Sites For Hydrogen Evolution Reaction Research Articles

Electrocatalytic hydrogen evolution reaction on sulfur-deficient MoS2 nanostructures

Molybdenum disulfide (MoS2) is a 2D layered structured material with a Mo:S of 1:2 and is a great attention seeker for hydrogen production through water-splitting. In the present work, we prepared nanostructured MoSx with different sulfur molar concentrations (x = 2, 1, 0.5) through a one-step hydrothermal method. The decrease in sulfur concentration resulted in a new phase that is MoO3 with a Mo:S of 1:0.5. The structural, morphological, and optical properties of all the samples were studied through X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Fourier Transform Infrared spectroscopy (FTIR), and Ultraviolet–Visible (UV–Vis) spectroscopy, respectively. Moreover, the electrochemical behavior was studied using cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), linear sweep voltammetry (LSV), and Tafel slope. Optimum properties were observed for Mo:S (1:1) with an onset potential of 96 mV, an overpotential of 130 mV for hydrogen evolution reaction (HER) coupled with a specific capacitance of 889 F/g and low charge transfer resistance of 43 Ω. Further, it was noted that the electrocatalytic activity of MoS1 was better than that of the composite and bare MoO3. It is proposed that the excellent electrochemical activity arises from sulfur vacancies which provide active sites for HER and a free path for ions to flow through the material.

P and Se-codopants triggered basal plane active sites in NbS2 3D nanosheets toward electrocatalytic hydrogen evolution

Promoting the intrinsic activity and accessibility of basal plane sites in transition metal dichalcogenides (TMDs) is an important way to optimize their catalytic performance for energy conversion and storage. Here, a simple liquid-phase phosphating selenization pyrolysis method is developed to prepare P and Se co-doped niobium disulfide (NbS2) 3D nanosheets with active basal plane for efficient catalyzing hydrogen evolution reaction (HER). Experimental results indicate that the P and Se co-doped NbS2 3D nanosheets exhibit significantly enhanced HER activity and stability compared to their undoped counterparts. It realizes 165 mV decreased overpotential at 10 mA cm−2 and a stable durability over 40 h continuous operation at 14 mA cm−2 without observable fading. Density functional theory (DFT) studies suggest that the P dopant is to activate the adjacent original inert Nb sites, where both S and Nb sites in P, Se co-doped NbS2 monolayer can together act as the active sites for HER. Furthermore, the addition of selenium can stabilize the catalytic activity. Our work provides a promising approach and theoretical framework for improving the electrocatalytic HER performance of NbS2, and may have general guidelines for other transition metal disulfides.

MnOx‐Decorated Nickel‐Iron Phosphides Nanosheets: Interface Modifications for Robust Overall Water Splitting at Ultra‐High Current Densities

AbstractExploring highly active and stable bifunctional water‐splitting electrocatalysts at ultra‐high current densities is remarkably desirable. Herein, 3D nickel‐iron phosphides nanosheets modified by MnOx nanoparticles are grown on nickel foam (MnOx/NiFeP/NF). Resulting from the electronic coupling effect enabled by interface modifications, the intrinsic activities of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are improved. Meanwhile, 3D nanosheets provide abundant active sites for HER and OER, leading to accelerating the reaction kinetics. Besides, the shell‐protection characteristic of MnOx improves the durability of MnOx/NiFeP/NF. Therefore, MnOx/NiFeP/NF shows exceptional bifunctional electrocatalytic activities toward HER (an overpotential of 255 mV at 500 mA cm−2), OER (overpotentials of 296 and 346 mV at 500 and 1000 mA cm−2, respectively), and overall water splitting (cell voltages of 1.796 and 1.828 V at 500 and 1000 mA cm−2, respectively). Furthermore, it owns remarkably outstanding stability for overall water splitting at ultra‐high current densities (120 and 70 h at 500 and 1000 mA cm−2, respectively), which outperforms almost all of the non‐noble metal electrocatalysts. This work presents efficient strategies of interface modifications, 3D nanostructures, and shell protection to afford ultra‐high current densities.

