Browse
Submit Data
Databases
API
Help

Dataset Information

28 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Electrocatalytic hydrogen evolution with gallium hydride and ligand-centered reduction.

ABSTRACT: GaIII chloride tetrakis(pentafluorophenyl)porphyrin (1) was synthesized and shown to be a highly active and stable post-transition metal-based electrocatalyst for the hydrogen evolution reaction (HER). Electrochemical and spectroscopic studies indicate that both the first and second reduction events of 1 are ligand-centered. The 2e-reduced form 1 2- reacts with a proton to give GaIII-H species (1-H), which undergoes protonolysis with Brønsted acids to produce H2. The identification of key intermediates 1 -, 1 2-, and 1-H leads to a catalytic cycle, which is valuable for the fundamental understanding of the HER. This study presents a rare but highly active HER electrocatalyst with unusual features, including ligand-centered electron transfer and formation of post-transition metal hydride.

SUBMITTER: Wang N

PROVIDER: S-EPMC6385664 | biostudies-literature | 2019 Feb

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Electrocatalytic hydrogen evolution with gallium hydride and ligand-centered reduction.

Wang Ni N Lei Haitao H Zhang Zongyao Z Li Jianfeng J Zhang Wei W Cao Rui R

Chemical science 20181227 8

GaIII chloride tetrakis(pentafluorophenyl)porphyrin (1) was synthesized and shown to be a highly active and stable post-transition metal-based electrocatalyst for the hydrogen evolution reaction (HER). Electrochemical and spectroscopic studies indicate that both the first and second reduction events of 1 are ligand-centered. The 2e-reduced form 1 2- reacts with a proton to give GaIII-H species (1-H), which undergoes protonolysis with B ...[more]

PMID: 30881656

Similar Datasets

Hydrogen bonding steers the product selectivity of electrocatalytic CO reduction.

Project description:The product selectivity of many heterogeneous electrocatalytic processes is profoundly affected by the liquid side of the electrocatalytic interface. The electrocatalytic reduction of CO to hydrocarbons on Cu electrodes is a prototypical example of such a process. However, probing the interactions of surface-bound intermediates with their liquid reaction environment poses a formidable experimental challenge. As a result, the molecular origins of the dependence of the product selectivity on the characteristics of the electrolyte are still poorly understood. Herein, we examined the chemical and electrostatic interactions of surface-adsorbed CO with its liquid reaction environment. Using a series of quaternary alkyl ammonium cations ([Formula: see text], [Formula: see text], [Formula: see text], and [Formula: see text]), we systematically tuned the properties of this environment. With differential electrochemical mass spectrometry (DEMS), we show that ethylene is produced in the presence of [Formula: see text] and [Formula: see text] cations, whereas this product is not synthesized in [Formula: see text]- and [Formula: see text]-containing electrolytes. Surface-enhanced infrared absorption spectroscopy (SEIRAS) reveals that the cations do not block CO adsorption sites and that the cation-dependent interfacial electric field is too small to account for the observed changes in selectivity. However, SEIRAS shows that an intermolecular interaction between surface-adsorbed CO and interfacial water is disrupted in the presence of the two larger cations. This observation suggests that this interaction promotes the hydrogenation of surface-bound CO to ethylene. Our study provides a critical molecular-level insight into how interactions of surface species with the liquid reaction environment control the selectivity of this complex electrocatalytic process.

| S-EPMC6511002 | biostudies-literature

A fundamental viewpoint on the hydrogen spillover phenomenon of electrocatalytic hydrogen evolution.

Project description:Hydrogen spillover phenomenon of metal-supported electrocatalysts can significantly impact their activity in hydrogen evolution reaction (HER). However, design of active electrocatalysts faces grand challenges due to the insufficient understandings on how to overcome this thermodynamically and kinetically adverse process. Here we theoretically profile that the interfacial charge accumulation induces by the large work function difference between metal and support (∆Φ) and sequentially strong interfacial proton adsorption construct a high energy barrier for hydrogen transfer. Theoretical simulations and control experiments rationalize that small ∆Φ induces interfacial charge dilution and relocation, thereby weakening interfacial proton adsorption and enabling efficient hydrogen spillover for HER. Experimentally, a series of Pt alloys-CoP catalysts with tailorable ∆Φ show a strong ∆Φ-dependent HER activity, in which PtIr/CoP with the smallest ∆Φ = 0.02 eV delivers the best HER performance. These findings have conclusively identified ∆Φ as the criterion in guiding the design of hydrogen spillover-based binary HER electrocatalysts.

| S-EPMC8190308 | biostudies-literature

Copper Metallopolymer Catalyst for the Electrocatalytic Hydrogen Evolution Reaction (HER).

