Defect-Engineered Mesoporous Undoped Carbon Nanoribbons for Benchmark Oxygen Reduction Reaction.

For large-scale fuel cell applications, it is significant to replace expensive Pt-based oxygen reduction reaction (ORR) electrocatalysts with nonprecious metal- or metal-free carbon-based catalysts with high activity. However, it is still challenging to deeply understand the role of intrinsic defects and the origin of ORR activity in pure nanocarbon. Therefore, a novel self-assembly and a pyrolysis strategy to fabricate defect-rich mesoporous carbon nanoribbons are presented. Due to the effective regulation of nanoarchitecture, a vast number of defective catalytic sites (edge defects and holes) are exposed, which thereby enhances the electron transfer kinetics and catalytic activity. Such undoped nanoribbons display a large half-wave potential of 0.837 V, excellent long-term stability, and exceptional methanol tolerance, surpassing the most undoped ORR catalysts and the commercial Pt/C (20 wt.%) catalyst. Structural characterizations and density functional theory (DFT) calculations confirm that the zigzag edge defects and the armchair pentagon at the hole defect are responsible for outstanding ORR performance.

Room-Temperature Synthesis of Carbon-Nanotube-Interconnected Amorphous NiFe-Layered Double Hydroxides for Boosting Oxygen Evolution Reaction.

The oxygen evolution reaction (OER) is a key half-reaction in electrocatalytic water splitting. Large-scale water electrolysis is hampered by commercial noble-metal-based OER electrocatalysts owing to their high cost. To address these issues, we present a facile, one-pot, room-temperature co-precipitation approach to quickly synthesize carbon-nanotube-interconnected amorphous NiFe-layered double hydroxides (NiFe-LDH@CNT) as cost-effective, efficient, and stable OER electrocatalysts. The hybrid catalyst NiFe-LDH@CNT delivered outstanding OER activity with a low onset overpotential of 255 mV and a small Tafel slope of 51.36 mV dec-1, as well as outstanding long-term stability. The high catalytic capability of NiFe-LDH@CNT is associated with the synergistic effects of its room-temperature synthesized amorphous structure, bi-metallic modulation, and conductive CNT skeleton. The room-temperature synthesis can not only offer economic feasibility, but can also allow amorphous NiFe-LDH to be obtained without crystalline boundaries, facilitating long-term stability during the OER process. The bi-metallic nature of NiFe-LDH guarantees a modified electronic structure, providing additional catalytic sites. Simultaneously, the highly conductive CNT network fosters a nanoporous structure, facilitating electron transfer and O2 release and enriching catalytic sites. This study introduces an innovative approach to purposefully design nanoarchitecture and easily synthesize amorphous transition-metal-based OER catalysts, ensuring their cost effectiveness, production efficiency, and long-term stability.

Hierarchical Ultrathin Layered GO-ZnO@CeO2 Nanohybrids for Highly Efficient Methylene Blue Dye Degradation.

Highly efficient interfacial contact between components in nanohybrids is a key to achieving great photocatalytic activity in photocatalysts and degradation of organic model pollutants under visible light irradiation. Herein, we report the synthesis of nano-assembly of graphene oxide, zinc oxide and cerium oxide (GO-ZnO@CeO2) nanohybrids constructed by the hydrothermal method and subsequently annealed at 300 °C for 4 h. The unique graphene oxide sheets, which are anchored with semiconducting materials (ZnO and CeO2 nanoparticles), act with a significant role in realizing sufficient interfacial contact in the new GO-ZnO@CeO2 nanohybrids. Consequently, the nano-assembled structure of GO-ZnO@CeO2 exhibits a greater level (96.66%) of MB dye degradation activity than GO-ZnO nanostructures and CeO2 nanoparticles on their own. This is due to the thin layers of GO-ZnO@CeO2 nanohybrids with interfacial contact, suitable band-gap matching and high surface area, preferred for the improvement of photocatalytic performance. Furthermore, this work offers a facile building and cost-effective construction strategy to synthesize the GO-ZnO@CeO2 nanocatalyst for photocatalytic degradation of organic pollutants with long-term stability and higher efficiency.

