Porous 2D Catalyst Covers Improve Photoelectrochemical Water-Oxidation Performance.

Confined catalysis under the cover of 2D materials has emerged as a promising approach for achieving highly effective catalysts in various essential reactions. In this work, a porous cover structure is designed to boost the interfacial charge and mass transfer kinetics of 2D-covered catalysts. The improvement in catalytic performance is confirmed by the photoelectrochemical oxidation evolution reaction (OER) on a photoanode based on an n-Si substrate modified with a NiOx thin-film model electrocatalyst covered with a porous graphene (pGr) monolayer. Experimental results demonstrate that the pGr cover enhances the OER kinetics by balancing the charge and mass transfer at the photoanode and electrolyte interface compared to the intrinsic graphene cover and cover-free control samples. Theoretical investigations further corroborate that the pore edges of the pGr cover boost the intrinsic catalytic activity of active sites on NiOx by reducing the reaction overpotential. Furthermore, the optimized pores, which can be easily controlled by plasma bombardment, allow oxygen molecules produced in the OER to pass through without peeling off the pGr cover, thus ensuring the structural stability of the catalyst. This study highlights the significant role of the porous cover structure in 2D-covered catalysts and provides new insight into the design of high-performance catalysts.

A facile covalent strategy for ultrafast negative photoconductance hybrid graphene/porphyrin-based photodetector.

As a powerful complement to positive photoconductance (PPC), negative photoconductance (NPC) holds great potential for photodetector. However, the slow response of NPC relative to PPC devices limits their integration. Here, we propose a facile covalent strategy for an ultrafast NPC hybrid 2D photodetector. Our transistor-based graphene/porphyrin model device with a rise time of 0.2 ms and decay time of 0.3 ms has the fastest response time in the so far reported NPC hybrid photodetectors, which is attributed to efficient photogenerated charge transport and transfer. Both the photosensitive porphyrin with an electron-rich and large rigid structure and the built-in graphene frame with high carrier mobility are prone to the photogenerated charge transport. Especially, the intramolecular donor-acceptor system formed by graphene and porphyrin through covalent bonding promotes photoinduced charge transfer. This covalent strategy can be applied to other nanosystems for high-performance NPC hybrid photodetector.

Modification of interface and electronic transport in van der Waals heterojunctions by UV/O3.

Two-dimensional (2D) van der Waals heterojunctions have many unique properties, and energy band modulation is central to applying these properties to electronic devices. Taking the 2D graphene/MoS2heterojunction as a model system, we demonstrate that the band structure can be finely tuned by changing the graphene structure of the 2D heterojunction via ultraviolet/ozone (UV/O3). With increasing UV/O3exposure time, graphene in the heterojunction has more defect structures. The varied defect levels in graphene modulate the interfacial charge transfer, accordingly the band structure of the heterojunction. And the corresponding performance change of the graphene/MoS2field effect transistor indicates the shift of the Schottky barrier height after UV/O3treatment. The result further proves the effective band structure modulation of the graphene/MoS2heterojunction by UV/O3. This work will be beneficial to both fundamental research and practical applications of 2D van der Waals heterojunction in electronic devices.

Nanoarray Structures for Artificial Photosynthesis.

Conversion and storage of solar energy into fuels and chemicals by artificial photosynthesis has been considered as one of the promising methods to address the global energy crisis. However, it is still far from the practical applications on a large scale. Nanoarray structures that combine the advantages of nanosize and array alignment have demonstrated great potential to improve solar energy conversion efficiency, stability, and selectivity. This article provides a comprehensive review on the utilization of nanoarray structures in artificial photosynthesis of renewable fuels and high value-added chemicals. First, basic principles of solar energy conversion and superiorities of using nanoarray structures in this field are described. Recent research progress on nanoarray structures in both abiotic and abiotic-biotic hybrid systems is then outlined, highlighting contributions to light absorption, charge transport and transfer, and catalytic reactions (including kinetics and selectivity). Finally, conclusions and outlooks on future research directions of nanoarray structures for artificial photosynthesis are presented.

Two-Dimensional Covalent Organic Framework-Graphene Photodetectors: Insight into the Relationship between the Microscopic Interfacial Structure and Performance.