Project description:Conjugated polymers with stabilizing coordination units for single-site catalytic centers are excellent candidates to minimize the use of expensive noble metal electrode materials. In this study, conjugated metallopolymer, POS[Cu], was synthesized and fully characterized by means of spectroscopical, electrochemical, and photophysical methods. The copper metallopolymer was found to be highly active for the electrocatalytic hydrogen generation (HER) in an aqueous solution at pH 7.4 and overpotentials at 300 mV vs. reversible hydrogen electrode (RHE). Compared to the platinum electrode, the obtained overpotential is only 100 mV higher. The photoelectrochemical tests revealed that the complexation of the conjugated polymer POS turned its intrinsically electron-accepting (p-type) properties into an electron-donor (n-type) with photocurrent responses ten times higher than the organic photoelectrode.

| S-EPMC6401685 | biostudies-literature

Graphene Supported Rhodium Nanoparticles for Enhanced Electrocatalytic Hydrogen Evolution Reaction.

Project description:Current research on catalysts for proton exchange membrane fuel cells (PEMFC) is based on obtaining higher catalytic activity than platinum particle catalysts on porous carbon. In search of a more sustainable catalyst other than platinum for the catalytic conversion of water to hydrogen gas, a series of nanoparticles of transition metals viz., Rh, Co, Fe, Pt and their composites with functionalized graphene such as RhNPs@f-graphene, CoNPs@f-graphene, PtNPs@f-graphene were synthesized and characterized by SEM and TEM techniques. The SEM analysis indicates that the texture of RhNPs@f-graphene resemble the dispersion of water droplets on lotus leaf. TEM analysis indicates that RhNPs of <10 nm diameter are dispersed on the surface of f-graphene. The air-stable NPs and nanocomposites were used as electrocatalyts for conversion of acidic water to hydrogen gas. The composite RhNPs@f-graphene catalyses hydrogen gas evolution from water containing p-toluene sulphonic acid (p-TsOH) at an onset reduction potential, Ep, -0.117 V which is less than that of PtNPs@f-graphene (Ep, -0.380 V) under identical experimental conditions whereas the onset potential of CoNPs@f-graphene was at Ep, -0.97 V and the FeNPs@f-graphene displayed onset potential at Ep, -1.58 V. The pure rhodium nanoparticles, RhNPs also electrocatalyse at Ep, -0.186 V compared with that of PtNPs at Ep, -0.36 V and that of CoNPs at Ep, -0.98 V. The electrocatalytic experiments also indicate that the RhNPs and RhNPs@f-graphene are stable, durable and they can be recycled in several catalytic experiments after washing with water and drying. The results indicate that RhNPs and RhNPs@f-graphene are better nanoelectrocatalysts than PtNPs and the reduction potentials were much higher in other transition metal nanoparticles. The mechanism could involve a hydridic species, Rh-H- followed by interaction with protons to form hydrogen gas.

| S-EPMC6863816 | biostudies-literature

Vertically Aligned Ultrathin 1T-WS2 Nanosheets Enhanced the Electrocatalytic Hydrogen Evolution.

Project description:Efficient evolution of hydrogen through electrocatalysis holds tremendous promise for clean energy. The catalytic efficiency for hydrogen evolution reaction (HER) strongly depends on the number and activity of active sites. To this end, making vertically aligned, ultrathin, and along with rich metallic phase WS2 nanosheets is effective to maximally unearth the catalytic performance of WS2 nanosheets. Metallic 1T polymorph combined with vertically aligned ultrathin WS2 nanosheets on flat substrate is successfully prepared via one-step simple hydrothermal reaction. The nearly vertical orientation of WS2 nanosheets enables the active sites of surface edge and basal planes to be maximally exposed. Here, we report vertical 1T-WS2 nanosheets as efficient catalysts for hydrogen evolution with low overpotential of 118 mV at 10 mA cm-2 and a Tafel slope of 43 mV dec-1. In addition, the prepared WS2 nanosheets exhibit extremely high stability in acidic solution as the HER catalytic activity and show no degradation after 5000 continuous potential cycles. Our results indicate that vertical 1T-WS2 nanosheets are attractive alternative to the precious platinum benchmark catalyst and rival MoS2 materials that have recently been heavily scrutinized for hydrogen evolution. Vertical 1T-WS2 for hydrogen evolution.

| S-EPMC5981154 | biostudies-literature

Molecular metal-Nx centres in porous carbon for electrocatalytic hydrogen evolution.