Electronic Modulation of Hierarchical Spongy Nanosheets toward Efficient and Stable Water Electrolysis.

The energy conversion efficiency of water electrolysis is determined by the activity of selected catalysts. Ideal catalysts should possess not only porous architecture for high-density assembly of active sites but also a subtle electronic configuration for the optimized activity at each site. In this context, the development of stable porous hosting materials that allow the incorporation of various metal elements is highly desirable for both experimental optimization and theoretical comparison/prediction. Herein, MOF-derived spongy nanosheet arrays constructed by assembly of carbon encapsulated hetero-metal doped Ni2 P nanoparticles is presented as a superior bifunctional electrocatalyst for water splitting. This hierarchical structure can be stably retained when secondary metal dopants are introduced, providing a flexible platform for electronic modulation. The catalytic origin of activity enhancement via metal (Fe, Cr, and Mn) doping is deciphered through experimental and theoretical investigations. Combining the advantages in both morphological and electronic structures, the optimized catalyst NiMn-P exhibits remarkable activity in both hydrogen and oxygen evolution in the alkaline media, with an ultrasmall cell voltage of 1.49 V (at 10 mA cm-2 ) and high durability for at least 240 h.

In Situ Construction of Mo2 C Quantum Dots-Decorated CNT Networks as a Multifunctional Electrocatalyst for Advanced Lithium-Sulfur Batteries.

The slow redox kinetics during cycling process and the serious shuttle effect caused by the solubility of lithium polysulfides (LiPSs) dramatically hinder the practical application of Li-S batteries. Herein, a facile and scalable spray-drying strategy is presented to construct conductive polar Mo2 C quantum dots-decorated carbon nanotube (CNT) networks (MCN) as an efficient absorbent and electrocatalyst for Li-S batteries. The results reveal that the MCN/S electrode exhibits a high specific capacity of 1303.3 mAh g-1 at 0.2 C, and ultrastable cycling stability with decay of 0.019% per cycle even at 1 C. Theoretical simulation uncovers that Mo2 C exhibits much stronger binding energies for S8 and Li2 Sn . The energy barrier for the conversion between Li2 S4 and Li2 S2 decreases from 1.02 to 0.72 eV when hybriding with Mo2 C. Furthermore, in situ discharge/charge-dependent Raman spectroscopy shows that long-chain Li2 S8 configuration is generated via S8 ring opening near the first plateaus at ≈2.36 V versus Li/Li+ and the S6 2- configuration in CNT/S electrode is maintained below the potential of ≈2.30 V versus Li/Li+ , indicating that the shuttle of soluble LiPSs happens during the whole discharge process. This work provides deep insights into the polar nanoarchitecture design and scalable fabrication for advanced Li-S batteries.

Fabrication of Highly Textured 2D SnSe Layers with Tunable Electronic Properties for Hydrogen Evolution.

Hydrogen is regarded to be one of the most promising renewable and clean energy sources. Finding a highly efficient and cost-effective catalyst to generate hydrogen via water splitting has become a research hotspot. Two-dimensional materials with exotic structural and electronic properties have been considered as economical alternatives. In this work, 2D SnSe films with high quality of crystallinity were grown on a mica substrate via molecular beam epitaxy. The electronic property of the prepared SnSe thin films can be easily and accurately tuned in situ by three orders of magnitude through the controllable compensation of Sn atoms. The prepared film normally exhibited p-type conduction due to the deficiency of Sn in the film during its growth. First-principle calculations explained that Sn vacancies can introduce additional reactive sites for the hydrogen evolution reaction (HER) and enhance the HER performance by accelerating electron migration and promoting continuous hydrogen generation, which was mirrored by the reduced Gibbs free energy by a factor of 2.3 as compared with the pure SnSe film. The results pave the way for synthesized 2D SnSe thin films in the applications of hydrogen production.

Improved surface-enhanced Raman scattering (SERS) sensitivity to molybdenum oxide nanosheets via the lightning rod effect with application in detecting methylene blue.

