skip to main content
Explore Scholarly Publications and Datasets in the NSF-PAR

  • NSF Public Access
  • Search Results
  • Accepted Manuscript: (Invited Talk): Designing smart materials for efficient energy conversion: The story of transition metal chalcogenides
Title: (Invited Talk): Designing smart materials for efficient energy conversion: The story of transition metal chalcogenides
Energy harvesting from solar and water has created ripples in materials energy research for the last several decades, complemented by the rise of Hydrogen as a clean fuel. Among these, water electrolysis leading to generation of oxygen and hydrogen, has been one of the most promising routes towards sustainable alternative energy generation and storage, with applications ranging from metal-​air batteries, fuel cells, to solar-​to-​fuel energy conversion systems. In fact, solar water splitting is one of the most promising method to produce Hydrogen without depleting fossil-​fuel based natural resources. However, the efficiency and practical feasibility of water electrolysis is limited by the anodic oxygen evolution reaction (OER)​, which is a kinetically sluggish, electron-​intensive uphill reaction. A slow OER process also slows the other half- cell reaction, i.e. the hydrogen evolution reaction (HER) at the cathode. Hence, designing efficient catalysts for OER process from earth-​abundant resources has been one of the primary concerns for advancing solar water splitting. In the Nath group we have focused on transition metal chalcogenides as efficient OER electrocatalysts. We have proposed the idea that these chalcogenides, specifically, selenides and tellurides will show much better OER catalytic activity due to increasing covalency around the catalytically active transition metal more » site, compared to the oxides caused by decreasing electronegativity of the anion, which in turn leads to variation of chem. potential around the transition metal center, [e.g. lowering the Ni 2+ -​-​> Ni 3+ oxidn. potential in Ni-​based catalysts where Ni 3+ is the actually catalytically active species]​. Based on such hypothesis, we have synthesized a plethora of transition metal selenides including those based on Ni, Ni-​Fe, Co, and Ni-​Co, which show high catalytic efficiency characterized by low onset potential and overpotential at 10 mA​/cm 2 [Ni 3 Se 2 - 200 - 290 mV; Co 7 Se 8 - 260 mV; FeNi 2 Se 4 -​NrGO - 170 mV (NrGO - N-​doped reduced graphene oxide)​; NiFe 2 Se 4 - 210 mV; CoNi 2 Se 4 - 190 mV; Ni 3 Te 2 - 180 mV]​. « less
Authors:
; ; ; ; ; ;
Award ID(s):
1710313
Publication Date:
NSF-PAR ID:
10064216
Journal Name:
255th ACS National Meeting & Exposition, New Orleans, LA, United States, March 18-22, 2018 (2018), ENFL-330
Sponsoring Org:
National Science Foundation
More Like this
  1. ; ; ( , Journal of Materials Chemistry A)
    Water splitting has been widely considered to be an efficient way to generate sustainable and renewable energy resources in fuel cells, metal–air batteries and other energy conversion devices. Exploring efficient electrocatalysts to expedite the anodic oxygen evolution reaction (OER) is a crucial task that needs to be addressed in order to boost the practical application of water splitting. Intensive efforts have been devoted to develop mixed transition metal based chalcogenides as effective OER electrocatalysts. Herein, we have reported synthesis of a series of mixed metal selenides containing Co, Ni and Cu employing combinatorial electrodeposition, and systematically investigated how the transitionmore »metal doping affects the OER catalytic activity in alkaline medium. Energy dispersive spectroscopy (EDS) was performed to detect the elemental compositions and confirm the feasibility of compositional control of 66 metal selenide thin films. It was observed that the OER catalytic activity is sensitive to the concentration of Cu in the catalysts, and the catalyst activity tended to increase with increasing Cu concentration. However, increasing the Cu concentration beyond a certain limit led to decrease in catalytic efficiency, and copper selenide by itself, although catalytically active, showed higher onset potential and overpotential for OER compared to the ternary and quaternary mixed metal selenides. Interestingly, the best quaternary composition (Co 0.21 Ni 0.25 Cu 0.54 ) 3 Se 2 showed similar crystal structure as its parent compound of Cu 3 Se 2 with slight decrease in lattice spacings of (101) and (210) lattice planes (0.0222 Å and 0.0148 Å, respectively) evident from the powder X-ray diffraction pattern. (Co 0.21 Ni 0.25 Cu 0.54 ) 3 Se 2 thin film exhibited excellent OER catalytic activity and required an overpotential of 272 mV to reach a current density of 10 mA cm −2 , which is 54 mV lower than Cu 3 Se 2 , indicating a synergistic effect of transition metal doping in enhancing catalytic activity.« less
  2. ; ; ; ; ; ; ( , Journal of Materials Chemistry A)
    Designing efficient electrocatalysts has been one of the primary goals for water electrolysis, which is one of the most promising routes towards sustainable energy generation from renewable sources. In this article, we have tried to expand the family of transition metal chalcogenide based highly efficient OER electrocatalysts by investigating nickel telluride, Ni 3 Te 2 as a catalyst for the first time. Interestingly Ni 3 Te 2 electrodeposited on a GC electrode showed very low onset potential and overpotential at 10 mA cm −2 (180 mV), which is the lowest in the series of chalcogenides with similar stoichiometry, Ni 3more »E 2 (E = S, Se, Te) as well as Ni-oxides. This observation falls in line with the hypothesis that increasing the covalency around the transition metal center enhances catalytic activity. Such a hypothesis has been previously validated in oxide-based electrocatalysts by creating anion vacancies. However, this is the first instance where this hypothesis has been convincingly validated in the chalcogenide series. The operational stability of the Ni 3 Te 2 electrocatalyst surface during the OER for an extended period of time in alkaline