Project description:Replacement of precious platinum with efficient and low-cost catalysts for electrocatalytic hydrogen evolution at low overpotentials holds tremendous promise for clean energy devices. Here we report a novel type of robust cobalt-nitrogen/carbon catalyst for the hydrogen evolution reaction (HER) that is prepared by the pyrolysis of cobalt-N4 macrocycles or cobalt/o-phenylenediamine composites and using silica colloids as a hard template. We identify the well-dispersed molecular CoNx sites on the carbon support as the active sites responsible for the HER. The CoNx/C catalyst exhibits extremely high turnover frequencies per cobalt site in acids, for example, 0.39 and 6.5?s(-1) at an overpotential of 100 and 200?mV, respectively, which are higher than those reported for other scalable non-precious metal HER catalysts. Our results suggest the great promise of developing new families of non-precious metal HER catalysts based on the controlled conversion of homogeneous metal complexes into solid-state carbon catalysts via economically scalable protocols.

| S-EPMC4918366 | biostudies-literature

Studies of cobalt-mediated electrocatalytic CO2 reduction using a redox-active ligand.

Project description:The cobalt complex [Co(III)N4H(Br)2](+) (N4H = 2,12-dimethyl-3,7,11,17-tetraazabicyclo-[11.3.1]-heptadeca-1(7),2,11,13,15-pentaene) was used for electrocatalytic CO2 reduction in wet MeCN with a glassy carbon working electrode. When water was employed as the proton source (10 M in MeCN), CO was produced (fCO= 45% ± 6.4) near the Co(I/0) redox couple for [Co(III)N4H(Br)2](+) (E1/2 = -1.88 V FeCp2(+/0)) with simultaneous H2 evolution (fH2= 30% ± 7.8). Moreover, we successfully demonstrated that the catalytically active species is homogeneous through the use of control experiments and XPS studies of the working glassy-carbon electrodes. As determined by cyclic voltammetry, CO2 catalysis occurred near the formal Co(I/0)redox couple, and attempts were made to isolate the triply reduced compound ("[Co(0)N4H]"). Instead, the doubly reduced ("Co(I)") compounds [CoN4] and [CoN4H(MeCN)](+) were isolated and characterized by X-ray crystallography. Their molecular structures prompted DFT studies to illuminate details regarding their electronic structure. The results indicate that reducing equivalents are stored on the ligand, implicating redox noninnocence in the ligands for H2 evolution and CO2 reduction electrocatalysis.

| S-EPMC4033636 | biostudies-literature

Reversible Ligand-Centered Reduction in Low-Coordinate Iron Formazanate Complexes.

Project description:Coordination of redox-active ligands to metals is a compelling strategy for making reduced complexes more accessible. In this work, we explore the use of redox-active formazanate ligands in low-coordinate iron chemistry. Reduction of an iron(II) precursor occurs at milder potentials than analogous non-redox-active ?-diketiminate complexes, and the reduced three-coordinate formazanate-iron compound is characterized in detail. Structural, spectroscopic, and computational analysis show that the formazanate ligand undergoes reversible ligand-centered reduction to form a formazanate radical dianion in the reduced species. The less negative reduction potential of the reduced low-coordinate iron formazanate complex leads to distinctive reactivity with formation of a new N-I bond that is not seen with the ?-diketiminate analogue. Thus, the storage of an electron on the supporting ligand changes the redox potential and enhances certain reactivity.

| S-EPMC6115202 | biostudies-literature

Hydride Reduction by a Sodium Hydride-Iodide Composite.

Project description:Sodium hydride (NaH) is widely used as a Brønsted base in chemical synthesis and reacts with various Brønsted acids, whereas it rarely behaves as a reducing reagent through delivery of the hydride to polar ??electrophiles. This study presents a series of reduction reactions of nitriles, amides, and imines as enabled by NaH in the presence of LiI or NaI. This remarkably simple protocol endows NaH with unprecedented and unique hydride-donor chemical reactivity.

| S-EPMC4797714 | biostudies-literature

Toward design of synergistically active carbon-based catalysts for electrocatalytic hydrogen evolution.

Project description:Replacement of precious Pt catalyst with cost-effective alternatives would be significantly beneficial for hydrogen production via electrocatalytic hydrogen evolution reaction (HER). All candidates thus far are exclusively metallic catalysts, which suffer inherent corrosion and oxidation susceptibility during acidic proton-exchange membrane electrolysis. Herein, based on theoretical predictions, we designed and synthesized nitrogen (N) and phosphorus (P) dual-doped graphene as a nonmetallic electrocatalyst for sustainable and efficient hydrogen production. The N and P heteroatoms could coactivate the adjacent C atom in the graphene matrix by affecting its valence orbital energy levels to induce a synergistically enhanced reactivity toward HER. As a result, the dual-doped graphene showed higher electrocatalytic HER activity than single-doped ones and comparable performance to some of the traditional metallic catalysts.

| S-EPMC4046781 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data