Impact of sulfur-impregnated biochar amendment on microbial communities and mercury methylation in contaminated sediment.

S-impregnation of biochar through elemental S streaming is known to increase its sorption performance against Hg and methyl mercury (MeHg). However, the effects of %S-loading on biochar's mechanism and sorption capacities for MeHg, and its consequent impact when used as an amendment material for Hg-contaminated sediments, are poorly understood, and thus, were investigated in this work. Our results showed that a minimum sulfur loading of 1% was the most effective in reducing MeHg levels in sediments. At higher %S-loading (3-20%), the reduction in surface area, pore blockage due to unreacted sulfur particles, and presence of poorly bound sulfur species resulted in lowered effectiveness for MeHg control. Increasing S-functionalization during impregnation shifted the sorption process of MeHg from Hg-O to Hg-S in S-impregnated biochar (BCS). Our 60-day slurry experiment showed a significant reduction in pore water THg (40-70%) and MeHg (30-55%), as well as sediment MeHg (50-60%) in biochar-amended sediments. The reduction in the bioavailable Hg resulted in lowered Hg methylation, as supported by the suppression of both the Fe- and SO42--reduction activities in the amended sediments. The microbial community structure in BCS-amended sediments showed a shift towards sulfur-consuming, iron-reducing, thiosulfate-oxidizing, and sulfate-reducing bacterial populations. At the genus level, the overall relative abundance of principal Hg methylators was also lower in the BCS treatment than in the unamended sediments. This study highlights the application of BCS as a promising strategy for remediation of Hg-contaminated sediments.

Direct Growth of Highly Conductive Large-Area Stretchable Graphene.

The direct synthesis of inherently defect-free, large-area graphene on flexible substrates is a key technology for soft electronic devices. In the present work, in situ plasma-assisted thermal chemical vapor deposition is implemented in order to synthesize 4 in. diameter high-quality graphene directly on 10 nm thick Ti-buffered substrates at 100 °C. The in situ synthesized monolayer graphene displays outstanding stretching properties coupled with low sheet resistance. Further improved mechanical and electronic performances are achieved by the in situ multi-stacking of graphene. The four-layered graphene multi-stack is shown to display an ultralow resistance of ≈6 Ω sq-1, which is consistently maintained during the harsh repeat stretching tests and is assisted by self-p-doping under ambient conditions. Graphene-field effect transistors fabricated on polydimethylsiloxane substrates reveal an unprecedented hole mobility of ≈21 000 cm2 V-1 s-1 at a gate voltage of -4 V, irrespective of the channel length, which is consistently maintained during the repeat stretching test of 5000 cycles at 140% parallel strain.

Chemical Patterning of Graphene via Metal-Assisted Highly Energetic Electron Irradiation for Graphene Homojunction-Based Gas Sensors.

To gain the target functionality of graphene for gas detection, nonfocused and large-scale compatible MeV electron beam irradiation on graphene with Ag patterns is innovatively adopted in air for chemical patterning of graphene. This strategy allows the metal-assisted site-specific oxidation of graphene to realize monolithically integrated graphene-chemically patterned graphene (CPG)-graphene homojunction-based gas sensors. The size-tunable CPG patterns can be mediated by regulating the size of Ag prepatterns. The impacts of highly energetic electron irradiation (HEEI) on graphene are summarized as follows: (i) the selective p-type doping and the defect generation of graphene by the HEEI-induced oxidation, (ii) the resistance of the homojunction devices manipulated by the HEEI dose, (iii) the band gap opening of graphene as well as the lowering of the Fermi level, (iv) the work function values for pristine graphene and CPG corresponding to 4.14 and 4.88 eV, respectively, and (v) graphene-CPG-graphene homojunction for NO2 gas, revealing an 839% enhanced gas response compared with that of the pristine graphene-based gas sensor.

Template Engineering of CuBi2 O4 Single-Crystal Thin Film Photocathodes.

