Surface Charge State Research Articles

ZnSe and CdS Co-Sensitized TiO2 Nanorod Arrays as Photoanodes for Bias-Free Solar Hydrogen Evolution.

The efficient charge separation and surface state reactions are significant in enhancing the efficiency of photoelectrochemical hydrogen evolution. Herein, we report a ternary heterostructure consisting of CdS/ZnSe sensitized TiO2 nanorod as a photoanode. The heterojunction photoanode considerably widens the photon absorption spectral range and thereby enhances the photocurrent density up to 2 mA/cm2 at 1.23 V versus RHE which is 10 times higher than pristine TiO2 photoanode. The photoelectrochemical results demonstrate a high photocurrent density of 2 mA/cm2 with a photon-to-current conversion efficiency of 1.5 % at a very low applied bias (0.2 V vs RHE). The improved PEC performances of the multidimensional hybrid photoanode could be ascribed to the efficient visible-light absorption of ZnSe and CdS nanocrystals decorated on the surface of 1D TiO2 . The rapid electron-transfer properties owing to higher carrier density, low carrier transport resistance, and an extended lifetime of photoexcited carriers in the multidimensional ZnSe/CdS/TiO2 heterostructure with suppressed surface charge recombination are responsible for enhanced hydrogen evolution activities.

Carbon defective g-C3N4 thin-wall tubes for drastic improvement of photocatalytic H2 production

Both morphology and defects play a vital role for boosting photocatalytic efficiency. Herein, a vapor-assisted surface reconstruction was developed to synthesize g-C3N4 thin-wall tubes with carbon defects. The significantly reduced wall thickness delivers rich disclosed active sites, ensures efficient the mass transport as well as suppresses interior recombination of photoexcited carriers. The intentionally introduced carbon defects in the heptazine rings owing to the altered surface charge state, optimizes the band structure and suppresses exterior recombination of photoexcited carriers. The resultant g-C3N4 with vigoroso reduction potential possess a tremendous improvement (25-fold) for H2 production under visible light, which outperforms the majority of the previously reported g-C3N4 tubes. With pressing research demands, the functionality of vapor-assisted surface reconstruction was deeply revealed by theoretical and experimental evidences. This clean strategy enriches the rational design of high-performance g-C3N4 photocatalysts.

Quadratic nodal line phonon with hybrid type in hexagonal compound SrCuSi

Topological phononics emerges as a new research field with the expansion of topological concept from the conventional electronic fermions. Even with a lot of common features, topological phononic states still exhibit many distinct properties. With the continuous development, the current research has even been further extended into high order dispersion conditions. Compared with the traditional linear dispersion, high order topological elements can feature very exotic behaviors, such as high topological charge and chiral surface states, and thus have attracted a lot of research attention. In this work, based on theoretical calculation and effective model analysis, we present an ideal quadratic nodal line phonon in the hexagonal compound SrCuSi. With the symmetry enforced protection, this nodal line also shows an interesting hybrid type combination. Moreover, prominent surface states with large separation from the bulk band can be very beneficial for further experimental investigation. Our theoretical results can immediately advance the relative studies in topological phononics and, especially, the proposed material can put forward an effective way to examine the topological nodal line phonon with quadratic order or hybrid type.

Spontaneous heteroassembly of 2D semiconducting van der Waals materials in random solution phase

van der Waals heterostructures (vdWHs), consisting of more than one type of atomically thin 2D crystal layers are emerging platforms for interesting electrical, optical, and catalytic applications. High yield production of vdWHs with atomic scale precision is crucial prerequisite for practical utilization. Here we present a generalized approach of random solution phase, high yield heteroassembly of semiconducting vdWHs by exploiting inherent surface charge states of 2D materials as well as chemical affinity of specific ligand end-functionalities. Facile removal of noncovalent functionalized ligands via simple pH reversal enables clean interfaces within vdWHs, yielding outstanding optoelectrical and electrochemical properties driven by fluent interfacial charge transfer among the layered 2D structures. The generality of this procedure is demonstrated by the formation of a series of different vdWHs such as WSe2-MoS2, graphene–MoS2 - and phospherene–WSe2 heterostructures. Atomically thin WSe2–MoS2 phototransistor displayed an exceptionally fast response time with high sensitivity. Graphene–MoS2 overcomes the inherent charge transfer issue of MoS2 for electrochemical catalyst. Phospherene–WSe2 successfully addresses poor ambient stability of phospherene together with enhanced surface activity towards chemical sensing.

