skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Cobalt porphyrin intercalation into zirconium phosphate layers for electrochemical water oxidation
A cobalt porphyrin molecule, namely CoTcPP (TcPP = the dianion of meso -tetra(4-carboxyphenyl)porphyrin), is intercalated into zirconium phosphate (ZrP) layers as an effective way to heterogenize a porphyrin-based molecular electrocatalyst. Fourier-transform infrared (FT-IR) spectroscopy, X-ray powder diffraction (XRPD) measurements, UV-Vis spectroscopy, elemental mapping, energy dispersive X-ray (EDX) analysis, inductively coupled plasma mass spectrometry (ICP-MS) and X-ray photoelectron spectroscopy (XPS) were utilized to determine the successful intercalation of CoTcPP into ZrP. While the CoTcPP molecule is not amendable to be used as a heterogeneous catalyst in basic environment due to the carboxylic groups, the intercalated species (CoTcPP/ZrP) is effective towards water oxidation from KOH aqueous solution when utilized as a heterogeneous electrocatalyst and shows remarkable catalytic durability. Electrochemical results show that CoTcPP/ZrP requires an overpotential of 0.467 V to achieve a current density of 10 mA cm −2 while the pristine α-ZrP shows negligible electrocatalytic OER behavior.  more » « less
Award ID(s):
1827622
PAR ID:
10227237
Author(s) / Creator(s):
; ; ; ; ; ; ; ;
Date Published:
Journal Name:
Sustainable Energy & Fuels
Volume:
5
Issue:
2
ISSN:
2398-4902
Page Range / eLocation ID:
430 to 437
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract Electrocatalytic hydrogen gas production is considered a potential pathway towards carbon‐neutral energy sources. However, the development of this technology is hindered by the lack of efficient, cost‐effective, and environmentally benign catalysts. In this study, a main‐group‐element‐based electrocatalyst,SbSalen, is reported to catalyze the hydrogen evolution reaction (HER) in an aqueous medium. The heterogenized molecular system achieved a Faradaic efficiency of 100 % at −1.4 V vs. NHE with a maximum current density of −30.7 mA/cm2. X‐ray photoelectron spectroscopy of the catalyst‐bound working electrode before and after electrolysis confirmed the molecular stability during catalysis. The turnover frequency was calculated as 43.4 s−1using redox‐peak integration. The kinetic and mechanistic aspects of the electrocatalytic reaction were further examined by computational methods. This study provides mechanistic insights into main‐group‐element electrocatalysts for heterogeneous small‐molecule conversion. 
    more » « less
  2. Titanium nitride and vanadium nitride–carbon-based composite systems, TiN/C and VN/C, were prepared using a new synthesis method based on the thermal decomposition of titanyl tetraphenyl porphyrin (TiOTPP) and vanadyl tetraphenyl porphyrin (VOTPP), respectively. The structure of the TiN/C and VN/C composite materials, as well as their precursors, were characterized using Fourier Transformed Infrared Spectroscopy, X-Ray diffraction (XRD), X-Ray energy dispersive (EDS) and X-Ray photoelectron spectroscopy (XPS). Morphologies of the TiN/C and VN/C composites were examined by means of scanning electron (SEM) and transmission electron (TEM) microscopy. The synthesis of the non-metalated tetraphenyl porphyrin, the titanium, and vanadium tetraphenyl porphyrin complexes were confirmed using FTIR. The thermal decomposition of the titanium and vanadium tetraphenyl porphyrin complexes produced the respective metal nitride encapsulated in a carbon matrix; this was confirmed by XRD, SEM, TEM, and XPS. From the XRD patterns, it was determined that the TiN and VN were presented in cubic form with expected space group FM-3M and 1:1 (metal:N) stoichiometry. The XPS results confirmed the presence of both TiN and VN in the carbon matrix without metal carbides. The SEM and TEM results showed that both TiN and VN nanoparticles formed small clusters throughout the carbon matrix; the EDS results revealed a uniform composition. The synthesis method presented in this work is novel and serves as an effective means to produce TiN and VN NPs with good structure and morphology embedded in a carbon matrix. 