To develop strategies for efficient photo-electrochemical water-splitting, it is important to understand the fundamental properties of oxide photoelectrodes by synthesizing and investigating their single-crystal thin films. However, it is challenging to synthesize high-quality single-crystal thin films from copper-based oxide photoelectrodes due to the occurrence of significant defects such as copper or oxygen vacancies and grains. Here, the CuBi2 O4 (CBO) single-crystal thin film photocathode is achieved using a NiO template layer grown on single-crystal SrTiO3 (STO) (001) substrate via pulsed laser deposition. The NiO template layer plays a role as a buffer layer of large lattice mismatch between CBO and STO (001) substrate through domain-matching epitaxy, and forms a type-II band alignment with CBO, which prohibits the transfer of photogenerated electrons toward bottom electrode. The photocurrent densities of the CBO single-crystal thin film photocathode demonstrate -0.4 and -0.7 mA cm-2 at even 0 VRHE with no severe dark current under illumination in a 0.1 m potassium phosphate buffer solution without and with H2 O2 as an electron scavenger, respectively. The successful synthesis of high-quality CBO single-crystal thin film would be a cornerstone for the in-depth understanding of the fundamental properties of CBO toward efficient photo-electrochemical water-splitting.

Sustainable removal of Hg(II) by sulfur-modified pine-needle biochar.

Sulfur-modified pine-needle biochar (BC-S) was produced for the removal of Hg(II) in aqueous media via post-pyrolysis S stream exposure. Fourier-transform infrared spectroscopy, elemental analysis, and X-ray photoelectron spectroscopy confirmed the addition of S(0) groups on the surface of BC-S. Hg(II) adsorption on BC-S was best described by the Freundlich isotherm with a KF of 21.0 mg L g-1 and a pseudo-second-order adsorption kinetics model with a rate of 0.35 g mg-1 min-1. Hg(II) removal on BC-S was found to be an endothermic process that relied on C-Hg and S-Hg interactions rather than reduction by S(0) groups. The adsorption increased with increasing solution pH and decreased with increasing dissolved organic matter concentration, but was unaffected by increasing salt concentrations. BC-S showed a maximum of 3 % S leaching in aqueous media after 28-d exposure time, and exposure to aqueous media did not convert Hg(II) to elemental Hg. Overall, BC-S exhibited superior Hg(II) removal performance over unmodified BC, thus having potential applications in natural water and wastewater treatment with no significant threat of secondary pollution.

Metal organic framework UiO-66 and activated carbon composite sorbent for the concurrent adsorption of cationic and anionic metals.

A composite sorbent for the simultaneous removal of both Hg2+ and SeO32- from aqueous media was produced from the solvothermal synthesis of a zirconium metal organic framework, UiO-66, in the presence of activated carbon. The composite sorbent has a large surface area of 1051 m2 g-1 with crystalized porous structures and has strong thermal stability up to 600 °C. The contaminant uptake of the sorbent follows a Langmuir adsorption isotherm with maximum sorption capacity of 205 mg g-1 and 168 mg g-1 for Hg2+ and SeO32-, respectively. Scanning electron microscopy-energy dispersive spectroscopy results show that the Se regions overlap exclusively with Zr-rich regions suggesting that SeO32- adsorption depends entirely on the exposed UiO-66 surface. In addition, X-ray photoelectron spectroscopy spectra of Se 3d and Hg 4f showed the association of SeO32- and Hg2+ on the UiO-66 and carbon surfaces, respectively. The sorbent could facilitate the development of a single process for the simultaneous removal of cationic Hg and anionic Se as well as other similar ionic metals with opposite charges from aqueous media.

Ultrahigh-Mobility and Solution-Processed Inorganic P-Channel Thin-Film Transistors Based on a Transition-Metal Halide Semiconductor.

The development of p-channel devices with comparable electrical performances to their n-channel counterparts has been delayed due to the lack of p-type semiconductor materials and device optimization. In this present work, we successfully demonstrated p-channel inorganic thin-film transistors (TFTs) with high hole mobilities similar to the values of n-channel devices. To boost the device performance, the solution-processed copper iodide (CuI) semiconductor was gated by a solid polymer electrolyte. The electrolyte gating could realize electrical double layer (EDL) formation and a three-dimensional carrier transport channel and thus substantially increased charge accumulation in the channel region and realized a high mobility above 90 cm2/(V s) (45.12 ± 22.19 cm2/(V s) on average). In addition, due to the high-capacitance EDL formed by electrolyte gating, the CuI TFTs exhibited a low operation voltage below 0.5 V (Vth = -0.045 V) and a high ON current level of 0.7 mA with an ON/OFF ratio of 1.52 × 103. We also evaluated the operational stabilities of CuI TFTs and the devices showed 80% retention under electrical/mechanical stress. All the active layers of the transistors were fabricated by solution processes at low temperatures (<100 °C), indicating their potential use for flexible, wearable, and high-performance electronic applications.