Graphene is an attractive material for photodetection and optoelectronic applications because it offers a broad spectral bandwidth and ultrafast response speed. However, because of the broad light absorption characteristic, graphene has a lack of selectivity to the wavelength, which limits the performance of graphene-based photodetectors. Here, we demonstrate a novel hybrid photodetector with monolayer graphene covered with an ultrathin film of surface covalent organic frameworks (COFs) with variable structures as the light-harvesting materials. Photodetectors based on surface COF-G show enhanced responsivity in comparison with unmodified graphene and graphene modified with monomers. The submolecular resolution of scanning tunneling microscopy allows us to get a direct insight into the relationship between the microscopic interfacial structure and the performance of the device. We prove that the enhancement in the device performance is directly related with the orderliness of surface COFs, which influences the interfacial charge transfer by tuning π-π stacking between surface COF and graphene.

Improving the Water Oxidation Efficiency with a Light-Induced Electric Field in Nanograting Photoanodes.

Severe charge recombination in solar water-splitting devices significantly limits their performance. To address this issue, we design a frustum of a cone nanograting configuration by taking the hematite and Au-based thin-film photoanode as a model system, which greatly improves the photoelectrochemical water oxidation activity, affording an approximately 10-fold increase in the photocurrent density at 1.23 V versus the reversible hydrogen electrode compared to the planar counterpart. The surface plasmon polariton-induced electric field in hematite plays a dominant role in efficiency enhancement by facilitating charge separation, thus dramatically increasing the incident photon-to-current efficiency (IPCE) by more than 2 orders of magnitude in the near band gap of hematite. And the relatively weak electric field caused by light scattering in the nanograting structure is responsible for the approximate maximum 20-fold increase in IPCE within a broadband wavelength range. Our scalable strategy can be generalized to other solar energy conversion systems.

Interaction-Dependent Interfacial Charge-Transfer Behavior in Solar Water-Splitting Systems.

Dual-band-gap systems are promising for solar water splitting due to their excellent light-harvesting capability and high charge-separation efficiency. However, a fundamental understanding of interfacial charge-transfer behavior in the dual-band-gap configuration is still incomplete. Taking CdS/reduced graphene oxide (CdS/RGO) nanoheterojunctions as a model solar water splitting system, we attempt here to highlight the interaction-dependent interfacial charge-transfer behavior based on both experimental observations and theoretical calculations. Experimental evidence points to charge transfer at the CdS-RGO interface playing a dominant role in the photocatalytic hydrogen production activity. By tuning the degree of reduction of RGO, the interfacial interaction, and, thereby, the charge transfer can be controlled at the CdS-RGO interface. This observation is supported by theoretical analysis, where we find that the interfacial charge transfer is a balance between the effective single-electron- and hole-transfer probability and the surface free electron and hole concentration, both of which are related to the surface potential and tailored by interfacial interaction. This mechanism is applicable to all systems for solar water splitting, providing a useful guidance for the design and study of heterointerfaces for high-efficiency energy conversion.

Antibacterial Carbon-Based Nanomaterials.

The emergence and global spread of bacterial resistance to currently available antibiotics underscore the urgent need for new alternative antibacterial agents. Recent studies on the application of nanomaterials as antibacterial agents have demonstrated their great potential for management of infectious diseases. Among these antibacterial nanomaterials, carbon-based nanomaterials (CNMs) have attracted much attention due to their unique physicochemical properties and relatively higher biosafety. Here, a comprehensive review of the recent research progress on antibacterial CNMs is provided, starting with a brief description of the different kinds of CNMs with respect to their physicochemical characteristics. Then, a detailed introduction to the various mechanisms underlying antibacterial activity in these materials is given, including physical/mechanical damage, oxidative stress, photothermal/photocatalytic effect, lipid extraction, inhibition of bacterial metabolism, isolation by wrapping, and the synergistic effect when CNMs are used in combination with other antibacterial materials, followed by a summary of the influence of the physicochemical properties of CNMs on their antibacterial activity. Finally, the current challenges and an outlook for the development of more effective and safer antibacterial CNMs are discussed.

Vertically Aligned Porous Organic Semiconductor Nanorod Array Photoanodes for Efficient Charge Utilization.

Because of inefficient charge utilization caused by localized π-electron conjugation and large exciton binding energy, the photoelectrochemical water-splitting efficiency of organic polymers is seriously limited. Taking the graphitic carbon nitride (g-CN) polymer as an example, we report a novel photoanode based on a vertically aligned g-CN porous nanorod (PNR) array prepared in situ, using a thermal polycondensation approach, with anodic aluminum oxide as the template. The g-CN PNR array exhibits an excellent photocurrent density of 120.5 µA cm-2 at 1.23 VRHE under one sun illumination, the highest reported incident photon-to-current efficiency of ∼15% at 360 nm, and an outstanding oxygen evolution reaction stability in 0.1 M Na2SO4 aqueous solution, which constitutes a benchmark performance among the reported g-CN-based polymer photoanodes without any sacrificial reagents. When compared with its planar counterpart, the enhanced performance of the PNR array results principally from its unique structure that enables a high degree of aromatic ring π-electron conjugation for higher mobility of charge carriers, provides a direct pathway for the electron transport to the substrate, produces a large portion of hole-accepting defect sites and space charge region to promote exciton dissociation, and also withstands more strain at the interface to ensure intimate contact with the substrate. This work opens a new avenue to develop nanostructured organic semiconductors for large-scale application of solar energy conversion devices.

