An official website of the United States government
Sustainable hydrogen gas production is critical for future fuel infrastructure. Here, a series of phosphorous-doped carbon nitride materials were synthesized by thermal annealing of urea and ammonium hexafluorophosphate, and platinum was atomically dispersed within the structural scaffold by thermal refluxing with Zeise's salt forming Pt–N/P/Cl coordination interactions, as manifested in X-ray photoelectron and absorption spectroscopic measurements. The resulting materials were found to exhibit markedly enhanced electrocatalytic activity towards the hydrogen evolution reaction (HER) in acidic media, as compared to the P-free counterpart. This was accounted for by P doping that led to a significantly improved charge carrier density within C 3 N 4 , and the sample with the optimal P content showed an overpotential of only −22 mV to reach the current density of 10 mA cm −2 , lower than that of commercial Pt/C (−26 mV), and a mass activity (7.1 mA μg−1Pt at −70 mV vs. reversible hydrogen electrode) nearly triple that of the latter. Results from the present study highlight the significance of P doping in the manipulation of the electronic structures of metal/carbon nitride nanocomposites for high-performance HER electrocatalysis.
more »
« less
Rapid preparation of carbon‐supported ruthenium nanoparticles by magnetic induction heating for efficient hydrogen evolution reaction in both acidic and alkaline media
Abstract Ruthenium has been hailed as a competitive alternative for platinum toward hydrogen evolution reaction (HER), a critical process in electrochemical water splitting. In this study, we successfully prepare metallic Ru nanoparticles supported on carbon paper by utilizing a novel magnetic induction heating (MIH) method. The samples are obtained within seconds, featuring a Cl‐enriched surface that is unattainable via conventional thermal annealing. The best sample within the series shows a remarkable HER activity in both acidic and alkaline media with an overpotential of only ‐23 and ‐12 mV to reach the current density of 10 mA/cm2, highly comparable to that of the Pt/C benchmark. Theoretical studies based on density functional theory show that the excellent electrocatalytic activity is accounted by the surface metal‐Cl species that facilitate charge transfer and downshift the d‐band center. Results from this study highlight the unique advantages of MIH in rapid sample preparation, where residual anion ligands play a critical role in manipulating the electronic properties of the metal surfaces and the eventual electrocatalytic activity.
more »
« less
- Award ID(s):
- 1900235
- PAR ID:
- 10445233
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- SusMat
- Volume:
- 2
- Issue:
- 3
- ISSN:
- 2692-4552
- Page Range / eLocation ID:
- p. 335-346
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Abstract The creation of metal‐metal oxide interfaces is an important approach to fine‐tuning catalyst properties through strong interfacial interactions. This article presents the work on developing interfaces between Pt and CeOxthat improve Pt surface energetics for the hydrogen evolution reaction (HER) within an alkaline electrolyte. The Pt‐CeOxinterfaces are formed by depositing size‐controlled Pt nanoparticles onto a carbon support already coated with ultrathin CeOxnanosheets. This interface structure facilitates substantial electron transfer from Pt to CeOx, resulting in decreased hydrogen binding energies on Pt surfaces, and water dissociation for the HER, as predicted by the density functional theory (DFT) calculations. Electrochemical testing indicates that both Pt specific activity and mass activity are improved by a factor of 2 to 3 following the formation of Pt‐CeOxinterfaces. This study underscores the significance and potential of harnessing robust interfacial effects to enhance electrocatalytic reactions.more » « less
-
Abstract M5X4MXenes, a subclass of 2D transition metal carbides, have attracted attention as the thickest 2D material synthesized. Early studies show their promising electrocatalytic activity but overlooked how metal composition and interlayer spacing affect hydrogen evolution reaction (HER). To address this gap, three M5X4MXenes, Mo4VC4, (TiTa)5C4, and (TiNb)5C4, are systematically studied and their interlayer spacing and composition modulated through ion exchange with tetramethyl ammonium (TMA+vs. Li+), providing new insights into their HER activity. These findings reveal that TMA+‐intercalated Mo4VC4exhibits superior HER activity, achieving areal and gravimetric overpotentials of 172 and 90 mV, respectively, due to its composition (presence of Mo) and expanded interlayer spacing that enhances proton accessibility. The Li+exchange increases the overpotential to 212 and 131 mV at 10 mA areal and gravimetric current density, respectively, as reduced interlayer spacing restricts access to active Mo sites. In contrast, (TiNb)5C4and (TiTa)5C4display higher overpotentials, making them more suitable for supercapacitor or aqueous battery applications due to the wider electrochemical window. This study provides critical insights into the interplay between metal composition and interlayer engineering in M5X4MXenes, establishing TMA‐Mo4VC4as a promising candidate for sustainable hydrogen production.more » « less
-
Abstract Development of high‐performance, low‐cost catalysts for electrochemical water splitting is key to sustainable hydrogen production. Herein, ultrafast synthesis of carbon‐supported ruthenium–copper (RuCu/C) nanocomposites is reported by magnetic induction heating, where the rapid Joule's heating of RuCl3and CuCl2at 200 A for 10 s produces Ru–Cl residues‐decorated Ru nanocrystals dispersed on a CuClxscaffold, featuring effective Ru to Cu charge transfer. Among the series, the RuCu/C‐3 sample exhibits the best activity in 1 mKOH toward both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), with an overpotential of only −23 and +270 mV to reach 10 mA cm−2, respectively. When RuCu/C‐3 is used as bifunctional catalysts for electrochemical water splitting, a low cell voltage of 1.53 V is needed to produce 10 mA cm−2, markedly better than that with a mixture of commercial Pt/C+RuO2(1.59 V). In situ X‐ray absorption spectroscopy measurements show that the bifunctional activity is due to reduction of the Ru–Cl residues at low electrode potentials that enriches metallic Ru and oxidation at high electrode potentials that facilitates the formation of amorphous RuOx. These findings highlight the unique potential of MIH in the ultrafast synthesis of high‐performance catalysts for electrochemical water splitting.more » « less
-
Abstract Transition‐metal borides (TMBs) have recently attracted attention as excellent hydrogen evolution (HER) electrocatalysts in bulk crystalline materials. Herein, we show for the first time that VB and V3B4have high electrocatalytic HER activity. Furthermore, we show that the HER activity (in 0.5 mH2SO4) increases with increasing boron chain condensation in vanadium borides: Using a −23 mV overpotential decrement derived from −0.296 mV (for VB at −10 mA cm−2current density) and −0.273 mV (for V3B4) we accurately predict the overpotential of VB2(−0.204 mV) as well as that of unstudied V2B3(−0.250 mV) and hypothetical “V5B8” (−0.227 mV). We then derived an exponential equation that predicts the overpotentials of known and hypothetical VxByphases containing at least a boron chain. These results provide a direct correlation between crystal structure and HER activity, thus paving the way for the design of even better electrocatalytic materials through structure–activity relationships.more » « less
