Surface restructuring Prussian blue analog-derived bimetallic CoFe phosphides by N-doped graphene quantum dots for electroactive hydrogen evolving catalyst

Fe-B alloy coupled with Fe clusters as an efficient cocatalyst for photocatalytic hydrogen evolution

Electrocatalysts for hydrogen evolution reaction (HER) from water splitting have been widely studied as one of the efficient energy storage methods by producing hydrogen (H2), the important clean energy resource. The best-known electrocatalyst for HER is platinum (Pt) that is expensive and scarce on earth. Molybdenum disulfide (MoS2) has attracted great attentions as one of promising catalysts for replacing Pt not only because of the relatively low cost and earth abundancy but also great HER activity, selectivity and stability as a great catalyst. Since the edge site of MoS2 was proved as an active site for HER, a great number of efforts on maximally exposing edge site have contributed to the studies about MoS2 based catalysts for HER. The basal plane of MoS2 is catalytically inert for HER since the free energy of adsorbed hydrogen (delGH*) known to a great descriptor for activation energy is thermodynamically uphill (~1.92eV) compared with that of active edge site (~0.06eV). However, sulfur (S) vacancy in the basal plane was very recently investigated as a new active site for HER demonstrating the basal plane that composes the majority part of MoS2 can be utilized for HER. Diverse methods to generate S-vacancy to make a use of the basal plane of MoS2 for efficient HER catalysts have been investigated such as Ar plasma treatment, hydrogen annealing and electrochemical desulfurization. However, HER activity of desulfurized MoS2-x still needs to be improved to be competitive with the HER activities of platinum. Cobalt is one of the non-precious metal promotors for MoS2 based catalysts for hydrogen evolution reaction, water gas shift reaction and oxygen reduction reaction. In very recently, Co was doped in the basal plane of S-vacancy rich MoS2 and Co-SMoS2 achieved a great catalytic activity for the hydrodeoxygenation (HDO) reaction. Since S-vacancy site is coordinatively unsaturated and has a high surface free energy like edge site, it is expected to provide a great nucleation site for doping or anchoring transition metal atoms or clusters. Thus, Co promotor can be employed for enhancing the catalytic activity of the basal plane of MoS2 based catalysts. Herein we report the great HER activity enhancement of the catalytically inert basal plane of MoS2 by combining the catalytic effects of S-vacancy and Co cluster addition as a non-precious metal oxide promotor. We use both density functional theory (DFT) calculations and experiments to support the claim. The polycrystalline 2H phase MoS2 multilayer whose basal plane is dominantly exposed was synthesized on fluorine-doped tin oxide (FTO) and carbon foam electrodes through thermolysis in the tube furnace. S-vacancy was generated on the basal plane of MoS2 through the same electrochemical desulfurization method. On top of that, Co cluster was electrodeposited to further promote the HER activity of the basal plane under different desulfurization conditions. Consequently, we demonstrate S-vacancy plays a critical role for Co nucleation during electrodeposition and thus both electrochemically active surface area and the intrinsic catalytic activity increased. Especially, the overpotential at -10 mA/cm2 was reduced around 300mV making the inert basal plane of MoS2 have comparable overpotential about -0.21 V vs. RHE at -10 mA/cm2 with the state of the art non-precious MoS2 based catalysts.

Transition metal phosphides (TMPs) have emerged as promising and cost-effective electrocatalysts for the hydrogen evolution reaction (HER). However, their practical applications are hindered by insufficient catalytic performance. Herein, we develop a tunable cation vacancy engineering strategy to enhance the HER activity of FeP, one of the most inexpensive TMPs, via facile phosphidation and acid etching of zinc iron hexacyanoferrate (ZnFeHCF) with controllable Zn sacrificial agents. The non-exclusive incorporation of Zn2+ into the ZnFeHCF precursor ensures a uniform distribution of vacancies, while the adjustable Zn2+ content enables precise control of vacancy concentrations over a broad range (0.3-33.6%). Systematic investigations reveal that an optimal level of cation vacancies elevates the d-band center and strengthens hydrogen adsorption, thereby boosting the HER activity of FeP. Conversely, excessive cation vacancies induce severe lattice distortion and surface oxidation, resulting in deteriorated catalytic performance. At the optimized cation vacancy concentration of 16.2%, FeP exhibits the best HER activity, showing a small overpotential of 119 mV at 10 mA cm-2, a low Tafel slope of 59.2 mV dec-1, and excellent stability. This study demonstrates not only an efficient catalyst for the HER but also an effective methodology for cation vacancy engineering of TMPs toward diverse applications.

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 V3B4 have high electrocatalytic HER activity. Furthermore, we show that the HER activity (in 0.5 m H2SO4) 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−2 current 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 VxBy phases 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.

Boosting the HER electrocatalytic activity over RuCu-supported carbon nanosheets as efficient pH-independent catalysts

Enhanced electrocatalysis of NiMnIn Heusler alloy films for hydrogen evolution reaction by magnetic field

Growth of iron diselenide nanorods on graphene oxide nanosheets as advanced electrocatalyst for hydrogen evolution reaction

Defect engineered Janus MoSiGeN4 as highly efficient electrocatalyst for hydrogen evolution reaction

Simultaneously achieving enhanced water adsorption and rapid adsorbed hydroxyl transfer toward MXene-based materials for highly efficient alkaline electrocatalytic hydrogen evolution

