skip to main content


Title: Critical Review of Platinum Group Metal-Free Materials for Water Electrolysis: Transition from the Laboratory to the Market : Earth-abundant borides and phosphides as catalysts for sustainable hydrogen production
To combat the global problem of carbon dioxide emissions, hydrogen is the desired energy vector for the transition to environmentally benign fuel cell power. Water electrolysis (WE) is the major technology for sustainable hydrogen production. Despite the use of renewable solar and wind power as sources of electricity, one of the main barriers for the widespread implementation of WE is the scarcity and high cost of platinum group metals (pgms) that are used to catalyse the cathodic hydrogen evolution reaction (HER) and the anodic oxygen evolution reaction (OER). Hence, the critical pgm-based catalysts must be replaced with more sustainable alternatives for WE technologies to become commercially viable. This critical review describes the state-of-the-art pgm-free materials used in the WE application, with a major focus on phosphides and borides. Several emerging classes of HER and OER catalysts are reviewed and detailed structure‐property correlations are comprehensively summarised. The influence of the crystallographic and electronic structures, morphology and bulk and surface chemistry of the catalysts on the activity towards OER and HER is discussed.  more » « less
Award ID(s):
1955456
NSF-PAR ID:
10248470
Author(s) / Creator(s):
; ; ;
Date Published:
Journal Name:
Johnson Matthey Technology Review
Volume:
65
Issue:
2
ISSN:
2056-5135
Page Range / eLocation ID:
207 to 226
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    A crucial step toward clean hydrogen (H2) energy production through water electrolysis is to develop high‐stability catalysts, which can be reliably used at high current densities for a long time. So far, platinum group metals (PGM) and their oxides, for example, Pt and iridium oxide (IrO2) have been well‐regarded as the criterion for hydrogen and oxygen evolution reactions (HER and OER) electrocatalysts. However, the PGM catalysts usually undergo severe performance decay during the long‐term operation. Herein, the in situ growth of iron phosphosulfate (Fe2P2S6) nanocrystals (NCs) catalysts on carbon paper synthesized by combing chemical vapor deposition with solvent‐thermal treatment is reported to show competitive performance and stability as compared to the state‐of‐the‐art PGM catalysts in a real water electrolyzer. A current density of 370 mA cm−2is achieved at 1.8 V when using Fe2P2S6NCs as bifunctional catalysts in an anion exchange membrane water electrolyzer. The Fe2P2S6NCs also show much better stability than the Pt‐IrO2catalysts at 300 mA cm−2for a continuous 24 h test. The surface generated FeOOH on Fe2P2S6is the real active site for OER. These results indicate that the Fe2P2S6NCs potentially can be used to replace PGM catalysts for practical water electrolyzers.

     
    more » « less
  2. Oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) are three critical reactions for energy-related applications, such as water electrolyzers and metal-air batteries. Graphene-supported single-atom catalysts (SACs) have been widely explored; however, either experiments or density functional theory (DFT) computations cannot screen catalysts at high speed. Herein, based on DFT computations of 104 graphene-supported SACs (M@C3, M@C4, M@pyridine-N4, and M@pyrrole-N4), we built up machine learning (ML) models to describe the underlying pattern of easily obtainable physical properties and limiting potentials (errors = 0.013/0.005/0.020 V for ORR/OER/HER, respectively), and employed these models to predict the catalysis performance of 260 other graphene-supported SACs containing metal-NxCy active sites (M@NxCy). We recomputed the top catalysts recommended by ML towards ORR/OER/HER by DFT, which confirmed the reliability of our ML model, and identified two OER catalysts (Ir@pyridine-N3C1 and Ir@pyridine-N2C2) outperforming noble metal oxides, RuO2 and IrO2. The ML models quantitatively unveiled the significance of various descriptors and fast narrowed down the potential list of graphene-supported single-atom catalysts. This approach can be easily used to screen and design other SACs, and significantly accelerate the catalyst design for many other important reactions. 
    more » « less
  3. 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 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]​. 
    more » « less
  4. 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) 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. 
    more » « less
  5. null (Ed.)
    Electrochemical water splitting is one of the most promising approaches for sustainable energy conversion and storage toward a future hydrogen society. This demands durable and affordable electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). In this study, we report the preparation of uniform Ni–P–O, Ni–S–O, and Ni–S–P–O electrocatalytic films on nickel foam (NF) substrates via flow cell-assisted electrodeposition. Remarkably, electrodeposition onto 12 cm 2 substrates was optimized by strategically varying critical parameters. The high quality and reproducibility of the materials is attributed to the use of a 3D-printed flow cell with a tailored design. Then, the as-fabricated electrodes were tested for overall water splitting in the same flow cell under alkaline conditions. The best-performing sample, NiSP/NF, required relatively low overpotentials of 93 mV for the HER and 259 mV for the OER to produce a current density of 10 mA cm −2 . Importantly, the electrodeposited films underwent oxidation into amorphous nickel (oxy)hydroxides and oxidized S and P species, improving both HER and OER performance. The superior electrocatalytic performance of the Ni–S–P–O films originates from the unique reconstruction process during the HER/OER. Furthermore, the overall water splitting test using the NiSP/NF couple required a low cell voltage of only 1.85 V to deliver a current density of 100 mA cm −2 . Overall, we demonstrate that high-quality electrocatalysts can be obtained using a simple and reproducible electrodeposition method in a robust 3D-printed flow cell. 
    more » « less