examined the thermal, mechanical and shape memory properties of the nanocomposites via methodical measurements from the microscale to the macroscale. The experimental results demonstrated that, compared with other samples, the nanocomposite sample with 1.0 wt% silica@graphene oxide exhibited the best mechanical and thermal performance, and the fabricated nanocomposites showed good shape memory properties. This new and feasible approach is likely to enable a new strategy for the design of interfaces for developing nanocomposites with high performance.

Though plasmonic effect is making some headway in the energy harvesting realm, its fundamental charge transfer mechanism to a large extent is attributed to the hot-carrier generation at the contact interface. Herein this work attempts to elucidate the physical origin of light induced plasmo-pyroelectric enhancement based on charge density manipulation on surface state in the vicinity of the metal-ferroelectric contact interface. More importantly, by tuning the band bending, it is shown that the charge density on the surface state of a hybrid plasmo-pyroelectric (BaTiO3 -Ag) nanosystem can be manipulated and largely increased under the resonant blue light illumination (363 nm). It is also demonstrated that owing to this effect, the spatial pyroelectric activity of a hybrid plasmo-pyroelectric nanosystem governs 46% enhancement in pyroelectric coefficient. This research highlights the optically regulated charge density in plasmo-pyroelectric nanosystems, which could pave a new avenue for energy harvesting/conversion devices with distinguished advantages in wireless, photonic-controlled, localized, and dynamic stimulation.

Electronic structure greatly determines the band structures and the charge carrier transport properties of semiconducting photocatalysts and consequently their photocatalytic activities. Here, by simply calcining the mixture of graphitic carbon nitride (g-C3 N4 ) and sodium borohydride in an inert atmosphere, boron dopants and nitrogen defects are simultaneously introduced into g-C3 N4 . The resultant boron-doped and nitrogen-deficient g-C3 N4 exhibits excellent activity for photocatalytic oxygen evolution, with highest oxygen evolution rate reaching 561.2 µmol h-1 g-1 , much higher than previously reported g-C3 N4 . It is well evidenced that with conduction and valence band positions substantially and continuously tuned by the simultaneous introduction of boron dopants and nitrogen defects into g-C3 N4 , the band structures are exceptionally modulated for both effective optical absorption in visible light and much increased driving force for water oxidation. Moreover, the engineered electronic structure creates abundant unsaturated sites and induces strong interlayer C-N interaction, leading to efficient electron excitation and accelerated charge transport. In the present work, a facile approach is successfully demonstrated to engineer the electronic structures and the band structures of g-C3 N4 with simultaneous introduction of dopants and defects for high-performance photocatalytic oxygen evolution, which can provide informative principles for the design of efficient photocatalysis systems for solar energy conversion.

The inorganic halide perovskite CsPbI3 has shown great promise for efficient solar cells, but the instability of its cubic phase remains a major challenge. We present a route for stabilizing the cubic α-phase of CsPbI3 through the control of vacancy defects. Analysis of the ionic chemical potentials is performed within an ab initio thermodynamic formalism, including the effect of solution. It is found that cation vacancies lead to weakening of the interaction between Cs and PbI6 octahedra in CsPbI3, with a decrease in the energy difference between the α- and δ-phases. Under I-rich growth conditions, which can be realized experimentally, we predict that the formation of cation vacancies can be controlled. Other synthetic strategies for cubic-phase stabilization include the growth of nanocrystals, surface capping ligands containing reductive functional groups, and extrinsic doping. Our analysis reveals mechanisms for polymorph stabilization that open a new pathway for structural control of halide perovskites. This work is supported as part of the fundamental research project “Design of Innovative Functional Materials for Energy and Environmental Application” (no. 2016-20) funded by the State Committee of Science and Technology, DPR Korea. The work in the UK has been supported by the Royal Society and the Leverhulme Trust.