Herein, two Laves intermetallic series, ZrCo1.75M0.25 and NbCo1.75M0.25 (M = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, and Pt), were synthesized, and their hydrogen evolution reaction (HER) activities were examined to reveal the influence of d electrons to the corresponding HER activities. Owing to the different electronegativity between Zr and Nb (χZr = 1.33; χNb = 1.60), Co and/or M elements receive more electrons in ZrCo1.75M0.25 than that of the Nb one. This leads to the overall weak H adsorption energy (ΔGHad) of ZrCo1.75M0.25 series compared to that of NbCo1.75M0.25 and rationalizes well the superior HER activity of the Rh member compared to that of the Pt one in the ZrCo1.75M0.25 series. Under industrial conditions (333 K, 6.0 M KOH), ZrCo1.75Rh0.25 only requires an overpotential of 110 mV to reach the current density of 500 mA/cm2 and can be operated at high current density over 400 h. This work demonstrates that with a proper combination between elements in intermetallic phases, one can manipulate d electrons of the active metal to be closer to the sweet spot (ΔGHad = 0). The Pt member may no longer exhibit the best HER activity in series, and all elements exhibit the potential to outperform the Pt member in the HER with careful control of the d electron population.

The production of hydrogen through electrochemical water splitting driven by clean energy becomes a sustainable route for utilization of hydrogen energy, while an efficient hydrogen evolution reaction (HER) electrocatalyst is required to achieve a high energy conversion efficiency. Nickel phosphides have been widely explored for electrocatalytic HER due to their unique electronic properties, efficient electrocatalytic performance, and a superior anti-corrosion feature. However, the HER activities of nickel phosphide electrocatalysts are still low for practical applications in electrolyzers, and further studies are necessary. Therefore, at the current stage, a specific comprehensive review is necessary to focus on the progresses of the nickel phosphide electrocatalysts. This review focuses on the developments of preparation approaches of nickel phosphides for HER, including a mechanism of HER, properties of nickel phosphides, and preparation and electrocatalytic HER performances of nickel phosphides. The progresses of the preparation and HER activities of the nickel phosphide electrocatalysts are mainly discussed by classification of the preparation method. The comparative surveys of their HER activities are made in terms of experimental metrics of overpotential at a certain current density and Tafel slope together with the preparation method. The remaining challenges and perspectives of the future development of nickel phosphide electrocatalysts for HER are also proposed.

Electricity driven proton exchange membrane-based water electrolysis (PEMWE) has demonstrated considerable credibility in recent years, establishing high competency enabling PEMWE technology for rapid generation of clean hydrogen fuel 1-7. In order to attain the high efficiency needed and successful commercialization of PEMWE, there is a critical need to identify highly active, robust, and earth-abundant electrocatalysts for accelerating the hydrogen evolution reaction (HER) with minimum energy input 8. In the pursuit of achieving this goal, in the present work, employing the density functional theory (DFT) based calculations for rationalizing the thermodynamics and reaction kinetics of HER, we have investigated the platinum group metal (PGM)-free, earth-abundant, transition metal non-oxide (TMN) based electrocatalysts for acid mediated HER in PEMWE. Based on the theoretical calculations, the as-synthesized TMN electrocatalyst compositions reveal optimized hydrogen adsorption free energies (ΔGH *) and beneficial electronic structures modification, offering superior charge transfer kinetics, lower reaction barrier, low water contact angle (7o) suggesting high wettability (Fig. 1), and high electrocatalytic activity for HER. Furthermore, the highly active electrocatalyst compositions display excellent long term electrochemical HER stability in acidic media, with no significant obvious degradation in current density. The as-synthesized electrocatalysts thus, has propensity for exhibiting robust HER performance with excellent structural and mechanical integrity. The experimental results are in excellent agreement with the DFT calculations which further accentuate the incorporation of suitable PGM-free dopants into the TMN compositions resulting in optimized electronic structures lowering the HER reaction barriers. The system therefore offers improved electrocatalytic performance for HER which is comparable to state-of-the-art Pt/C electrocatalysts. Accordingly, the as-synthesized PGM-free electrocatalysts can be considered as reliable HER candidates, vital for the development of acid mediated PEM based water splitting employing PGM-free electrocatalysts. Results of this study will be presented and discussed. Acknowledgements: Financial support of NSF-CBET grant# 1511390, Edward R. Weidlein Chair Professorship funds and the Center for Complex Engineered Multifunctional Materials (CCEMM) is acknowledged.

Asymmetrical radial strain energy strategy of M–N–SWCNT single atom catalysts for highly efficient hydrogen evolution: A high-throughput DFT study

Transition metal phosphides (MPs) are emerging earth-abundant catalysts for hydrogen evolution reaction (HER) due to their promising activity and stability. Even though further development is needed to meet real-world application needs, fundamental understanding of how MP catalysts can be improved is low. In this work, we present several different approaches to uncover the relationships of bulk (electronic structure) and surface (active sites) of the catalysts with HER activity and stability. We studied well-ordered crystalline materials as model systems to elucidate the aforementioned relationships. Anionic Si/P substitution in NiSi1-xPx compounds showed that the density of the states (DOS) at EF could be one of the key determinants on HER activity. The impact of DOS was further investigated by studying two polymorphs of Fe2P where upward shift of the d-band position was shown to enhance HER activity. Several surface termination effects were demonstrated on the mm-sized single crystals of Ni2P, Co2P, and Fe2P upon facet-dependent HER activity studies. Lastly, operando X-ray absorption spectroscopy of Ni and P K-edges of Ni-P catalysts clearly demonstrated that during the HER process, reduction occurred on the catalyst surface, but reduced state was only stable under applied reductive bias and quickly oxidized after turning off the potential, and this oxidized species did not appear to return to its original state.

Highly active electrocatalysis of hydrogen evolution reaction in alkaline medium by Ni–P alloy: A capacitance-activity relationship