Vertically oriented Ni-doped MoS2 nanosheets supported on hollow carbon microtubes for enhanced hydrogen evolution reaction and water splitting

Developing efficient hydrogen evolution reaction (HER) electrocatalysts is extremely important for large-scale hydrogen production from water splitting. In this work, ultra-small MoS 2 nanosheets with 5% Ni doping grown on both sides of hollow carbon microtubes (5%-Ni-MoS 2 /aCMT) are prepared by a hydrothermal method . The vertically oriented Ni-doped MoS 2 nanosheets provide more active sites for HER, while open porous structure promotes ions transport, and hollow carbon microtube substrate accelerates electrons transport as well as hydrogen release. Density functional theory (DFT) analysis proves that the optimal amount of Ni doping can effectively adjust the electronic structure of MoS 2 . As a result, 5%-Ni-MoS 2 /aCMT electrode exhibits enhanced kinetics for HER in both acidic and alkaline conditions. To deliver the current density of 10 mA cm −2 , it requires overpotentials of 140 and 88 mV in 1 M KOH and 0.5 M H 2 SO 4 . 5%-Ni-MoS 2 /aCMT exhibits better stability than commercial Pt/C at a high current density of 200 mA cm −2 . Moreover, 5%-Ni-MoS 2 /aCMT/NF (nickel foam) || RuO 2 /NF electrolyzer exhibits ultra-long stability of 30 h at the current density of 100 mA cm −2 and excellent overall water splitting performance with requiring low cell voltages of 1.52 and 1.71 V to generate current densities of 10 and 50 mA cm −2 . • The Ni doping with an optimized content adjusted the electronic structure of MoS 2 , and improved the intrinsic activity. • The ultra-small vertically oriented and defect-rich Ni-doped MoS 2 nanosheets provide more active sites for HER. • The natural N-doped aCMT substrate promotes electron transport during the HER process. • 5%-Ni-MoS 2 /aCMT behaves an enhanced kinetics process based on EIS and DFT analysis.

CoS2 quantum dots modified by ZIF-67 and anchored on reduced graphene oxide as an efficient catalyst for hydrogen evolution reaction

Hydrogen energy has become one of the most potential sources for replacing fossil fuels due to its environmental friendliness and high energy conversion rate. Electrolyzed water is a hydrogen evolution process with high efficiency, no by-products, and high hydrogen purity. Here, we propose to use ZIF-67 as the precursor to prepare three-dimensional multilayer rGO supported CoS2 quantum dots (CoS2QDs@rGO) through a two-step hydrothermal method and one-step calcinations method. The as-prepared electrocatalyst with maximum exposure of edge active sites is highly efficient for hydrogen evolution reaction (HER), delivering an extremely small Tafel slope of 78 mV dec-1, and prominent durability. Density functional theory (DFT) calculations reveal that decoration of CoS2QDs not only obviously changes Gibbs free energy of hydrogen adsorption (ΔGH*), but also offers more active sites for HER, conspicuous promoting the catalytic activity of as-obtained electrode materials. It can be expected that our CoS2 quantum dots mounted on three-dimensional multilayer rGO with ZIF-67 as the precursor, will provide a novel, high-yield and effective catalytic material for energy conversion applications.

Boron leaching: Creating vacancy-rich Ni for enhanced hydrogen evolution

Creating vacancy is often highly effective in enhancing the hydrogen evolution performance of transition metal-based catalysts. Vacancy-rich Ni nanosheets have been fabricated via topochemical formation of two-dimentional (2D) Ni2B on graphene precursor followed by boron leaching. Anchored on graphene, a few atomic layered Ni2B nanosheets are first obtained by reduction and annealing. Large number of atomic vacancies are then generated in the Ni2B layer via leaching boron atoms. When used for hydrogen evolution reaction (HER), the vacancy-rich Ni/Ni(OH)2 heterostructure nanosheets demonstrate remarkable performance with a low overpotential of 159 mV at a current density of 10 mA·cm−2 in alkaline solution, a dramatic improvement over 262 mV of its precursor. This enhancement is associated with the formation of vacancies which introduce more active sites for HER along Ni/Ni(OH)2 heterointerfaces. This work offers a facile and universal route to introduce vacancies and improve catalytic activity.