In Situ Growth of Nanostructured BiVO4-Bi2O3 Mixed-Phase via Nonequilibrium Deposition Involving Metal Exsolution for Enhanced Photoelectrochemical Water Splitting.

Nonequilibrium deposition is a remarkable method for the in situ growth of unique nanostructures and phases for the functionalization of thin films. We introduce a distinctive structure of a mixed-phase, composed of BiVO4 and ß-Bi2O3, for photoelectrochemical water splitting. The mixed-phase is fabricated via nonequilibrium deposition by adjusted oxygen partial pressure. According to density functional theory calculations, we find that vanadium exsolution can be facilitated by introducing oxygen vacancies, enabling the fabrication of a nanostructured mixed-phase. These unique structures enhance charge migration by increasing the interfacial area and properly aligning the band offset between two crystalline phases. Consequently, the photocurrent density of the nanostructured mixed-phase thin films is about twice that of pristine BiVO4 thin films at 1.23 VRHE. Our work suggests that nonequilibrium deposition provides an innovative route for the structural engineering of photoelectrodes for the understanding of fundamental properties and improving the photocatalytic performance for solar water splitting.

Atomic-Level Customization of 4 in. Transition Metal Dichalcogenide Multilayer Alloys for Industrial Applications.

Despite many encouraging properties of transition metal dichalcogenides (TMDs), a central challenge in the realm of industrial applications based on TMD materials is to connect the large-scale synthesis and reproducible production of highly crystalline TMD materials. Here, the primary aim is to resolve simultaneously the two inversely related issues through the synthesis of MoS2(1- x ) Se2 x ternary alloys with customizable bichalcogen atomic (S and Se) ratio via atomic-level substitution combined with a solution-based large-area compatible approach. The relative concentration of bichalcogen atoms in the 2D alloy can be effectively modulated by altering the selenization temperature, resulting in 4 in. scale production of MoS1.62 Se0.38 , MoS1.37 Se0.63 , MoS1.15 Se0.85 , and MoS0.46 Se1.54 alloys, as well as MoS2 and MoSe2 . Comprehensive spectroscopic evaluations for vertical and lateral homogeneity in terms of heteroatom distribution in the large-scale 2D TMD alloys are implemented. Se-stimulated strain effects and a detailed mechanism for the Se substitution in the MoS2 crystal are further explored. Finally, the capability of the 2D alloy for industrial application in nanophotonic devices and hydrogen evolution reaction (HER) catalysts is validated. Substantial enhancements in the optoelectronic and HER performances of the 2D ternary alloy compared with those of its binary counterparts, including pure-phase MoS2 and MoSe2 , are unambiguously achieved.

Hierarchical carbon-silicon nanowire heterostructures for the hydrogen evolution reaction.

Silicon nanowires (SiNWs) opened up exciting possibilities in a variety of research fields due to their unique anisotropic morphologies, facile tuning capabilities, and accessible fabrication methods. The SiNW-based photoelectrochemical (PEC) conversion has recently been known to provide an efficiency superior to that of various photo-responsive semiconductor heterostructures. However, a challenge still remains in designing optimum structures to minimize photo-oxidation and photo-corrosion of the Si surface in a liquid electrolyte. Here, we report a simple method to synthesize hierarchically branched carbon nanowires (CNWs) on SiNWs utilizing copper vapor as the catalyst in a chemical vapor deposition (CVD) process, which exhibits outstanding photocatalytic activities for hydrogen generation along with excellent chemical stability against oxidation and corrosion. Thus, we believe that the CNW-SiNW photoelectrodes would provide a new route to developing high-performing cost-effective catalysts essential for advanced energy conversion and storage technologies.