medium was confirmed through surface-sensitive analytical techniques such as XPS, as well as electrochemical methods which showed that the telluride surface did not undergo any corrosion, degradation, or compositional change. More importantly we have compared the catalyst activation step (Ni 2+ → Ni 3+ oxidation) in the chalcogenide series, through electrochemical cyclic voltammetry studies, and have shown that catalyst activation occurs at lower applied potential as the electronegativity of the anion decreases. From DFT calculations we have also shown that the hydroxyl attachment energy is more favorable on the Ni 3 Te 2 surface compared to the Ni-oxide, confirming the enhanced catalytic activity of the telluride. Ni 3 Te 2 also exhibited efficient HER catalytic activity in alkaline medium making it a very effective bifunctional catalyst for full water splitting with a cell voltage of 1.66 V at 10 mA cm −2 . It should be noted here that this is the first report of OER and HER activity in the family of Ni-tellurides.« less
  3. ; ; ; ; ; ; ( , Energy & Environmental Science)
    The two polymorphs of lithium cobalt oxide, LiCoO 2 , present an opportunity to contrast the structural requirements for reversible charge storage (battery function) vs. catalysis of water oxidation/oxygen evolution (OER; 2H 2 O → O 2 + 4H + + 4e − ). Previously, we reported high OER electrocatalytic activity from nanocrystals of the cubic phase vs. poor activity from the layered phase – the archetypal lithium-ion battery cathode. Here we apply transmission electron microscopy, electron diffraction, voltammetry and elemental analysis under OER electrolysis conditions to show that labile Li + ions partially deintercalate from layered LiCoO 2 ,more »initiating structural reorganization to the cubic spinel LiCo 2 O 4 , in parallel with formation of a more active catalytic phase. Comparison of cubic LiCoO 2 (50 nm) to iridium (5 nm) nanoparticles for OER catalysis (commercial benchmark for membrane-based systems) in basic and neutral electrolyte reveals excellent performance in terms of Tafel slope (48 mV dec −1 ), overpotential ( η = ∼420 mV@10 mA cm −2 at pH = 14), faradaic yield (100%) and OER stability (no loss in 14 hours). The inherent OER activity of cubic LiCoO 2 and spinel LiCo 2 O 4 is attributed to the presence of [Co 4 O 4 ] n+ cubane structural units, which provide lower oxidation potential to Co 4+ and lower inter-cubane hole mobility. By contrast, the layered phase, which lacks cubane units, exhibits extensive intra-planar hole delocalization which entropically hinders the four electron/hole concerted OER reaction. An essential distinguishing trait of a truly relevant catalyst is efficient continuous operation in a real electrolyzer stack. Initial trials of cubic LiCoO 2 in a solid electrolyte alkaline membrane electrolyzer indicate continuous operation for 1000 hours (without failure) at current densities up to 400 mA cm −2 and overpotential lower than proven PGM (platinum group metal) catalysts.« less
  4. ; ; ; ; ; ; ; ; ( , Sustainable Energy & Fuels)
    Solar water splitting using photoelectrochemical cells (PEC's) is a promising pathway toward clean and sustainable storage of renewable energy. Practical realization of solar-driven synthesis of hydrogen and oxygen integrating light absorption and electrolysis of water has been challenging because of (1) the limited stability of good photovoltaic materials under the required electrochemical conditions, and (2) photovoltaic efficiency losses due to light absorption by catalysts, the electrolyte, and generated bubbles, or reflection at their various interfaces. Herein, we evaluate a novel integrated solar water splitting architecture using efficient silicon heterojunction photovoltaic cells that avoids such losses and exhibits a solar-to-hydrogen (STH)more »efficiency in excess of 10%. Series-connected silicon Heterojunction with Intrinsic Thin layer (HIT) cells generate sufficient photovoltage for unassisted water splitting, with one of the cells acting as the photocathode. Platinum is deposited on the back (dark) junction of this HIT cell as the catalyst for the hydrogen evolution reaction (HER). The photocathode is protected from corrosion by a TiO 2 layer deposited by atomic layer deposition (ALD) interposed between the HIT cell and the Pt, enabling stable operation for >120 hours. Combined with oxygen evolution reaction (OER) catalysts deposited on a porous metal dark anode, these PEC's achieve stable water splitting with a record high STH efficiency for an integrated silicon photosynthesis device.« less
  5. ; ( , Journal of Materials Chemistry A)
    Electrochemical water splitting produces clean hydrogen fuel as one of the pivotal alternative energies to fossil fuels in the near future. However, the anodic oxygen evolution reaction (OER) is a significant bottleneck that curtails large-scale applications of electrochemical water splitting technology, owing to its sluggish reaction kinetics. In the past few decades, various methods have been proposed to improve the OER kinetics. Among them, doping is a simple and efficient method to mold the OER kinetics of a catalyst by incorporating different or hetero atoms into the host lattice. These efforts are vital to design highly efficient OER catalysts formore »real-world applications. However, the OER mechanism of a doped catalyst varies, depending on the host lattice and the dopant. This review highlights different doping strategies and associated OER mechanisms of state-of-the-art catalysts, including oxides (noble metal oxides, perovskite oxides, spinel oxides, hydroxides and others), non-oxides (metal sulfides, metal selenides, metal phosphides, metal nitrides and metal carbides), and carbon-based catalysts (graphene, carbon nanotubes and others). Fundamental understanding of the doping effects on the OER from combined experimental and theoretical research provides guidelines for designing efficient catalysts.« less
  • Citation Formats
  • MLA
  • APA
  • Chicago
  • BibTeX
  • Save / Share this Record
  • Send to Email