Synergistic effect between sulfur and CoFe alloys embedded in N-doped carbon nanosheets for efficient hydrogen evolution under neutral condition

Seeking novel low-cost non-noble metal based electrocatalysts with high efficiency is of great significance to promote industrial application of hydrogen evolution reaction (HER). Herein, we originally demonstrate sulfur on CoFe alloys embedded in nitrogen-doped carbon nanosheets (S-CoFe@NC) catalyst with extremely robust HER activity in neutral media. The present sample exhibits active HER performance with ultralow overpotential of 37 mV at current density of 10 mA cm−2 and Tafel slope of 34 mV dec-1, which is the same as commercial Pt/C. Systemic studies show that strong interaction between bridging Sn2- and CoFe@NC introduces M−Sn2- as the robust catalysis sites for HER, which is also beneficial for the charge exchange. The specific structure of NC nanosheet interconnected network provides structure advantages for easily accessible active sites and fast charge transfer for electrocatalysis. Thus, this work paves a way for the development of new class of sulfur based electrocatalyst with efficient HER performance for neutral water splitting.

Branch-leaf-shaped CuNi@NiFeCu nanodendrites as highly efficient electrocatalysts for overall water splitting

Engineering structural and electronic properties of electrocatalysts is a direct method to boost water splitting. Herein, distinctive branch-leaf-shaped CuNi@NiFeCu nanodendrites are successfully synthesized by a novel bionic design strategy. Importantly, this unique catalyst can display superior performance for overall water splitting, which only requires 42 mV at 10 mA cm−2 for hydrogen evolution reaction (HER) and 285 mV at 50 mA cm−2 for oxygen evolution reaction (OER). Further mechanism studies disclosed that Cu atoms in nanosheet edges not only act as key active sites for HER, but also draw electron in eg orbital of Fe active sites, which weakens the adsorption strength of oxygen-intermediate and accordingly enhances OER activity. Moreover, the optimized structure can prevent the agglomeration of nanosheets, provide numerous crystalline-amorphous interfaces and oxygen vacancies, which is beneficial to the enhancement of reaction kinetics. This work paved an original strategy to improve the activity of 2D materials.

Bifunctional Pd@RhPd Core-Shell Nanodendrites for Methanol Electrolysis.

Methanol electrolysis is a promising strategy to achieve energy-saving and efficient electrochemical hydrogen (H2) production. In this system, the advanced electrocatalysts with high catalytic performance for both the methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER) are highly desirable. Inspired by the complementary catalytic properties of rhodium (Rh) and palladium (Pd) for MOR and HER, herein, several Pd core-RhPd alloy shell nanodendrites (Pd@RhPd NDs) are synthesized through the galvanic replacement reaction between Pd nanodendrites (Pd NDs) and rhodium trichloride. For MOR, Pd@RhPd NDs exhibit Rh content-determined catalytic activity, in which Pd@Rh0.07Pd NDs have an optimal combination of oxidation potential and oxidation current due to the synergistic catalytic process of Pd/Rh double active sites. For HER, the introduction of Rh greatly improves the catalytic activity of Pd@RhPd NDs compared to that of Pd NDs, suggesting that Rh is the main activity site for HER. Unlike MOR, however, the HER activity of Pd@RhPd NDs is not sensitive to the Rh content. Using Pd@Rh0.07Pd NDs as robust bifunctional electrocatalysts, the as-constructed two-electrode methanol electrolysis cell shows a much lower voltage (0.813 V) than that of water electrolysis (1.672 V) to achieve electrochemical H2 production at 10 mA cm-2, demonstrating the application prospect of methanol electrolysis for H2 production.