MoO2 nanomaterials show a superior surface-enhanced Raman scattering (SERS) property due to their high concentration of free electrons and low resistivity. However, the physical process of semiconductor-based SERS is still elusive because there are many factors that affect the local electromagnetic field intensity and the subsequent Raman intensity of the molecules in close proximity to the semiconductor nanomaterials. Herein, we investigate the important contribution of surface morphology to molybdenum oxide SERS. The MoO3/MoO2 nanosheets (NSs) are synthesized by oxidizing MoO2 NS, and the surface roughness of MoO3 can be controlled through adjusting the oxidization time. Compared with the MoO2 NS before oxidization, the MoO3/MoO2 NSs exhibit a much stronger SERS signal, which favors their application as a SERS substrate to detect trace amounts of methylene blue molecules. The minimum detectable concentration is up to 10-9 M and the maximum enhancement factor is about 1.4 × 105. Meanwhile, excellent signal reproducibility is also observed using the MoO3/MoO2 NSs as the SERS substrate. A simulated electric field distribution shows that a stronger electric field enhancement is formed due to the lightning rod effect in the gap of corrugated MoO3 NSs. These results demonstrate that the surface topography of molybdenum oxide may play a more important role than their oxidation state in SERS signal enhancement.

Hierarchically Porous W-Doped CoP Nanoflake Arrays as Highly Efficient and Stable Electrocatalyst for pH-Universal Hydrogen Evolution.

It is still challenging to develop high-efficiency and low-cost non-noble metal-based electrocatalysts for hydrogen evolution reaction (HER) in pH-universal electrolytes. Herein, hierarchically porous W-doped CoP nanoflake arrays on carbon cloth (W-CoP NAs/CC) are synthesized via facile liquid-phase reactions and a subsequent phosphorization process. The W-CoP NAs/CC hybrid can be directly employed as a binder-free electrocatalyst and delivers superior HER performance in pH-universal electrolytes. Especially, it delivers very low overpotentials of 89, 94, and 102 mV to reach a current density of 10 mA cm-2 in acidic, alkaline, and neutral electrolytes, respectively. Furthermore, it shows a nearly 100% Faradaic efficiency as well as superior long-term stability with no decreasing up to 36 h in pH-universal electrolytes. The outstanding electrocatalytic performance of W-CoP NAs/CC can be mainly attributed to the porous W-doped nanoflake arrays, which not only afford rich exposed active sites, but also accelerate the access of electrolytes and the diffusion of H2 bubbles, thus efficiently promoting the HER performance. This work provides a new horizon to rationally design and synthesize highly effective and stable non-noble metal phosphide-based pH-universal electrocatalysts for HER.

Graphene-Enhanced Brillouin Optomechanical Microresonator for Ultrasensitive Gas Detection.

Chemical sensing is one of the most important applications of nanoscience, whose ultimate aim is to seek higher sensitivity. In recent years, graphene with intriguing quantum properties has spurred dramatic advances ranging from materials science to optoelectronics and mechanics, showing its potential to realize individual molecule solid-state sensors. However, for optical sensing the single atom thickness of graphene greatly limits the light-graphene interactions, bottlenecking their performances. Here we demonstrate a novel approach based on the forward phase-matched Brillouin optomechanics in a graphene inner-deposited high Q (>2 × 106) microfluidic resonator, expanding the "electron-photon" interaction in conventional graphene optical devices to the "electron-phonon-photon" process. The molecular adsorption induced surface elastic modulation in graphene enables the Brillouin optomechanical modes (mechanical Q ≈ 43,670) extremely sensitive (200 kHz/ppm) in ammonia gas detection, achieving a noise equivalent detection limit down to 1 ppb and an unprecedented dynamic range over five orders-of-magnitude with fast response. This work provides a new platform for the researches of graphene-based optomechanics, nanophotonics, and optical sensing.

Tunable terahertz reflection of graphene via ionic liquid gating.

We report a highly efficient tunable THz reflector in graphene. By applying a small gate voltage (up to ±3 V), the reflectance of graphene is modulated from a minimum of 0.79% to a maximum of 33.4% using graphene/ionic liquid structures at room temperature, and the reflection tuning is uniform within a wide spectral range (0.1-1.5 THz). Our observation is explained by the Drude model, which describes the THz wave-induced intraband transition in graphene. This tunable reflectance of graphene may contribute to broadband THz mirrors, deformable THz mirrors, variable THz beam splitters and other optical components.

