Charge transfer doping of graphene without degrading carrier mobility

Density functional calculations are used to analyze the charge transfer doping mechanism by molecules absorbed onto graphene. Typical dopants studied are AuCl3, FeCl3, SbF5, HNO3, MoO3, Cs2O, O2, and OH. The Fermi level shifts are correlated with the electron affinity or ionization potential of the dopants. We pay particular attention to whether the dopants form direct chemisorptive bonds which cause the underlying carbon atoms to pucker to form sp3 sites as these interrupt the p bonding of the basal plane, and cause carrier scattering and thus degrade the carrier mobility. Most species even those with high or low electronegativity do not cause puckering. In contrast, reactive radicals like -OH cause puckering of the basal plane, creating sp3 sites which degrade mobility

Band edge states, intrinsic defects, and dopants in monolayer HfS2 and SnS2

Although monolayer HfS2 and SnS2 do not have a direct bandgap like MoS2, they have much higher carrier mobilities. Their band offsets are favorable for use with WSe2 in tunnel field effect transistors. Here, we study the effective masses, intrinsic defects, and substitutional dopants of these dichalcogenides. We find that HfS2 has surprisingly small effective masses for a compound that might appear partly ionic. The S vacancy in HfS2 is found to be a shallow donor while that in SnS2 is a deep donor. Substitutional dopants at the S site are found to be shallow. This contrasts with MoS2 where donors and acceptors are not always shallow or with black phosphorus where dopants can reconstruct into deep non-doping configurations. It is pointed out that HfS2 is more favorable than MoS2 for semiconductor processing because it has the more convenient CVD precursors developed for growing HfO2.We thank EPSRC Grant No. EP/P005152/1 and CSC for support

Electronic structure of metallic and insulating phases of vanadium dioxide and its oxide alloys

VO2 attracts much attention due to its metal-insulator transition. Alloying VO2 with MgO and GeO2 allows the band gap and the transition temperature to be varied. We find that the spin order plays a key role in creating the band gap in the low-temperature M1 phase. For MgO alloying, the alloying fraction n(MgnV1−nO2−n) is varied from 12.5 to 33.3%. The minimum band gap does not change without a structural rearrangement because both band edges of insulating VO2 consist of only V 3d states on sixfold-coordinated V sites. A crystal search finds that if the Mg fraction in the alloy is large enough (>20%), fivefold-coordinated V sites can have lower energy than the sixfold sites, and the band gaps are doubled. For GeO2 alloying, the insulating M1 structure reverts to rutile because GeO2 has a rutile phase. The result matches the experimental observation and is very important in guiding VO2's applications such as smart coating and nonlinear resistor.The authors acknowledge funding from Engineering and Physical Sciences Research Council (EPSRC) Grant No. EP/P005152/1 and European Commissio

Hybrid and Composite Crystalline Materials

A facile approach for developing an interfacial solar evaporator by heat localization of solar-thermal energy conversion at water-air liquid composed by in-situ polymerization of Fe2O3 nanoparticles (Fe2O3@PPy) deposited over a facial sponge is proposed. The demonstrated system consists of a floating solar receiver having a vertically cross-linked microchannel for wicking up saline water. The in situ polymerized Fe2O3@PPy interfacial layer promotes diffuse reflection and its rough black surface allows Omni-directional solar absorption (94%) and facilitates efficient thermal localization at the water/air interface and offers a defect-rich surface to promote heat localization (41.9 °C) and excellent thermal management due to cellulosic content. The self-floating composite foam reveals continuous vapors generation at a rate of 1.52 kg m−2 h−1 under one 1 kW m−2 and profound evaporating efficiency (95%) without heat losses that dissipates in its surroundings. Indeed, long-term evaporation experiments reveal the negligible disparity in continuous evaporation rate (33.84 kg m−2/8.3 h) receiving two sun solar intensity, and ensures the stability of the device under intense seawater conditions synchronized with excellent salt rejection potential. More importantly, Raman spectroscopy investigation validates the orange dye rejection via Fe2O3@PPy solar evaporator. The combined advantages of high efficiency, self-floating capability, multimedia rejection, low cost, and this configuration are promising for producing large-scale solar steam generating systems appropriate for commercial clean water yield due to their scalable fabrication

Progress in electrolyte-free fuel cells

Solid oxide fuel cell (SOFC) represents a clean electrochemical energy conversion technology with characteristics of high conversion efficiency and low emissions. It is one of the most important new energy technologies in the future. However, the manufacture of SOFCs based on the structure of anode/electrolyte/cathode is complicated and time-consuming. Thus, the cost for the entire fabrication and technology is too high to be affordable, and challenges still hinder commercialization. Recently, a novel type of electrolyte-free fuel cell (EFFC) with single component was invented, which could be the potential candidate for the next generation of advanced fuel cells. This paper briefly introduces the EFFC, working principle, performance, and advantages with updated research progress. A number of key R&D issues about EFFCs have been addressed, and future opportunities and challenges are discussed

Cascade NH3 Oxidation and N2O Decomposition via Bifunctional Co and Cu Catalysts

The selective catalytic oxidation of NH3 (NH3-SCO) to N2 is an important reaction for the treatment of diesel engine exhaust. Co3O4 has the highest activity among non-noble metals but suffers from N2O release. Such N2O emissions have recently been regulated due to having a 300× higher greenhouse gas effect than CO2. Here, we design CuO-supported Co3O4 as a cascade catalyst for the selective oxidation of NH3 to N2. The NH3-SCO reaction on CuO-Co3O4 follows a de-N2O pathway. Co3O4 activates gaseous oxygen to form N2O. The high redox property of the CuO-Co3O4 interface promotes the breaking of the N-O bond in N2O to form N2. The addition of CuO-Co3O4 to the Pt-Al2O3 catalyst reduces the full NH3 conversion temperature by 50 K and improves the N2 selectivity by 20%. These findings provide a promising strategy for reducing N2O emissions and will contribute to the rational design and development of non-noble metal catalysts

Phase boundary engineering of metal-organic-framework-derived carbonaceous nickel selenides for sodium-ion batteries

Abstract: Sodium-ion batteries (SIBs) are promising power sources due to the low cost and abundance of battery-grade sodium resources, while practical SIBs suffer from intrinsically sluggish diffusion kinetics and severe volume changes of electrode materials. Metal-organic framework (MOFs) derived carbonaceous metal compound offer promising applications in electrode materials due to their tailorable composition, nanostructure, chemical and physical properties. Here, we fabricated hierarchical MOF-derived carbonaceous nickel selenides with bi-phase composition for enhanced sodium storage capability. As MOF formation time increases, the pyrolyzed and selenized products gradually transform from a single-phase Ni3Se4 into bi-phase NiSex then single-phase NiSe2, with concomitant morphological evolution from solid spheres into hierarchical urchin-like yolk-shell structures. As SIBs anodes, bi-phase NiSex@C/CNT-10h (10 h of hydrothermal synthesis time) exhibits a high specific capacity of 387.1 mAh/g at 0.1 A/g, long cycling stability of 306.3 mAh/g at a moderately high current density of 1 A/g after 2,000 cycles. Computational simulation further proves the lattice mismatch at the phase boundary facilitates more interstitial space for sodium storage. Our understanding of the phase boundary engineering of transformed MOFs and their morphological evolution is conducive to fabricate novel composites/hybrids for applications in batteries, catalysis, sensors, and environmental remediation