Hydrazine hydrate-assisted adjustment of sulfur-rich MoS2 as hydrogen evolution electrocatalyst

The activity of MoS2 toward hydrogen evolution reaction (HER) originated from different sulfur configurations and phases. Metallic 1T phase of MoS2 with good electronic conductivity and abundant electrocatalytic active sites is favorable for electrocatalysis. In addition, bridging S22- has been verified as the major active sites for HER. However, there is a lack of in-depth understanding for the coexistence of 1T phase and bridging S22- of MoS2. Herein, a facile hydrazine hydrate-assisted method is reported to synthesize sulfur-rich MoS2. Specifically, when higher ratio of 1T to 2H phase was obtained, a higher proportion of bridging S22- to terminal S22- was produced simultaneously. With an optimum amount of hydrazine hydrate, MoS2 exhibits a low overpotential of 173 mV at a current density of 10 mA cm−2, a small Tafel slope of 56.6 mV dec−1, and long-term stability in 0.5 M H2SO4 solution. This work provides a new insight for improving the electrocatalytic activity of MoS2 via a simple method.

Exploring the Dominant Role of Atomic- and Nano-Ruthenium as Active Sites for Hydrogen Evolution Reaction in Both Acidic and Alkaline Media.

Ru nanoparticles (NPs) and single atoms (SAs)‐based materials have been investigated as alternative electrocatalysts to Pt/C for hydrogen evolution reaction (HER). Exploring the dominant role of atomic‐ and nano‐ruthenium as active sites in acidic and alkaline media is very necessary for optimizing the performance. Herein, an electrocatalyst containing both Ru SAs and NPs anchored on defective carbon (RuSA+NP/DC) has been synthesized via a Ru–alginate metal–organic supramolecules conversion method. RuSA+NP/DC exhibits low overpotentials of 16.6 and 18.8 mV at 10 mA cm−2 in acidic and alkaline electrolytes, respectively. Notably, its mass activities are dramatically improved, which are about 1.1 and 2.4 times those of Pt/C at an overpotential of 50 mV in acidic and alkaline media, respectively. Theoretical calculations reveal that Ru SAs own the most appropriate H* adsorption strength and thus, plays a dominant role for HER in acid electrolyte, while Ru NPs facilitate the dissociation of H2O that is the rate‐determining step in alkaline electrolyte, leading to a remarkable HER activity.

Revealing the catalytic micro-mechanism of MoN, WN and WC on hydrogen evolution reaction

Catalytic performance of MoN, WN and WC on hydrogen evolution reaction (HER)were investigated by first-principles calculations, especially considering the effect of strain. From the calculation we can see the catalytic ability has an opposite trend with the adsorption capacity. H coverage was found to affect WN catalytic activity obviously, however has no effect on MoN and WC. Comparing with the experiments, we inferred that although the top site has the strongest potential catalytic ability, the actual catalytic site for HER is hollow1 site. Some specific transition metal doping (Ni > Fe > Mn > W for MoN, Fe > Co for WN, Ni > Co > Fe> Mn for WC) may indirectly improve the HER catalytic performance. It is worth noting that applying a certain strain (e.g. 2.5% tensile strain for MoN, 5% compressive strain for WN, WC) is helpful for improving the HER catalytic performance. Our work is instructive for HER catalyst development in terms of doping and strain.

Hierarchical tubular MoP/MoS2 composite with enhanced electrochemical hydrogen evolution activity

Electrocatalytic production of hydrogen from water is a promising and sustainable strategy. Herein, hierarchical tubular MoP/MoS2 composites with the wall composed of loosely stacked nanosheets were fabricated through partially phosphating the tubular MoS2. As an electrocatalyst for hydrogen evolution reaction (HER), the hierarchical tubular MoP/MoS2 composite displayed a superior HER activity with a low overpotential (101 mV) to obtain a current density of 10 mA/cm2, small Tafel slope (56 mV/dec). Moreover, the MoP/MoS2 composite demonstrate superior long-term durability in acid electrolytes. The excellent catalytic activity of MoP/MoS2 composite may be ascribed to its hierarchical structure: hierarchical porous structure can offer mass diffusion pathways, and the nanosheets with MoP/MoS2 heterojunctions can provide rich active sites for HER. Density functional theory calculations reveal that more favorable H* adsorption kinetics on the surface of the MoP/MoS2 composite during the HER process than pristine MoP and MoS2. This work can offer a strategy to design high performance electrocatalysts for HER applications.