Heterostructures with abundant phase boundaries are compelling for surface-mediated electrochemical applications. However, rational design of such bifunctional electrocatalysts for efficient hydrogen and oxygen evolution reactions (HER and OER) is still challenging. Here, due to the well-matched lattice parameters, we easily achieved the epitaxy of two-dimensional ternary nickel thiophosphate (NiPS3) nanosheets with in-grown dinickel phosphide (Ni2P) through an in situ growth strategy. Density functional theory calculations reveal that the NiPS3/Ni2P heterojunction significantly decreases the kinetic barrier for hydrogen adsorption and accelerates electron transfer due to the built-in electric field at the epitaxial interfaces. The significantly improved electrocatalytic performance is shown to be closely related to the epitaxial interfacial area rather than the amount of secondary phase. Notably, the resultant NiPS3/Ni2P heterostructures enable an overall water splitting electrolyzer to achieve 50 mA cm–2 at a lower bias of 1.65 V compared to that for the pristine NiPS3 alone (2.02 V) and even the benchmark Pt/C//IrO2 electrocatalysts (1.69 V). MOE (Min. of Education, S’pore) Accepted version

Nanoscale zero-valent iron has been widely applied in environmental remediation and toxic waste treatment, especially for the degradation of persistent organic pollutants (POPs). However, the dechlorination activity of Fe nanoparticles (Fe NPs) can be suppressed by the precipitation of iron oxides generated from the corrosion of Fe-Pd NPs under alkaline conditions, leading to a decreased dechlorination efficiency. Faced with this challenge, we report a highly effective dechlorination system that functions over a broad pH range and especially well under alkaline conditions in this work. Procyanidin (PROC), a natural polyphenol, was utilized as a stabilizer to manipulate the size distribution of Fe-Pd NPs and, more importantly, as a scavenger of Fe ions to prevent iron oxide precipitation. Experiments and theoretical calculations reveal that the generated Fe ions was mainly present in the form of bis- and tris-PROC-Fe complexes in the reaction solution. Compared with pristine Fe-Pd NPs, the PROC-modified Fe-Pd NPs had a dechlorination efficiency that was increased 20-fold (pH 9.0). Notably, a normalized rate constant was enhanced by more than 2 orders of magnitude compared to the previously reported dechlorination systems. The PROC-modified Fe-Pd NPs showed excellent dechlorination efficiency over a wide pH range (2.3–13.0). Nanyang Technological University This work was supported by the National Natural Science Foundation of China (21621004, 51473115, 21776212), Tianjin Municipal Science and Technology Bureau, China (16JCZDJC37900, 18YFHBZC00010, 18YFZCSF00590), and the Ministry of Education (grant No. NCET-11-0372). JY thanks to a start-up grant of NTU, M4082049.070.

Photocatalytic CO2 reduction has been regarded as an appealing pathway for CO2 conversion to hydrocarbon fuels. To boost the CO2 photoreduction performance, developing suitable cocatalyst on the photocatalysts is an efficient strategy. Herein, Co2N is employed as novel noble-metal-free cocatalyst to promote the CO2 photoreduction performance of BiOBr ultrathin nanosheets. The optimal Co2N/BiOBr delivers a high selectivity CO formation rate of 67.8 µmol g−1 h−1 in pure water without sacrificial reagent or extra photosensitizer, roughly 6 times higher than BiOBr. Co2N can create strong electronic interactions with BiOBr, steering the electron transfer from BiOBr, across the interface to metallic Co2N and finally to the surface. Apart from the charge separation steering, the activation energy barrier can be lowered on Co2N surface via stabilize COOH* intermediates, tuning the rate-limiting step from the formation of COOH* on BiOBr to the formation of CO* on Co2N, jointly optimize the CO2 photoreduction activity. This strategy affords an accessible pathway for designing cocatalysts for efficient CO2 photoreduction.

The poor environmental stability of organometallic halide perovskite solar cells presents a big challenge for its commercialization, which is mainly due to the degradation of perovskite materials in humid air. The role played by water molecules has been extensively studied in the degradation processes, where strong interactions between water molecules and perovskite surfaces are found. Using first-principles simulations, we find that oxygen molecules also have strong interactions with (001) surfaces of tetragonal CH3NH3PbI3 through the formation of a chemical Pb–O bond on the PbI2-terminated surface and a hydrogen bond on the CH3NH3I-terminated surface. The adsorbed oxygen molecules introduce empty states near the Fermi level of the surfaces, which can facilitate charge transfer between the surface and oxygen molecules. Furthermore, when an oxygen molecule is located atop a Pb atom on PbI2-terminated surface, the calculated adsorption energies indicate that the surface is more attractive to water molecule...