    more » « less
  3. Abstract Electrocatalytic proton reduction to form dihydrogen (H2) is an effective way to store energy in the form of chemical bonds. In this study, we validate the applicability of a main‐group‐element‐based tin porphyrin complex as an effective molecular electrocatalyst for proton reduction. A PEGylated Sn porphyrin complex (SnPEGP) displayed high activity (−4.6 mA cm−2at −1.7 V vs. Fc/Fc+) and high selectivity (H2Faradaic efficiency of 94 % at −1.7 V vs. Fc/Fc+) in acetonitrile (MeCN) with trifluoroacetic acid (TFA) as the proton source. The maximum turnover frequency (TOFmax) for H2production was obtained as 1099 s−1. Spectroelectrochemical analysis, in conjunction with quantum chemical calculations, suggest that proton reduction occurs via an electron‐chemical‐electron‐chemical (ECEC) pathway. This study reveals that the tin porphyrin catalyst serves as a novel platform for investigating molecular electrocatalytic reactions and provides new mechanistic insights into proton reduction. 
    more » « less
  4. Encapsulation of an active electrocatalyst with a permeable overlayer is an attractive approach to simultaneously enhance its stability, activity, and selectivity. However, the structure–property relationships that govern the performance of encapsulated electrocatalysts are poorly understood, especially those describing the electrocatalytic behavior of the buried interface between the overlayer and active electrocatalyst. Using planar silicon oxide (SiO x )-encapsulated platinum (Pt)/titanium (Ti) bilayer thin films as model electrodes, the present study investigates the physical and electrochemical properties of the SiO x |Pt buried interface. Through a combination of X-ray photoelectron spectroscopy and electroanalytical measurements, it is revealed that a platinum oxide (PtO x ) interlayer can exist between the SiO x overlayer and Pt thin film. The thickness and properties of the PtO x interlayer can be altered by modifying (i) the thickness of the SiO x overlayer or (ii) the thickness of the Pt layer, which may expose the buried interface to oxophilic Ti. Importantly, SiO x |Pt electrodes based on ultrathin Pt/Ti bilayers possess thinner PtO x interlayers while exhibiting reduced permeabilities for Cu 2+ and H + and enhanced stability during cycling in 0.5 M H 2 SO 4 . These findings highlight the tunability of buried interfaces while providing new insights that are needed to guide the design of complex electrocatalysts that contain them. 
    more » « less
  5. W e present a scalable solution-processing method for fabricating high-quality graphene and graphene/1T-MoS 2 heterostructure films. The process begins with the synthesis of potassium-intercalated graphite (KC 8 ), which is exfoliated in tetrahydrofuran (THF) to produce stable dispersions of negatively charged (electron rich) graphene sheets. The graphene is subsequently transferred to water, forming a surfactant-free aqueous dispersion suitable for creating homogenous graphene films via vacuum filtration and stamping. Additionally, graphene is combined with 1T-MoS 2 nanosheets to fabricate graphene/1T-MoS 2 bulk heterostructure films. Comprehensive characterization, including X-ray diffraction (XRD), absorption spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy ( TEM), Raman spectroscopy, and X-ray photon emission spectroscopy (XPS), reveals that the heterostructure films exhibit enhanced optical and electronic properties, including improved light absorption, which could lead to novel photo-responsive devices. Raman spectroscopy shows significant changes in the graphene’s structural a nd electronic properties upon interaction with MoS 2 , indicating strong interlayer coupling and potential charge transfer between the layered components. The g raphene films demonstrate highly sensitive detection of dopamine (DA), while the graphene/1T-MoS 2 b ulk heterostructure films exhibit capacitance values up to 3 8.3 Fg − 1 at 5 mV/s in non-aqueous electrolytes. These results highlight the potential of these films for advanced applications in molecular sensing and energy storage. 
    more » « less