Facile Integration between Si and Catalyst for High-Performance Photoanodes by a Multifunctional Bridging Layer.

Designing high-quality interfaces is crucial for high-performance photoelectrochemical (PEC) water-splitting devices. Here, we demonstrate a facile integration between polycrystalline n+p-Si and NiFe-layered double hydroxide (LDH) nanosheet array by a partially activated Ni (Ni/NiOx) bridging layer for the excellent PEC water oxidation. In this model system, the thermally deposited Ni interlayer protects Si against corrosion and makes good contact with Si, and NiOx has a high capacity of hole accumulation and strong bonding with the electrodeposited NiFe-LDH due to the similarity in material composition and structure, facilitating transfer of accumulated holes to the catalyst. In addition, the back illumination configuration makes NiFe-LDH sufficiently thick for more catalytically active sites without compromising Si light absorption. This earth-abundant multicomponent photoanode affords the PEC performance with an onset potential of ∼0.78 V versus reversible hydrogen electrode (RHE), a photocurrent density of ∼37 mA cm-2 at 1.23 V versus RHE, and retains good stability in 1.0 M KOH, the highest water oxidation activity so far reported for the crystalline Si-based photoanodes. This bridging layer strategy is efficient and simple to smooth charge transfer and make robust contact at the semiconductor/electrocatalyst interface in the solar water-splitting systems.

Sacrificial Interlayer for Promoting Charge Transport in Hematite Photoanode.

The semiconductor/electrolyte interface plays a crucial role in photoelectrochemical (PEC) water-splitting devices as it determines both thermodynamic and kinetic properties of the photoelectrode. Interfacial engineering is central for the device performance improvement. Taking the cheap and stable hematite (α-Fe2O3) wormlike nanostructure photoanode as a model system, we design a facile sacrificial interlayer approach to suppress the crystal overgrowth and realize Ti doping into the crystal lattice of α-Fe2O3 in one annealing step as well as to avoid the consequent anodic shift of the photocurrent onset potential, ultimately achieving five times increase in its water oxidation photocurrent compared to the bare hematite by promoting the transport of charge carriers, including both separation of photogenerated charge carriers within the bulk semiconductor and transfer of holes across the semiconductor-electrolyte interface. Our research indicates that understanding the semiconductor/electrolyte interfacial engineering mechanism is pivotal for reconciling various strategies in a beneficial way, and this simple and cost-effective method can be generalized into other systems aiming for efficient and scalable solar energy conversion.

A photoelectrochemical investigation on the synergetic effect between CdS and reduced graphene oxide for solar-energy conversion.

CdS modified with reduced graphene oxide (RGO) has been widely demonstrated to be effective in the field of solar-energy conversion. However, the inherent mechanism of this superior property is still not thoroughly understood. Thus the photoelectrochemical method was employed to systemically investigate the synergetic effect between CdS and RGO. The result shows that the photoelectrochemical properties of RGO/CdS samples are sensitive to the relative ratio of RGO to CdS, and the photoelectrode with 1.0 wt% ratio of RGO possesses the best photoelectrochemical performance. Further investigation demonstrates that the synergetic effect between CdS and RGO directly influences the charge-transport property and band-structure of the composite, which is also supported by the X-ray photoelectron spectroscopy data and first-principle simulation, respectively.

Graphene-based materials for hydrogen generation from light-driven water splitting.

Hydrogen production from solar water splitting has been considered as an ultimate solution to the energy and environmental issues. Over the past few years, graphene has made great contribution to improving the light-driven hydrogen generation performance. This article provides a comprehensive overview of the recent research progress on graphene-based materials for hydrogen evolution from light-driven water splitting. It begins with a brief introduction of the current status and basic principles of hydrogen generation from solar water splitting, and tailoring properties of graphene for application in this area. Then, the roles of graphene in hydrogen generation reaction, including an electron acceptor and transporter, a cocatalyst, a photocatalyst, and a photosensitizer, are elaborated respectively. After that, the comparison between graphene and other carbon materials in solar water splitting is made. Last, this review is concluded with remarks on some challenges and perspectives in this emerging field.

