Scalable heating-up synthesis of monodisperse Cu2ZnSnS4 nanocrystals

Monodisperse Cu2ZnSnS4 (CZTS) nanocrystals (NCs), with quasi spherical shape, were prepared by a facile, high-yield, scalable, and high-concentration heat-up procedure. The key parameters to minimize the NC size distribution were efficient mixing and heat transfer in the reaction mixture through intensive argon bubbling and improved control of the heating ramp stability. Optimized synthetic conditions allowed the production of several grams of highly monodisperse CZTS NCs per batch, with up to 5 wt % concentration in a crude solution and a yield above 90%

Colloidal Ni2- : XCoxP nanocrystals for the hydrogen evolution reaction

A cost-effective and scalable approach was developed to produce monodisperse NiCoP nanocrystals (NCs) with composition tuned over the entire range (0 ≤ x ≤ 2). NiCoP NCs were synthesized using low-cost, stable and low-toxicity triphenyl phosphite (TPP) as a phosphorus source, metal chlorides as metal precursors and hexadecylamine (HDA) as a ligand. The synthesis involved the nucleation of amorphous Ni-P and its posterior crystallization and simultaneous incorporation of Co. The composition, size and morphology of the NiCoP NCs could be controlled simply by varying the ratio of Ni and Co precursors and the amounts of TPP and HDA. Ternary NiCoP-based electrocatalysts exhibited enhanced electrocatalytic activity toward the hydrogen evolution reaction (HER) compared to binary phosphides. In particular, NiCoP electrocatalysts displayed the lowest overpotential of 97 mV at J = 10 mA cm and an excellent long-term stability. DFT calculations of the Gibbs free energy for hydrogen adsorption at the surface of NiCoP NCs showed NiCoP to have the most appropriate composition to optimize this parameter within the whole NiCoP series. However, the hydrogen adsorption energy was demonstrated not to be the only parameter controlling the HER activity in NiCoP

Chromium phosphide CrP as highly active and stable electrocatalysts for oxygen electroreduction in alkaline media

Catalysts for oxygen reduction reaction (ORR) are key components in emerging energy technologies such as fuel cells and metal-air batteries. Developing low-cost, high performance and stable electrocatalysts is critical for the extensive implementation of these technologies. Herein, we present a procedure to prepare colloidal chromium phosphide CrP nanocrystals and we test their performance as ORR electrocatalyst. CrP-based catalysts exhibited remarkable activities with a limiting current density of 4.94 mA cm at 0.2 V, a half-potential of 0.65 V and an onset potential of 0.8 V at 1600 rpm, which are comparable to commercial Pt/C. Advantageously, CrP-based catalysts displayed much higher stabilities and higher tolerances to methanol in alkaline solution. Using density functional theory calculations, we demonstrate CrP to provide a very strong chemisorption of O that facilitates its reduction and explains the excellent ORR performance experimentally demonstrated

Triphenyl phosphite as the phosphorus source for the scalable and cost-effective production of transition metal phosphides

Transition metal phosphides have great potential to optimize a number of functionalities in several energy conversion and storage applications, particularly when nanostructured or in nanoparticle form. However, the synthesis of transition metal phosphide nanoparticles and its scalability is often limited by the toxicity, air sensitivity, and high cost of the reagents used. We present here a simple, scalable, and cost-effective "heating up" procedure to produce metal phosphides using inexpensive, low-toxicity, and air-stable triphenyl phosphite as source of phosphorus and chlorides as metal precursors. This procedure allows the synthesis of a variety of phosphide nanoparticles, including phosphides of Ni, Co, and Cu. The use of carbonyl metal precursors further allowed the synthesis of FeP and MoP nanoparticles. The fact that minor modifications in the experimental parameters allowed producing nanoparticles with different compositions and even to tune their size and shape shows the high potential and versatility of the triphenyl phosphite precursor and the presented method. We also detail here a methodology to displace organic ligands from the surface of phosphide nanoparticles, which is a key step toward their application in energy conversion and storage systems

SnP nanocrystals as anode materials for Na-ion batteries

Tin monophosphide is a layered material consisting of Sn-P-P-Sn sandwiches that are stacked on top of each other to form a three dimensional crystallographic structure. Its composition and crystal structure makes it an excellent candidate anode material for sodium-ion batteries (SIBs). However, SnP is yet to be explored for such and other applications due to its challenging synthesis. In the present work, we report the synthesis of SnP nanocrystals (NCs) from the reaction of hexamethylphosphorous triamide (HMPT) and a tin phosphonate prepared from tin oxalate and a long chain phosphonic acid. SnP NCs obtained from this reaction displayed a spherical geometry and a trigonal crystallographic phase with a superstructure attributed to ordered diphosphorus pairs. Such NCs were mixed with carbon black and used as anode materials in SIBs. SIBs based on SnP NCs and sodium(i) bis(fluorosulfonyl)imide (NaFSI) electrolyte displayed a high reversible capacity of 600 mA h g at a current density of 100 mA g and cycling stability for over 200 cycles. Their excellent cycling performance is associated with both the small size of the crystal domains and the particular composition and phase of SnP which prevent mechanical disintegration and major phase separation during sodiation and desodiation cycles. These results demonstrate SnP to be an attractive anode material for sodium ion batteries

Growth and reductive transformation of a gold shell around pyramidal cadmium selenide nanocrystals

We report the growth of an unstable shell-like gold structure around dihexagonal pyramidal CdSe nanocrystals in organic solution and the structural transformation to spherical domains by two means: i) electron beam irradiation (in situ) and (ii) addition of a strong reducing agent during synthesis. By varying the conditions of gold deposition, such as ligands present or the geometry of the CdSe nanocrystals, we were able to tune the gold domain size between 1.4 nm to 3.9 nm and gain important information on the role of surface chemistry in hetero nanoparticle synthesis and seed reactivity, both of which are crucial points regarding the chemical design of new materials for photocatalysis and optoelectronic applications.Comment: 5 pages, 4 figure

Library based identification and characterisation of polymers with nano-FTIR and IR-sSNOM imaging

AFM is a technique widely applied in the nanoscale characterisation of polymers and their surface properties. With nano-FTIR and IR-sSNOM imaging an optical dimension is added to this technique that allows for straightforward high resolution characterisation and spectroscopy of polymers. As the volume sampled by these near-field techniques depends mostly on the radius of the cantilever tip, typically 10 nm, it is orders of magnitude smaller than in conventional techniques. Nevertheless, comparability of nano-FTIR near-field spectra and data from macroscopic methods has been shown. Some relevant polymers such as polystyrene however, prove to be more difficult to detect than others. Furthermore, the small sampled volume suggests lower signal quality of nano-FTIR data and proof of its suitability for a reliable library search identification is lacking. To evaluate the techniques especially towards automatic and higher throughput identification of nanoscale polymers, for example in blends or environmental samples, we examined domain distributions in a PS-LDPE film and spectral responses of foils of the most relevant commercial polymers. We demonstrate the successful library search identification of all samples with nano-FTIR data measured in less than seven minutes/spectrum with a free IR spectra database in combination with established commercial OPUS 7.5 software and recently released freeware siMPle. We discuss aspects affecting the accuracy of the identification for different polymers and show that already the small spectral range of 1700-1300 cm-1 leads to similar success in differentiating between polymer types with near-field data as with conventional far-field FTIR spectroscopy. Even a polymer sample weathered in the environment can be identified without prior cleaning, proving wide fields of applications for characterisation and identification of diverse polymer samples. Finally, we propose measurement and analysis strategies for known and unknown samples with this novel technique