Interfacial engineering boosting charge extraction for efficient photocatalytic hydrogen evolution

In heterostructure photocatalyst, metal–support interaction plays a key role in determining the photocatalytic reaction, which is rarely studied due to its complicated mechanism involving interfacial bonding, internal electric field, and charge transfer etc. Here we report an interfacial engineering to promote the photocatalytic hydrogen evolution of the model photocatalyst Pt/TiO2. A stable oxidized Cu+ layer was inserted as an interlayer between Pt nanoparticles and TiO2 support, which boosts the efficiency of photoinduced charge extraction and regulates the surface charge state of the photocatalyst. The synthesized photocatalyst Pt/Cu/TiO2 exhibits highly efficient hydrogen evolution of 1 L g−1h−1, which is 63% higher than the photocatalyst Pt/TiO2. This charge extraction strategy is also evidenced on photocatalysts Pt/(Rh, Co or Ni)/TiO2. Our findings not only provide insight into interfacial interaction in photocatalyst, but also offer effective guidelines for the design and fabrication of high-performance photocatalysts.

(Keynote) Deciphering Electrocatalytic Reactions with Theory and Computation: The Case of CO2 Reduction

The interfacial region between metal surface and aqueous electrolyte is of central importance for electrochemical reactions. The need to understand the properties of this electrochemical double layer (EDL) region drives extensive research.1,2 A foremost goal of research in electrocatalysis is the development of a theoretical-computational framework. The fundamental task for such a framework is to unravel the complex interplay of electronic structure effects of the catalyst material, potential-induced variations of the chemisorption state, local reaction conditions on the electrolyte side, and electrochemical kinetics of reactions of interest. A recently developed theoretical approach revealed the non-monotonic charging behaviour of a Pt electrode3 and it was thereafter used to decipher the oxygen reduction reaction.4 In the present work, we adapt this approach to study how the local reaction environment dictates the mechanism and kinetics of reduction to CO at an Ag electrode. Our hierarchical model accounts for the multistep reaction kinetics of surface reactions, local chemical equilibria (involving CO2, HCO3 -, CO3 2-, OH-, H+), the specific surface charging state at a given electrode potential, solvent polarization and ion density variations, and reactant/product transport. It integrates interface and pore-level models to account for this interplay. The combined approach rationalizes the impact of the considered effects on the kinetics of the reaction, manifested experimentally in changes of the effective Tafel slope as a function of electrode potential. Lateral interactions between chemisorbed species are seen to contribute to the decrease of the CO current density at high electrode potentials, in addition to mass transport effects, surface charging effects and pH increase. We will conclude with a discussion of the parameters that allow tuning the local reaction environment and thus the electrocatalytic activity and selectivity of the electrocatalyst. 1O.M. Magnussen and A. Gross, Toward an Atomic-Scale Understanding of Electrochemical Interface Structure and Dynamics, J. Am. Chem. Soc. 141, 4777–4790 (2019). 2M.J. Eslamibidgoli and M.H. Eikerling, Approaching the Self-consistency Challenge of Electrocatalysis with Theory and Computation, Current Opinion in Electrochemistry 9, 189-197 (2018). 3J. Huang, A. Malek, J. Zhang and M.H. Eikerling, Non-monotonic Surface Charging Behavior of Platinum: A Paradigm Change, J. Phys. Chem. C 120, 13587-13595 (2016). 4J. Huang, J. Zhang and M. Eikerling, Unifying Theoretical Framework for Deciphering the Oxygen Reduction Reaction on Platinum, Phys. Chem. Chem. Phys. 20, 11776-11786 (2018).