Strong two-photon-induced fluorescence from photostable, biocompatible nitrogen-doped graphene quantum dots for cellular and deep-tissue imaging.

Bright two-photon fluorescent probes are highly desirable to be able to optically probe biological activities deep inside living organisms with larger imaging depth, minor autofluorescence background, and less photodamage. In this study, we report the biocompatible nitrogen-doped graphene quantum dots (N-GQDs) as efficient two-photon fluorescent probes for cellular and deep-tissue imaging. The N-GQD was prepared by a facile solvothermal method using dimethylformamide as a solvent and nitrogen source. The two-photon absorption cross-section of N-GQD reaches 48,000 Göppert-Mayer units, which far surpasses that of the organic dyes and is comparable to that of the high performance semiconductor QDs, achieving the highest value ever reported for carbon-based nanomaterials. More importantly, a study of penetration depth in tissue phantom demonstrates that the N-GQD can achieve a large imaging depth of 1800 µm, significantly extending the fundamental two-photon imaging depth limit. In addition, the N-GQD is nontoxic to living cells and exhibits super photostability under repeated laser irradiation. The high two-photon absorption cross-section, large imaging depth, good biocompatibility, and extraordinary photostability render the N-GQD an attractive alternative probe for efficient two-photon imaging in biological and biomedical applications.

Chiral zinc phenylalanine nanofibers with fluorescence.

Chiral Zn(II)/D-,L-phenylalanine (Phe) bio-coordination polymer nanofibers with fluorescence were prepared by fast coordination-assisted assembly. The synthetic strategy is based on the fact that the Zn2+ ions were linked to oxygen atoms from carboxylate groups of the D- or L-amino acid by coordination interactions to form the chiral polymers. The Zn(II)/D-,L-Phe nanofibers had homogeneous diameters in the range of 700-900 nm and ultra-long length in several hundred micrometers, and the surface of the fiber was extremely smooth. In addition, the enantiomers of Zn(II)/Phe nanofibers exhibited both optical activity and fluorescent property in the solid state, which has great potential for application in the field of biomimetic nanofabrication and micro-/nano-optoelectronics.

Highly efficient visible-light-driven photocatalytic hydrogen production of CdS-cluster-decorated graphene nanosheets.

The production of clean and renewable hydrogen through water splitting using photocatalysts has received much attention due to the increasing global energy crises. In this study, a high efficiency of the photocatalytic H(2) production was achieved using graphene nanosheets decorated with CdS clusters as visible-light-driven photocatalysts. The materials were prepared by a solvothermal method in which graphene oxide (GO) served as the support and cadmium acetate (Cd(Ac)(2)) as the CdS precursor. These nanosized composites reach a high H(2)-production rate of 1.12 mmol h(-1) (about 4.87 times higher than that of pure CdS nanoparticles) at graphene content of 1.0 wt % and Pt 0.5 wt % under visible-light irradiation and an apparent quantum efficiency (QE) of 22.5% at wavelength of 420 nm. This high photocatalytic H(2)-production activity is attributed predominantly to the presence of graphene, which serves as an electron collector and transporter to efficiently lengthen the lifetime of the photogenerated charge carriers from CdS nanoparticles. This work highlights the potential application of graphene-based materials in the field of energy conversion.

Controllable N-doping of graphene.

Opening and tuning an energy gap in graphene are central to many electronic applications of graphene. Here we report N-doped graphene obtained by NH3 annealing after N(+)-ion irradiation of graphene samples. First, the evolution of the graphene microstructure was investigated following N(+)-ion irradiation at different fluences using Raman spectroscopy, showing that defects were introduced in plane after irradiation and then restored after annealing in N2 or in NH3. Auger electron spectroscopy (AES) of the graphene annealed in NH3 after irradiation showed N signal, however, no N signal was observed after annealing in N2. Last, the field-effect transistor (FET) was fabricated using N-doped graphene and monitored by the source-drain conductance and back-gate voltage (Gsd-Vg) curves in the measurement. The transport property changed compared to that of the FET made by intrinsic graphene, that is, the Dirac point position moved from positive Vg to negative Vg, indicating the transition of graphene from p-type to n-type after annealing in NH3. Our approach, which provides a physical mechanism for the introduction of defect and subsequent hetero dopant atoms into the graphene material in a controllable fashion, will be promising for producing graphene-based devices for multiple applications.