Wet Pretreatment-Induced Modification of Cu(In,Ga)Se2/Cd-Free ZnTiO Buffer Interface.

We report a novel Cd-free ZnTiO buffer layer deposited by atomic layer deposition for Cu(In,Ga)Se2 (CIGS) solar cells. Wet pretreatments of the CIGS absorbers with NH4OH, H2O, and/or aqueous solution of Cd2+ ions were explored to improve the quality of the CIGS/ZnTiO interface, and their effects on the chemical state of the absorber and the final performance of Cd-free CIGS devices were investigated. X-ray photoelectron spectroscopy (XPS) analysis revealed that the aqueous solution etched away sodium compounds accumulated on the CIGS surface, which was found to be detrimental for solar cell operation. Wet treatment with NH4OH solution led to a reduced photocurrent, which was attributed to the thinning (or removal) of an ordered vacancy compound (OVC) layer on the CIGS surface as evidenced by an increased Cu XPS peak intensity after the NH4OH treatment. However, the addition of Cd2+ ions to the NH4OH aqueous solution suppressed the etching of the OVC by NH4OH, explaining why such a negative effect of NH4OH is not present in the conventional chemical bath deposition of CdS. The band alignment at the CIGS/ZnTiO interface was quantified using XPS depth profile measurements. A small cliff-like conduction band offset of -0.11 eV was identified at the interface, which indicates room for further improvement of efficiency of the CIGS/ZnTiO solar cells once the band alignment is altered to a slight spike by inserting a passivation layer with a higher conduction band edge than ZnTiO. Combination of the small cliff conduction band offset at the interface, removal of the Na compound via water, and surface doping by Cd ions allowed the application of ZnTiO buffer to CIGS treated with Cd solutions, exhibiting an efficiency of 80% compared to that of a reference CIGS solar cell treated with the CdS.

Roll-to-Roll Production of Layer-Controlled Molybdenum Disulfide: A Platform for 2D Semiconductor-Based Industrial Applications.

A facile methodology for the large-scale production of layer-controlled MoS2 layers on an inexpensive substrate involving a simple coating of single source precursor with subsequent roll-to-roll-based thermal decomposition is developed. The resulting 50 cm long MoS2 layers synthesized on Ni foils possess excellent long-range uniformity and optimum stoichiometry. Moreover, this methodology is promising because it enables simple control of the number of MoS2 layers by simply adjusting the concentration of (NH4 )2 MoS4 . Additionally, the capability of the MoS2 for practical applications in electronic/optoelectronic devices and catalysts for hydrogen evolution reaction is verified. The MoS2 -based field effect transistors exhibit unipolar n-channel transistor behavior with electron mobility of 0.6 cm2 V-1 s-1 and an on-off ratio of ≈10³. The MoS2 -based visible-light photodetectors are fabricated in order to evaluate their photoelectrical properties, obtaining an 100% yield for active devices with significant photocurrents and extracted photoresponsivity of ≈22 mA W-1 . Moreover, the MoS2 layers on Ni foils exhibit applicable catalytic activity with observed overpotential of ≈165 mV and a Tafel slope of 133 mV dec-1 . Based on these results, it is envisaged that the cost-effective methodology will trigger actual industrial applications, as well as novel research related to 2D semiconductor-based multifaceted applications.

Double-Layer Graphene Outperforming Monolayer as Catalyst on Silicon Photocathode for Hydrogen Production.

Photoelectrochemical cells are used to split hydrogen and oxygen from water molecules to generate chemical fuels to satisfy our ever-increasing energy demands. However, it is a major challenge to design efficient catalysts to use in the photoelectochemical process. Recently, research has focused on carbon-based catalysts, as they are nonprecious and environmentally benign. Interesting advances have also been made in controlling nanostructure interfaces and in introducing new materials as catalysts in the photoelectrochemical cell. However, these catalysts have as yet unresolved issues involving kinetics and light-transmittance. In this work, we introduce high-transmittance graphene onto a planar p-Si photocathode to produce a hydrogen evolution reaction to dramatically enhance photon-to-current efficiency. Interestingly, double-layer graphene/Si exhibits noticeably improved photon-to-current efficiency and modifies the band structure of the graphene/Si photocathode. On the basis of in-depth electrochemical and electrical analyses, the band structure of graphene/Si was shown to result in a much lower work function than Si, accelerating the electron-to-hydrogen production potential. Specifically, plasma-treated double-layer graphene exhibited the best performance and the lowest work function. We electrochemically analyzed the mechanism at work in the graphene-assisted photoelectrode. Atomistic calculations based on the density functional theory were also carried out to more fully understand our experimental observations. We believe that investigation of the underlying mechanism in this high-performance electrode is an important contribution to efforts to develop high-efficiency metal-free carbon-based catalysts for photoelectrochemical cell hydrogen production.