Persistence of correlation-driven surface states in SmB6 under pressure

The proposed topological Kondo insulator SmB$_{6}$ hosts a bulk Kondo hybridization gap that stems from strong electronic correlations and a metallic surface state whose effective mass remains disputed. Thermopower and scanning tunneling spectroscopy measurements argue for heavy surface states that also stem from strong correlations, whereas quantum oscillation and angle-resolved photoemission measurements reveal light effective masses that would be consistent with a Kondo breakdown scenario at the surface. Here we investigate the evolution of the surface state via electrical and thermoelectric transport measurements under hydrostatic pressure, a clean symmetry-preserving tuning parameter that suppresses the Kondo gap and increases the valence of Sm from 2.6+ towards a 3+ magnetic metallic state. Electrical resistivity measurements reveal that the surface carrier density increases with increasing pressure, whereas thermopower measurements show an unchanged Fermi energy under pressure. As a result, the effective mass of the surface state charge carriers linearly increases with pressure as the Sm valence approaches 3+. Our results are consistent with the presence of correlation-driven surface states in SmB$_{6}$ and suggest that the surface Kondo effect persists under pressure to 2 GPa.

Surface State-Assisted Delayed Photocurrent Response of Au Nanocluster/TiO2 Photoelectrodes.

Gold nanoclusters (NCs) can be used as sensitizers to extend the absorption capabilities of TiO2 as photoelectrodes. However, the adsorption of NCs also creates additional surface states on the TiO2 surface, which gives rise to intricacies in the understanding of various interfacial phenomena occurring in NC-sensitized TiO2. One of the complexities that have recently been discovered is the size-dependent hole-transfer mechanism. In this work, we reveal another anomalous behavior in the hole-transfer process that the hole scavenging ability of the electrolyte also plays a role in determining the hole-transfer mechanism in the NC-TiO2 system, which is unprecedented in other photoelectrode systems. In the presence of an efficient hole scavenger (Na2SO3), the hole transfer in Au18-TiO2 occurs directly through the highest occupied molecular orbital (HOMO) of Au18 NCs. However, in the presence of a less efficient hole scavenger (ethylenediaminetetraacetic acid), hole transfer in Au18-TiO2 does not occur through the HOMO and shifts to surface state-assisted hole transfer. Due to surface state charging, this surface state-assisted hole-transfer mechanism results in delayed photocurrent response in Au18-TiO2. Evidence for this exotic hole-transfer mechanism shift is provided by photoelectrochemical electrochemical impedance spectroscopy, and its implications are discussed.

The interfacial interactions of nanomaterials with human serum albumin.

The fates of nanomaterials (NMs) in vivo are greatly dependent on their interactions with human serum proteins. However, the interfacial molecular details of NMs-serum proteins are still difficult to be probed. Herein, the molecular interaction details of human serum albumin (HSA) with Au and SiO2 nanoparticles have been systematically interrogated and compared by using lysine reactivity profiling mass spectrometry (LRP-MS). We demonstrated the biocompatibility of Au is better than SiO2 nanoparticles and the NMs surface charge state played a more important role than particle size in the combination of NMs-HSA at least in the range of 15-40nm. Our results willcontribute to the fundamental mechanism understanding of NMs-serum protein interactions as well as the NMs rational design.

Regulation of the Structure of Zirconium-Based Porphyrinic Metal-Organic Framework as Highly Electrochemiluminescence Sensing Platform for Thrombin.

An electrochemiluminescence (ECL) sensor provides a sensitive and convenient method for early diagnosis of diseases; however, it is still a challenge to develop simple and sensitive sensing platforms based on efficient ECL signals and luminophore groups. Porphyrin-based metal-organic frameworks (MOFs) show great potential in ECL sensing; however, the mechanism and structure-activity relationship, as well as application, are rarely reported. Herein, hydrothermal reactions obtained porphyrin Zr-MOFs (PCN-222) with different specific surface areas, pore sizes, structures, and surface charge states by tuning the reaction time were developed, which served both as the ECL luminophore, coreaction promoter for S2O82-, and a connection in the ECL immunoassay. By progressively controlling the condition of the hydrothermal reaction, PCN-222 with large surface area-abundant micropores can be obtained, which has good conductivity and positively charged surfaces, obtaining excellent ECL performance. The ECL performance and the enhancement mechanism were investigated in detail. Using PCN-222-6h with the best ECL intensity as the immobilization matrix for the aptamer, a highly sensitive and selective assay for thrombin was developed. The decrease of the ECL signal was logarithmically linear with the concentration of thrombin in the range from 50 fg mL-1 to 100 pg mL-1 with a low detection limit of 2.48 fg/mL. This proposed strategy provides a brand new approach for tuning of the structures of MOFs as effective ECL signal probes, thus providing wider possibilities for effective ECL immunoassays in the detection of other biomarkers in diagnosis of diseases.