Flexible terahertz modulator based on coplanar-gate graphene field-effect transistor structure.

The terahertz (THz) modulators, as an essential component of the THz system, have been developed by many efforts until now. However, the development of flexible THz modulators is hindered due to the lack of flexible THz modulating materials. Herein, for the first time to the best of our knowledge, we demonstrated the feasibility of flexible THz modulators based on the coplanar-gate field-effect transistor (FET) structure of ion-gel/graphene/polyethylene terephthalate. The THz transmittance through this THz graphene modulator can be well controlled with a modulation depth up to 22% by tuning the carrier concentration of graphene via electrical gating. Furthermore, because of the integration of high flexibilities of graphene, ion-gel, and polyethylene terephthalate (PET), the proposed THz graphene modulator shows superior flexible performance, where the modulation properties can be maintained almost unchanged, not only under bending deformations, but also before and after bending 1000 times. In addition, due to the unique structure of ion-gel/graphene/PET, the flexible THz graphene modulator has a low insertion loss (1.2 dB). Therefore, this Letter is expected to be beneficial for the potential applications, ranging from the traditional compact THz system to a new flexible THz technology.

Flexible, transparent and high-power triboelectric generator with asymmetric graphene/ITO electrodes.

The reported flexible and transparent triboelectric generator (FTTG) can only output ultralow power density (∼2 µW cm(-2)), which has seriously hindered its further development and application. The low power density of FTTG is mainly limited by the transparent material and the electrode structure. Herein, for the first time, a FTTG with a superior power density of 60.7 µW cm(-2) has been fabricated by designing asymmetric electrodes where graphene and indium tin oxide (ITO) act as top and bottom electrodes respectively. Moreover, the performance of FTTG with graphene/ITO (G/I) asymmetric electrodes (GI-FTTG) almost remains unchanged even after 700 cycles, indicating excellent mechanical stability. The excellent performance of GI-FTTG can be attributed to the suitable materials and unique asymmetric electrode structure: the extraordinary flexibility of the graphene top electrode ensures the GI-FTTG excellent mechanical robustness and stability even after longer cycles, and the bottom electrode with very low sheet resistance guarantees lower internal resistance and higher production rate of induction charges to obtain higher output power density. It shows that light-emitting diodes (LED) can be easily powered by GI-FTTG, which demonstrates that the GI-FTTG is very promising for harvesting electrical energy from human activities by using flexible and transparent devices.

Graphene-coated microfiber Bragg grating for high-sensitivity gas sensing.

A graphene coated microfiber Bragg grating (GMFBG) for gas sensing is reported in this Letter. Taking advantage of the surface field enhancement and gas absorption of a GMFBG, we demonstrate an ultrasensitive approach to detect the concentration of chemical gas. The obtained sensitivities are 0.2 and 0.5 ppm for NH3 and xylene gas, respectively, which are tens of times higher than that of a GMFBG without graphene for tiny gas concentration change detection. Experimental results indicate that the GMFBG-based NH3 gas sensor has fast response due to its highly compact structure. Such a miniature fiber-optic element may find applications in high sensitivity gas sensing and trace analysis.

Demonstration of complex refractive index of graphene waveguide by microfiber-based Mach-Zehnder interferometer.

The complex refractive index (CRI) of graphene waveguide (GW) is of great importance for modeling and developing graphene-based photonic or optoelectronic devices. In this paper, the CRI of the GW is investigated theoretically and experimentally, it is found that the CRI of the GW will modulate the intensity and phase of transmitting light. The phase alterations are obtained spectrally by a Microfiber-based Mach-Zehnder interferometer (MMZI), experimental results demonstrate that the CRIs of the GW vary from 2.91-i13.92 to 3.81-i14.64 for transmitting wavelengths ranging from 1510 to 1590 nm. This method cannot only be used to determine the CRI of the GW optically and provide one of the fundamental parameters for designing graphene-based optic devices for communication and sensing applications, but also is adoptable in graphene-based transformation optics for determination of the CRI of the GW at other wavelengths.