Enhanced Photocatalytic Performance Depending on Morphology of Bismuth Vanadate Thin Film Synthesized by Pulsed Laser Deposition.

We have fabricated high quality bismuth vanadate (BiVO4) polycrystalline thin films as photoanodes by pulsed laser deposition (PLD) without a postannealing process. The structure of the grown films is the photocatalytically active phase of scheelite-monoclinic BiVO4 which was obtained by X-ray diffraction (XRD) analysis. The change of surface morphology for the BIVO4 thin films depending on growth temperature during synthesis has been observed by scanning electron microscopy (SEM), and its influence on water splitting performance was investigated. The current density of the BiVO4 film grown on a glass substrate covered with fluorine-doped tin oxide (FTO) at 230 °C was as high as 3.0 mA/cm2 at 1.23 V versus the potential of the reversible hydrogen electrode (VRHE) under AM 1.5G illumination, which is the highest value so far in previously reported BiVO4 films grown by physical vapor deposition (PVD) methods. We expect that doping of transition metal or decoration of oxygen evolution catalyst (OEC) in our BiVO4 film might further enhance the performance.

Strain Relaxation of Graphene Layers by Cu Surface Roughening.

The surface morphology of copper (Cu) often changes after the synthesis of graphene by chemical vapor deposition (CVD) on a Cu foil, which affects the electrical properties of graphene, as the Cu step bunches induce the periodic ripples on graphene that significantly disturb electrical conduction. However, the origin of the Cu surface reconstruction has not been completely understood yet. Here, we show that the compressive strain on graphene induced by the mismatch of thermal expansion coefficient with Cu surface can be released by forming periodic Cu step bunching that depends on graphene layers. Atomic force microscopy (AFM) images and the Raman analysis show the noticeably longer and higher step bunching of Cu surface under multilayer graphene and the weaker biaxial compressive strain on multilayer graphene compared to monolayer. We found that the surface areas of Cu step bunches under multilayer and monolayer graphene are increased by ∼1.41% and ∼0.77% compared to a flat surface, respectively, indicating that the compressive strain on multilayer graphene can be more effectively released by forming the Cu step bunching with larger area and longer periodicity. We believe that our finding on the strain relaxation of graphene layers by Cu step bunching formation would provide a crucial idea to enhance the electrical performance of graphene electrodes by controlling the ripple density of graphene.

Formation of Frustrated Lewis Pairs in Ptx -Loaded Zeolite†NaY.

The formation of a frustrated Lewis pair consisting of sodium hydride (Na(+) H(-) ) and a framework-bound hydroxy proton O(H(+) ) is reported upon H2 treatment of zeolite NaY loaded with Pt nanoparticles (Ptx /NaY). Frustrated Lewis pair formation was confirmed using in situ neutron diffraction and spectroscopic measurements. The activity of the intrazeolite NaH as a size-selective catalyst was verified by the efficient esterification of acetaldehyde (a small aldehyde) to form the corresponding ester ethyl acetate, whereas esterification of the larger molecule benzaldehyde was unsuccessful. The frustrated Lewis pair (consisting of Na(+) H(-) and O(H(+) )) generated within zeolite NaY may be a useful catalyst for various catalytic reactions which require both H(-) and H(+) ions, such as catalytic hydrogenation or dehydrogenation of organic compounds and activation of small molecules.

An electrochemical approach to graphene oxide coated sulfur for long cycle life.