Sensing mechanism of acetone adsorption on charged ZnO and ZnSe surfaces: Insights from DFT calculations

Acetone sensing is meaningful for human health, food safety and animal safety. In this work, the sensing mechanism of acetone adsorption on charged II-VI semiconductor (ZnO and ZnSe) is systematically investigated by density functional theoretical calculations. It is found that compared with charged ZnO surfaces, charged ZnSe surfaces possess stronger acetone adsorption strength. Both positive and negative surface charges could enhance acetone sensing of ZnO surface while only negative surface charges could enhance acetone sensing on ZnSe surface. The appropriate charge states of ZnO or ZnSe are of significance to realize fast recovery. Because acetone desorption process could be endothermic with added energy under some charge states. Additionally, the acetone selectivity of sensing surface could be controlled by surface charge states. Moreover, acetone sensing could be effectively improved by the synergistic effect of surface charge states and ZnSe/ZnO heterostructures. Our results extend the knowledge into the acetone sensing mechanisms induced by surface charge states.

Tuning charge distribution of Ru nanoparticles via coupling ammonium tungsten bronze as Pt-Like electrocatalyst for hydrogen evolution reaction

Reasonable structure design and fine electronic modulation are the keys to achieving the platinum-like hydrogen evolution reaction (HER) performance on Ru-based catalyst, but also challenges. Here, the integration of uniformly dispersed ultra-fine Ru nanoparticles with β-hexagonal ammonium tungsten bronze (β-HATB) nanowires is reported as an efficient acidic electrocatalyst. Due to the strong metal-support interaction, the surface charge state of Ru is effectively regulated, forming a mixed valence state composed of zero valence and offset state. The prepared Ru@β-HATB/CC exhibits a Pt-like catalytic activity with a small overpotential of 25 mV and a very low Tafel slope of 27.6 mV dec−1. In-situ Raman spectroscopy and electrochemical analysis reveal that β-HATB does not directly participate in HER reaction and hydrogen spillover effect (Hads from β-HATB to Ru NPs) is not the main reason for the hydrogen evolution activity, but β-HATB can optimize the kinetics of hydrogen adsorption/desorption behavior on Ru surface and provide a stable and fast charge transfer channel, thus improving HER activity.

Fluorescence of nanodiamond cocktails: pH-induced effects through interactions with comestible liquids

Fluorescent nanodiamonds with nitrogen-vacancy centers have become important nanoscale probes for sensing and imaging. The surface chemistry of the nanodiamonds influences their emission, interactions, and quantum properties. In this work, we propose to utilize fluorescent nanodiamonds as photostable markers for investigation of comestible liquids. We prepared nanodiamond/comestibles suspensions/cocktails with a wide range of pH levels and studied the samples via fluorescence, wettability, and zeta potential. The composition of the created cocktails revealed a strong impact on the properties of the nanodiamond and its surface chemistry, mainly induced by pH but also tuned by specific quenching compounds. Moreover, the stability of the nanodiamonds in the cocktail media was studied, along with various nature-originated compounds influencing their surface termination, polarity, and charge states. Thanks to the stability and biocompatibility of the nanodiamond, it can be applied in monitoring the condition of foodstuffs, and in the detection of toxins and pathogens in them.

Synthesis, Characterization, and Antifungal Activity of Silver Nanoparticles Embedded in Pullulan Matrices.