We have predicted extremely high electromagnetic hot spots using the extended–localized coupled surface plasmon resonance configuration. With this unique configuration, we found that an array of particles shows the critical importance of the interparticle gap on the enhancement factor, which was confirmed experimentally using surface-enhanced Raman scattering (SERS). The extended plasmon wave excited in the Kretschmann–Raether configuration propagates on the silver film surface and couples with the gold nanoparticles dispersed on top through excitation of the localized plasmons. A monomolecular layer of 4-aminothiophenol sandwiched between the metal film and the nanoparticles showed an SERS enhancement factor of the order of 1010 per molecule in the hot spots. The configuration was optimized, both by simulations and experiments, with respect to the size of the nanoparticles and the interparticle distances. It is demonstrated that the ultrahigh SERS enhancement does occur only when the extended surface pla...

Metal-organic frameworks (MOFs) have drawn increasing attentions as promising candidates for functional devices. Herein, we present MOF films in constructing memory devices with alcohol mediated resistance switching property, where the resistance state is controlled by applying alcohol vapors to achieve multilevel information storage. The ordered packing mode and the hydrogen bonding system of the guest molecules adsorbed in MOF crystals are shown to be the reason for the alcohol mediated electrical switching. This chemically mediated memory device can be a candidate in achieving environment-responsive devices and exhibits potential applications in wearable information storage systems. ASTAR (Agency for Sci., Tech. and Research, S’pore) MOE (Min. of Education, S’pore) Accepted version

Current microscale tracking of chemical kinetics is limited to destructive ex situ methods. Here we utilize Ag nanocube-based plasmonic liquid marble (PLM) microreactor for in situ molecular-level identification of reaction dynamics. We exploit the ultrasensitive surface-enhanced Raman scattering (SERS) capability imparted by the plasmonic shell to unravel the mechanism and kinetics of aryl-diazonium surface grafting reaction in situ, using just a 2-μL reaction droplet. This reaction is a robust approach to generate covalently functionalized metallic surfaces, yet its kinetics remain unknown to date. Experiments and simulations jointly uncover a two-step sequential grafting process. An initial Langmuir chemisorption of sulfonicbenzene diazonium (dSB) salt onto Ag surfaces forms an intermediate sulfonicbenzene monolayer (Ag-SB), followed by subsequent autocatalytic multilayer growth of Ag-SB3. Kinetic rate constants reveal 19-fold faster chemisorption than multilayer growth. Our ability to precisely decipher molecular-level reaction dynamics creates opportunities to develop more efficient processes in synthetic chemistry and nanotechnology.

Label-free and real time far-field super-resolution imaging (hyperlensing) at the nanoscale is of significant interest where sub-λ imaging remains a constraint because of Abbe's diffraction limit. Though by utilizing anisotropic permittivities, metal-dielectric multilayers have been successful in reconstructing high-frequency components of sub-λ objects, yet they remain cumbersome and expensive to make. Most of the multilayer structures require multiple vacuum deposition cycles and are plagued by stringent requirements on the surface roughness of metallic layers. In contrast to the multilayer structure here we propose a 3D hyperbolic metamaterial model composed of metallic nanorods arranged in a sea-urchin geometry as a hyper-lensing device, which is capable of projecting and magnifying diffraction limited information into the far-field at Near-infrared (NIR) frequencies. The hyperlens generates a band of flat hyperbolic dispersions in spherical coordinates, which in turn supports the propagation of high wave-vector spatial harmonics leading to far-field super-resolution imaging. Using full-wave finite-difference time-domain (FDTD) simulations with diffraction limited trimer, quadrumer and ringed objects etched on thin perfect electric conductor (PEC) films, we show that the hyperlens model can achieve magnification factors of up to 10× in the far-field (∼4.5λ from the object's surface) under a light source with a wavelength of 1 μm, with successful resolution down to 220 nm (∼λ/5). The magnified image field distribution projected into the far-field is shown to follow the object under a reduction in the symmetry. These results are important for making progress in the realization of real-time biomolecular imaging systems, eliminating the need for near-field scanning, destructive electron microscopy and various image post-processing techniques.