Owing to the possibilities of achieving high theoretical energy density and gravimetric capacity, sulfur has been considered as a promising cathode material for rechargeable lithium batteries. However, sulfur shows rapid capacity fading due to the irreversible loss of soluble polysulfides and the decrease in active sites needed for conducting agents. Furthermore, the low electrical conductivity of sulfur hampers the full utilization of active materials. Here we report that graphene oxide coated sulfur composites (GO-S/CB) exhibit improved electrochemical stability as well as enhanced rate performance, evidenced by various electrochemical analyses. The cyclic voltammetry and the galvanostatic cycling analysis revealed that the GO plays key roles in homogenizing the nanocomposite structures of the electrodes, in improving the electrochemical contact, and in minimizing the loss of soluble polysulfide intermediates. An electrochemical impedance spectroscopy analysis also confirms the enhanced structural stability of the GO-S/CB composites after battery operation. As a result, the GO-S/CB exhibited excellent cycle stability and specific capacity as high as ∼723.7 mA h g(-1) even after 100 cycles at 0.5 C.

Opening and reversible control of a wide energy gap in uniform monolayer graphene.

For graphene to be used in semiconductor applications, a 'wide energy gap' of at least 0.5 eV at the Dirac energy must be opened without the introduction of atomic defects. However, such a wide energy gap has not been realized in graphene, except in the cases of narrow, chemically terminated graphene nanostructures with inevitable edge defects. Here, we demonstrated that a wide energy gap of 0.74 eV, which is larger than that of germanium, could be opened in uniform monolayer graphene without the introduction of atomic defects into graphene. The wide energy gap was opened through the adsorption of self-assembled twisted sodium nanostrips. Furthermore, the energy gap was reversibly controllable through the alternate adsorption of sodium and oxygen. The opening of such a wide energy gap with minimal degradation of mobility could improve the applicability of graphene in semiconductor devices, which would result in a major advancement in graphene technology.

Rotated domains in chemical vapor deposition-grown monolayer graphene on Cu(111): an angle-resolved photoemission study.

Copper is considered to be the most promising substrate for the growth of high-quality and large area graphene by chemical vapor deposition (CVD), in particular, on the (111) facet. Because the interactions between graphene and Cu substrates influence the orientation, quality, and properties of the synthesized graphene, we studied the interactions using angle-resolved photoemission spectroscopy. The evolution of both the Shockley surface state of the Cu(111) and the π band of the graphene was measured from the initial stage of CVD growth to the formation of a monolayer. Graphene growth was initiated along the Cu(111) lattice, where the Dirac band crossed the Fermi energy (EF) at the K point without hybridization with the d-band of Cu. Then two rotated domains were additionally grown as the area covered with graphene became wider. The Dirac energy was about -0.4 eV and the energy of the Shockley surface state of Cu(111) shifted toward the EF by ~0.15 eV upon graphene formation. These results indicate weak interactions between graphene and Cu, and that the electron transfer is limited to that between the Shockley surface state of Cu(111) and the π band of graphene. This weak interaction and slight lattice mismatch between graphene and Cu resulted in the growth of rotated graphene domains (9.6° and 8.4°), which showed no significant differences in the Dirac band with respect to different orientations. These rotated graphene domains resulted in grain boundaries which would hinder a large-sized single monolayer growth on Cu substrates.

Fabrication of carbon nanotube-emitters on Ag-Cu alloy film by thermal welding.

A field emission electron source was fabricated on a Si substrate using Ag-Cu alloy (ACa) and carbon nanotubes (CNTs). The ACa was adopted as a binder material due to its excellent electrical conductivity, oxidation stability, and suitable melting point (783 degrees C). The surface morphology of the ACa-film was improved by introducing an Nb layer as an adhesion layer between the ACa-film and the Si substrate. The ACa-film thickness was varied from 100 to 500 nm. The spray method was employed to deposit a CNT film on the ACa/Nb/Si substrate for large area fabrication. After annealing the substrate at 700 degrees C for 10 min, the CNT film was tightly welded on the ACa-films, and the CNT-emitters fabricated on the 400-nm-thick ACa-film exhibited high current density and stability with a low turn-on voltage. It is worth noting that ACa could be applied to the glass substrate because the CNT-emitters fabricated at 500 degrees C exhibited good field emission characteristics.