Steady developments made in nanotechnology-based products have facilitated new perspectives for combating drug-resistant fungi. Silver nanoparticles represent one of the most attractive nanomaterials in biomedicine due to their exclusive optical, electromagnetic, and catalytic properties and antifungal potency compared with other metal nanoparticles. Most studies show that the physicochemical parameters affecting the antifungal potential of AgNPs include the shape, size, surface charge, and concentration and colloidal state. For the present study, pullulan (P) and its oxidized counterpart (PO) have been selected as matrices for the silver nanoparticles’ generation and stabilization (AgNPs). The TEMPO (2,2,6,6-tetramethylpiperidin-1-yl radical)–sodium hypochlorite–sodium bromide system was used for the C6 selective oxidation of pullulan in order to introduce negatively charged carboxylic groups in its structure. The structure and morphology of the synthesized AgNPs were analyzed using FTIR and EDX. The main objective of this study was to elucidate the antifungal activity of AgNPs on the clinical yeasts isolates and compare the performance of AgNPs with the conventional antifungals. In this study, different concentrations of AgNPs were tested to examine antifungal activity on various clinical isolates.

Electrochemical CO2 Reduction at Silver from a Local Perspective

The electrochemical reduction of CO2 to chemical fuels and value-added chemicals is a viable pathway to store renewably generated electrical energy and to mitigate the negative impact of anthropogenic CO2 production. Herein, we study how the local reaction environment dictates the mechanism and kinetics of CO2 reduction to CO at an Ag electrode. The local reaction environment is determined using a hierarchical model that accounts for multistep reaction kinetics, specific surface charging state at a given electrode potential, and mass transport phenomena. The model reveals vital mechanistic insights into the reaction behavior. The increasing Tafel slope with overpotential is seen to be influenced by the surface charging relation and mass transport effects. In addition, the decrease of the CO current density at high overpotentials is found to be caused not only by the decrease in CO2 concentration due to mass transport, surface charge effects, and pH increase but also by lateral interactions between HCOOad, COOHad, and Had. Moreover, we explore how the electrolyte properties, including bicarbonate concentration, solvated cation size, and CO2 partial pressure, tune the local reaction environment.

Key Parameters That Determine the Magnitude of the Decrease in Current in Nanopore Blockade Sensors.

Nanopore blockade sensors were developed to address the challenges of sensitivity and selectivity for conventional nanopore sensors. To date, the parameters affecting the current of the sensor have not been elucidated. Herein, the impacts of nanopore size and charge and the shape, size, surface charge, and aggregation state of magnetic nanoparticles were assessed. The sensor was tolerant to all parameters contrary to predictions from electronic or geometric arguments on the current change. Theoretical models showed the greater importance of the polymers around nanoparticles and the access resistance of nanopores to the current, when compared with translocation-based nanopore sensors. The signal magnitude was dominated by the change in access resistance of ∼4.25 MΩ for all parameters, resulting in a robust system. The findings provide understandings of changes in current when nanopores are blocked, like in RNA trapping or nanopore blockade sensors, and are important for designing sensors based on nanopore blockades.

Elucidating the Surface Chemistry of Atomic Layer Deposition on Complex Metal Oxide Cathode Materials

Current research in the field of lithium-ion batteries (LIBs) is geared towards stabilizing the electrode-electrolyte interfaces to improve the LIB cycling stability and storage capacity. In particular, irreversible reactions between non-aqueous electrolytes and metal oxide cathode surfaces can corrode the active material and reduce LIB performance. Protective coatings on the cathode surface can mitigate these issues, and atomic layer deposition (ALD) is well-suited to prepare ultrathin, conformal, corrosion-resistant barrier layers on the surface of the electrodes. While there are reports that some metal oxide and metal fluoride barrier coatings on select cathodes can improve LIB performance, there is no general understanding of why certain ALD coating/cathode combinations are beneficial while others are not. This problem is complicated by the move towards complex LIB cathodes such as lithium nickel manganese cobalt oxide (NMC) materials that may have multiple phases present on the surface including hydroxides and carbonates. Understanding how the ALD precursors react on these materials to create protective coatings is challenging and requires a systematic study to elucidate the surface chemistry of the ALD precursors with each component of the complex oxide surface. Therefore, this work aims at understanding the effects of ALD precursor exposures and ALD coatings on the surface electronic structure of LIB cathode materials.Al2O3 and AlF3 were selected as prototypical metal oxide and metal fluoride surface coatings as they are widely reported in literature due to their ability to act as barrier coatings on cathodes. Additionally, the ALD precursor vapors used for these coatings, i.e., trimethyl aluminium (TMA) and hydrogen fluoride pyridine (HFpy), were adsorbed on the surfaces of these cathode materials under typical ALD conditions to observe their effect on the surface composition and electronic state. The cathode materials chosen for this study included all of the component oxides for NMC cathodes (i.e. Li, Ni, Mn, and Co) in all common oxidation states (e.g., MnO, MnO2, and Mn2O3) as well as selected ternary, quaternary, and quinary forms. In each case, the substrate surface was characterized using X-ray photoelectron spectroscopy (XPS) before and after surface treatment to elucidate changes in the surface composition and charge state induced by the individual ALD precursors and the ultrathin coating. Overall, this fundamental study will assist in the design and synthesis of novel ALD barrier coatings that demonstrate the highest sensitivity on multi-element cathode materials, ultimately leading to robust electrode-electrolyte interfaces for high-performance LIBs.

