Thermoelectric power of bulk black-phosphorus

The potential of bulk black-phosphorus for thermoelectric applications has been experimentally studied. The Seebeck Coefficient (S) has been measured in the temperature range from 300 K to 385 K, finding a value of S = +335 +- 10 uV/K at room temperature (indicating a naturally occurring p-type conductivity). S increases with temperature, as expected for p-type semiconductors, which can be attributed to an increase of the charge carrier density. The electrical resistance drops up to a 40 % while heating in the studied temperature range. As a consequence, the power factor at 385 K is 2.7 times higher than that at room temperature. This work demonstrates the feasibility of black-phosphorus in thermoelectric applications, such as thermal energy scavenging, which typically require devices with high performance at temperatures above room temperature.Comment: 3 figure

A Graphene Acid - TiO2 Nanohybrid as Multifunctional Heterogeneous Photocatalyst for the Synthesis of 1,3,4-Oxadiazoles

The immobilization of TiO2 nanoparticles on graphene acid (GA), a conductive graphene derivative densely functionalized with COOH groups, is presented. The interaction between the carboxyl groups of the surface and the titanium precursor leads to a controlled TiO2 heterogenization on the nanosheet according to microscopic and spectroscopic characterizations. Electronic communication shared among graphene and semiconductor nanoparticles shifts the hybrid material optical features toward less energetic radiation but maintaining the conductivity. Therefore, GA-TiO2 is employed as heterogeneous photocatalyst for the synthesis of 2,5-disubstituted 1,3,4-oxadiazoles using ketoacids and hydrazides as substrates. The material presented enhanced photoactivity compared to bare TiO2, being able to yield a large structural variety of oxadiazoles in reaction times as fast as 1 h with full recyclability and stability. The carbocatalytic character of GA is the responsible for the substrates condensation and the GA-TiO2 light interaction ability is able to photocatalyze the cyclization to the final 1,3,4-oxadiazoles, demonstrating the optimal performance of this multifunctional photocatalytic materialFinancial support was provided by the Spanish Government (RTI2018-095038-B-I00), FotoaArt “Comunidad de Madrid”, and European Structural Funds (S2018/NMT-4367) proyectos sinérgicos I+D (Y2020/NMT-6469) and Comunidad Autónoma de Madrid (SI1/PJI/2019-00237). M.B. and M.B. thank the Spanish MICINN for the Juan de la Cierva Incorporación contracts (IJC2019-042157-I and IJC2019- 042430-I). We also acknowledge the electron microscopy analysis from CNME. This work was supported by the national project NovaCO2 (PID2020-118593RB-C22) funded by MCIN/AEI/10.13039/50110001103

Targeting the affective brain-a randomized controlled trial of real-time fMRI neurofeedback in patients with depression.

open access articleFunctional magnetic resonance imaging neurofeedback (fMRI-NF) training of areas involved in emotion processing can reduce depressive symptoms by over 40% on the Hamilton Depression Rating Scale (HDRS). However, it remains unclear if this efficacy is specific to feedback from emotion-regulating regions. We tested in a single-blind, randomized, controlled trial if upregulation of emotion areas (NFE) yields superior efficacy compared to upregulation of a control region activated by visual scenes (NFS). Forty-three moderately to severely depressed medicated patients were randomly assigned to five sessions augmentation treatment of either NFE or NFS training. At primary outcome (week 12) no significant group mean HDRS difference was found (B = −0.415 [95% CI −4.847 to 4.016], p = 0.848) for the 32 completers (16 per group). However, across groups depressive symptoms decreased by 43%, and 38% of patients remitted. These improvements lasted until follow-up (week 18). Both groups upregulated target regions to a similar extent. Further, clinical improvement was correlated with an increase in self-efficacy scores. However, the interpretation of clinical improvements remains limited due to lack of a sham-control group. We thus surveyed effects reported for accepted augmentation therapies in depression. Data indicated that our findings exceed expected regression to the mean and placebo effects that have been reported for drug trials and other sham-controlled high-technology interventions. Taken together, we suggest that the experience of successful self-regulation during fMRI-NF training may be therapeutic. We conclude that if fMRI-NF is effective for depression, self-regulation training of higher visual areas may provide an effective alternative

Hydroxamate Titanium−Organic Frameworks and the Effect of Siderophore-Type Linkers over Their Photocatalytic Activity