Graphene/liquid crystal based terahertz phase shifters.

Due to its high electrical conductivity and excellent transmittance at terahertz frequencies, graphene is a promising candidate as transparent electrodes for terahertz devices. We demonstrate a liquid crystal based terahertz phase shifter with the graphene films as transparent electrodes. The maximum phase shift is 10.8 degree and the saturation voltage is 5 V with a 50 µm liquid crystal cell. The transmittance at terahertz frequencies and electrical conductivity depending on the number of graphene layer are also investigated. The proposed phase shifter provides a continuous tunability, fully electrical controllability, and low DC voltage operation.

Freestanding ReS2/Graphene Heterostructures as Binder-Free Anodes for Lithium-Ion Batteries.

It is still challenging to develop anode materials with high capacity and long cycling stability for lithium-ion batteries (LIBs). To address such issues, herein, for the first time, we present a three-dimensional and freestanding ReS2/graphene heterostructure (3DRG) as an anode synthesized via a one-pot hydrothermal method. The hybrid shows a hierarchically sandwich-like, nanoporous, and conductive three-dimensional (3D) network constructed by two-dimensional (2D) ReS2/graphene heterostructural nanosheets, which can be directly utilized as a freestanding and binder-free anode for LIBs. When the current density is 100 mA g-1, the 3DRG anode delivers a high reversible specific capacity of 653 mAh g-1. The 3DRG anode also delivers higher rate capability and cycling stability than the bare ReS2 anode. The markedly boosted electrochemical properties derive from the unique nanoarchitecture, which guarantees massive electrochemical active sites, short channels of lithium-ion diffusion, fast electron/ion transportation, and inhibition of the volume change of ReS2 for LIBs.

Atomic Fe/Zn anchored N, S co-doped nano-porous carbon for boosting oxygen reduction reaction.

Dual-single-atom catalysts are well-known due to their excellent catalytic performance of oxygen reduction reaction (ORR) and the tunable coordination environment of the active sites. However, it is still challengable to finely modulate the electronic states of the metal atoms and facilely fabricate a catalyst with dual-single atoms homogeneously dispersed on conductive skeletons with good mass transport. Herein, atomic FeNx/ZnNx sites anchored N, S co-doped nano-porous carbon plates/nanotubes material (Fe0.10ZnNSC) is rationally prepared via a facile room-temperature reaction and high-temperature pyrolysis. The as-prepared Fe0.10ZnNSC catalyst exhibits a positive onset potential of 0.956 V, an impressive half-wave potential of 0.875 V, excellent long-term durability, and a high methanol resistance, outperforming the benchmark Pt/C. The outstanding ORR performance of Fe0.10ZnNSC is due to its unique nanoarchitecture: a large specific surface area (1092.8 cm2 g-1) and well-developed nanopore structure ensure the high accessibility of active sites; the high conductivity of the carbon matrix guarantees a strong ability to transport electrons to the active sites; and the optimized electronic states of FeNx and ZnNx sites possess good oxygen intermediate adsorption/desorption capacity. This strategy can be extended to design and fabricate other non-precious dual-single-atom ORR catalysts.

Rationally Designed Ag@polymer@2-D LDH Nanoflakes for Bifunctional Efficient Electrochemical Sensing of 4-Nitrophenol and Water Oxidation Reaction.

The rational design and demonstration of a facile sequential template-mediated strategy to construct noble-metal-free efficient bifunctional electrocatalysts for efficient oxygen evolution reaction (OER) and electrocatalytic detection of hazardous environmental 4-nitrophenol (4-NP) have continued as a major challenging task. Herein, we construct a novel Ag@polymer/NiAl LDH (designated as APL) nanohybrid as an efficient bifunctional electrocatalyst by a simple hydrolysis method. The well-fabricated APL/GCE exhibited an extensive linear range from 0.1 to 100 µM in optimized conditions. It showed a detection limit (LOD) of 0.0096 µM (9.6 nM) (S/N = 3) for 4-NP in pH 6 by differential pulse voltammetry (DPV). Meanwhile, the newly fabricated APL exhibited outstanding OER activity with a very low overpotential of 259 mV to deliver 10 mA cm-2 current density (J) at a scan rate of 5 mV/s. The Tafel plot value of APL is low (97 mV/dec) compared to that of the benchmark RuO2 due to a fast kinetic reaction. Besides, the durability of the electrocatalyst was assessed by a chronoamperometry test (CA) for 36 h at 1.55 mV vs RHE, and the long-term cycling stability was analyzed by using cyclic voltammetry (CV); after 5000 cycles, the electrocatalyst was highly stable. These demonstrated results could lead to an alternative electrocatalyst construction for the bifunctionally efficient electrochemical sensing of 4-nitrophenol and oxygen evolution reaction.