Surficial charge state tuning of tungsten carbide for catalyzing alkaline hydrogen evolution reaction

Rational tuning the surface charge state for catalysts is an attractive strategy to promote their catalytic activity toward catalyzing diverse chemical and electrochemical reactions. In this work, we modified the surface of a pure tungsten carbide (WC) material with an ultra-thin nitrogen doped carbon (NC) layer (WC@NC) for catalyzing alkaline hydrogen evolution reaction (HER). The XPS studies revealed an increased electron density on WC when the NC layer was introduced on its surface. Thus, a significant decrease of 282 mV in overpotential at 10 mA cm−2 was observed on WC@NC electrode in comparison with the pristine WC electrode. The higher electrochemical active surface area, lower activation energy barrier, and excellent durability were identified by various electrochemical measurements. The three-dimensional charge density difference was also calculated and the results indicated that an electron-transfer process occurred from the NC layer (donor) to the WC layer (acceptor) through the interface of WC@NC composite material. The analysis explained the underlying mechanism for the promotion of the HER activity. Such a comprehensive study is expected to provide useful guidance for promoting the catalytic performance of diverse catalysts toward different reactions.

Surface states regulation of sulfide-based photoanode for photoelectrochemical water splitting

Regulating the surface states distribution on the photoanode/electrolyte interface is crucial to photoelectrochemical (PEC) water splitting. Here we develop a CdIn2S4/InOx/NiFe-LDH adaptive junction to improve the PEC performance and stability of bare CdIn2S4, which achieves a photocurrent density of 5.47 mA cm−2 at 1.23 VRHE as well as good durability under AM 1.5G illumination without sacrificial reagent. The experimental characterizations evidence that both the charge carrier density (Nd) and surface states distribution (Nss) alter along with the interfacial structural regulation in the CdIn2S4/InOx/NiFe-LDH photoanode, and a proper ratio of Nss/Nd guarantee the optimal photocurrent. Meanwhile, a strained surface states distribution and negative shifted Nss center facilitate the charge transfer and interfacial water oxidation kinetics as well. This work highlights the influence of interfacial structural regulation on the entangled surface states distribution and charge carrier density and may inspire more excellent work on designing other efficient photoanodes.

Gate Alignment of Liquid Water Molecules in Electric Double Layer.

The behavior of liquid water molecules near an electrified interface is important to many disciplines of science and engineering. In this study, we applied an external gate potential to the silica/water interface via an electrolyte-insulator-semiconductor (EIS) junction to control the surface charging state. Without varying the ionic composition in water, the electrical gating allowed an efficient tuning of the interfacial charge density and field. Using the sum-frequency vibrational spectroscopy, we found a drastic enhancement of interfacial OH vibrational signals at high potential in weakly acidic water, which exceeded that from conventional bulk-silica/water interfaces even in strong basic solutions. Analysis of the spectra indicated that it was due to the alignment of liquid water molecules through the electric double layer, where the screening was weak because of the low ion density. Such a combination of strong field and weak screening demonstrates the unique tuning capability of the EIS scheme, and would allow us to investigate a wealth of phenomena at charged oxide/water interfaces.