The chemistry of Metal-Organic Frameworks (MOFs) relies on the controlled linking of organic molecules and inorganic secondary building units to assemble an unlimited number of reticular frameworks. However, the design of porous solids with chemical stability remains still limited to carboxylate or azolate groups. There is a timely opportunity to develop new synthetic platforms that make use of unexplored metal binding groups to produce metal-linker joints with hydrolytical stability. Living organisms use siderophores (iron carriers in greek) to effectively assimilate iron in soluble form. These compounds make use of hard oxodonors as hydroxamate or catecholate groups to coordinate metal Lewis acids like iron, aluminium or titanium to form metal complexes very stable in water. Inspired by the chemistry of these microorganisms, we report the first hydroxamate MOF prepared by direct synthesis. MUV-11 (MUV = Materials of Universidad de Valencia) is a crystalline, porous material (close to 800 m2·g-1) that combines photoactivity with good chemical stability in acid conditions. By using a high-throughput approach, we also demonstrate that this new chemistry is compatible with the formation of single crystalline phases for multiple titanium salts, thus expanding the scope of precursors accessible. Titanium frameworks are regarded as promising materials for photocatalytic applications. Our photoelectrochemical and catalytic tests suggests important differences for MUV-11. Compared to other Ti-MOFs, changes in the photoelectrochemical and photocatalytic activity have been rationalized with computational modelling revealing how the chemistry of siderophores can introduce changes to the electronic structure of the frontier orbitals, relevant to the photocatalytic activity of these solids

Photoinduced Charge Transfer and Trapping on Single Gold Metal Nanoparticles on TiO2

We present a study of the effect of gold nanoparticles (Au NPs) on TiO2 on charge generation and trapping during illumination with photons of energy larger than the substrate band gap. We used a novel characterization technique, photoassisted Kelvin probe force microscopy, to study the process at the single Au NP level. We found that the photoinduced electron transfer from TiO2 to the Au NP increases logarithmically with light intensity due to the combined contribution of electron-hole pair generation in the space charge region in the TiO2-air interface and in the metal-semiconductor junction. Our measurements on single particles provide direct evidence for electron trapping that hinders electron-hole recombination, a key factor in the enhancement of photo(electro)catalytic activity.This work was supported by the Office of Basic Energy Sciences (BES) of the U.S. Department of Energy (DOE) under contract DE-AC02-05CH11231 through the Structure and Dynamics of Materials Interfaces Program (FWP KC31SM) and the Molecular Foundry. M.L. acknowledges funds from Comunidad de Madrid (P2018/EMT-4308), a Fulbright grant PRX16/00564, and the MCIU-AEI-FEDERUE (RTI2018-096937-B-C22 and MAT2014-59772-C2-1-P). J.C. acknowledges financial support from Ministerio de Ciencia e Innovación (MICINN) and the European Union through the project PID2019-104272RB-C52. Also, Y.H. acknowledges financial support from MCIU through MAT2014-59772-C2-2- P and L.M. from EC through ERC-2013-SYG-610256. V.A.P.O. and M.B. acknowledge the financial support from EC through ERC CoG HyMAP 648319, MINECO PID2019- 106315RB-I00 and ENE2017-89170-R, ″Comunidad de Madrid″ and European Structural Funds (FotoArt-CM project S2018/NMT-4367) and Fundación Ramón Areces (Art-Leaf project). M.B. also thanks the Juan de la Cierva Incorporación contract (IJC2019042430-I). X.Z. was supported by the NSF-BSF 359 grant number 1906014. The authors thank Prof. Eran Edri, María Ujué González Sagardoy, and Judit Meseguer- Oliver for fruitful discussions and Asylum customer support for help with modifications of the AFM

Unravelling the effect of charge dynamics at the plasmonic metal/semiconductor interface for CO2 photoreduction

Sunlight plays a critical role in the development of emerging sustainable energy conversion and storage technologies. Light-induced CO2 reduction by artificial photosynthesis is one of the cornerstones to produce renewable fuels and environmentally friendly chemicals. Interface interactions between plasmonic metal nanoparticles and semiconductors exhibit improved photoactivities under a wide range of the solar spectrum. However, the photo-induced charge transfer processes and their influence on photocatalysis with these materials are still under debate, mainly due to the complexity of the involved routes occurring at different timescales. Here, we use a combination of advanced in situ and time-resolved spectroscopies covering different timescales, combined with theoretical calculations, to unravel the overall mechanism of photocatalytic CO2 reduction by Ag/TiO2 catalysts. Our findings provide evidence of the key factors determining the enhancement of photoactivity under ultraviolet and visible irradiation, which have important implications for the design of solar energy conversion materials