Template free-synthesis of cobalt-iron chalcogenides [Co0.8Fe0.2L2, L = S, Se] and their robust bifunctional electrocatalysis for the water splitting reaction and Cr(vi) reduction.

The ease of production of materials and showing multiple applications are appealing in this modern era of advanced technology. This paper reports the synthesis of a pair of novel cobalt-iron chalcogenides [Co0.8Fe0.2S2 and Co0.8Fe0.2Se2] with enhanced electro catalytic activities. These ternary metal chalcogenides were synthesized by a one-step template-free approach via a hexamethyldisilazane (HMDS)-assisted synthetic method. Transient photocurrent (TPC) studies and electrochemical impedance spectra (EIS) of these materials showed free electron mobility. Their bifunctional activities were verified in both the electrochemical oxygen evolution reaction (OER) and in the electrochemical reduction of toxic inorganic heavy metal ions [Cr(vi)] in polluted water. The materials showed robust catalytic ability in the oxygen evolution reaction with minimum possible over potential (345 and 350 mV @ η10) as determined by linear sweep voltammetry and the lower Tafel values (52.4 and 84.5 mV dec-1) for Co0.8Fe0.2Se2 and Co0.8Fe0.2S2 respectively. Surprisingly, both the materials also showed an excellent activity towards electrochemical Cr(vi) reduction to Cr(iii). Besides the maximum current achieved for Co0.8Fe0.2S2, a minimum value for the Limit of detection (LOD) was obtained for Co0.8Fe0.2S2 (0.159 µg L-1) compared to Co0.8Fe0.2Se2 (0.196 µg L-1). We tested the durability of catalysts, the critical factor for the prolonged use of catalysts, through the recyclability measurements of these materials as catalysts. Both the catalysts presented outstanding durability and balanced electro catalytic activities for up to 1500 CV cycles, and chronoamperometry studies also confirmed exceptional stability. The enhanced catalytic activities of these materials are ascribed to the free electron movement, evidenced by the increased TPC measured and EIS. Therefore, the template-free synthesis of these electro catalysts containing non-noble metal illustrates the practical approach to develop such types of catalysts for multiple functions.

Dual Fe, Zn single atoms anchored on carbon nanotubes inlaid N, S-doped hollow carbon polyhedrons for boosting oxygen reduction reaction.

It is still challengeable but significant to rationally develop dual-metal single-atom catalysts with rich accessible active sites and excellent intrinsic catalytic activity towards oxygen reduction reaction (ORR). Herein, we present a novel dual-metal single-atom catalyst, Fe and Zn single atoms homogenously anchored on carbon nanotubes inlaid N, S-doped hollow carbon polyhedrons (FeZn-NSC), synthesized by facile iron-salt impregnation and high-temperature pyrolysis for zeolitic imidazolate framework-8. Due to the synergistic effects of the hierarchical porous nanoarchitecture with high specific surface area (795.48 m2 g-1), N, S co-doped hollow carbon polyhedrons, in-situ grown highly conductive carbon nanotubes, and high loading of dual-metal single-atoms of Fe (3.12 wt%) and Zn (3.71 wt%), the optimized FeZn-NSC delivers outstanding ORR performance with high half-wave potential of 0.87 V, low Tafel slope of 44.7 mV dec-1, long-term durability, and strong tolerance of methanol crossover. This work provides a strategy to rationally design and facilely synthesize dual-metal single-atom catalysts with high ORR activity.