Robust crystalline aromatic imide-linked two-dimensional covalent organic frameworks confining ruthenium nanoparticles as efficient hydrogen evolution electrocatalyst

The hydrogen evolution reaction (HER) is the crucial step in electrochemical water splitting. To succeed in real applications, one of the major challenges faced by HER is the development of robust and efficiency electrocatalysts. Herein, robust highly crystalline aromatic imide-based two-dimensional covalent organic frameworks (COFs) were prepared through a high temperature solvothermal process, taking advantage of the uniform pore size and specialized pore environment, efficient HER catalyst Cryst-2D-PMPI-Ru were synthesized in which ruthenium (Ru) nanoclusters are uniform dispersed with small particle size (less than 2 nm). In alkaline media, Cryst-2D-PMPI-Ru requires overpotential of only 35.1 mV to afford a current density of 10 mA/cm2, which outperforms the benchmark 20% Pt/C catalyst (37.3 mV). The excellent performance of was presumably attributed to the uniform and ultrasmall Ru nanoclusters with a satisfied dispersion, which provides the massive active sites for HER. In acid solution, the overpotential of Cryst-2D-PMPI-Ru (55.3 mV) is close to Pt/C (40.3 mV). The Tafel slope of PMDA/MA-Ru-180-800 is 36.5 mV/dec and the mechanism of the reaction is of the Volmer-Heyrovsky type. Besides, compared with their counterpart with low degree of crystllinity, the Cryst-2D-PMPI-Ru electrocatalyst also exhibits superior performance stability due to the stability of COF. The results provide important evidence that high crystallinity and robust aromatic structure of the polymeric frameworks precursors can substantially enhance their electrocatalytic performance and stability.

Atomic interactions of two-dimensional PtS2 quantum dots/TiC heterostructures for hydrogen evolution reaction

Two-dimensional quantum dots (2D QDs) comprising PtS2 with low Pt loading (0.002 wt.%) distributed on a distinctive CVD-grown titanium carbide substrate (PtS2/TiC) was successfully synthesized and employed for a hydrogen evolution reaction (HER). Notably, despite the low loading of the former component, PtS2/TiC showed excellent HER activity with a superior overpotential (55 mV at 10 mA/cm−2) to that of commercial Pt/C (50 mV at 10 mA/cm−2). The Faraday efficiency of PtS2/TiC was found to be 92.5 %, revealing the superior properties of hydrogen production. The In-situ Raman spectra reveal the important role of S atoms in PtS2 as the active sites for HER, as evidenced by SH bonding formation at 2532 cm-1 during the HER process. This study provides a fundamental understanding essential for the design of more efficient catalysts in the field of electrochemical applications.

Microstrain Engineered NixS2/PtNi Porous Nanowires for Boosting Hydrogen Evolution Activity

The rational design and fabrication of Pt-based electrocatalysts with multiple active sites for hydrogen evolution reaction (HER) are urgently needed for water splitting. Herein, through microstrai...

Three-Dimensional Flower-like Fe, C-Doped-MoS2/Ni3S2 Heterostructures Spheres for Accelerating Electrocatalytic Oxygen and Hydrogen Evolution

The exploration of high-efficiency bifunctional electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) has long been challenging. The rational design of a catalyst by constructing heterostructures and a doping element are possibly expected to achieve it. Herein, the utilization of flower-like Fe/C-doped-MoS2/Ni3S2-450 spherical structural materials for electrocatalytic HER and OER is introduced in this study. The carboxyferrocene-incorporated molybdenum sulfide/nickel sulfide (MoySx/NiS) nanostructures were prepared by solvothermal method. After annealing, the iron and carbon elements derived from ferrocenecarboxylic acid enhanced the electrical transport performance and provided rich electronic sites for HER and OER in alkaline media. Specifically, the optimized flower-like Fe/C-doped-MoS2/Ni3S2-450 exhibited efficient bifunctional performance in alkaline electrolyte, with low overpotentials of 188 and 270 mV required to deliver a current density of 10 mA cm−2 for HER and OER, respectively. This work provides valuable insights for the rational design of energy storage and conversion materials by the incorporation of transition metal and carbon elements into metal sulfide structures utilizing metallocene.

Trifunctional iridium-based electrocatalysts for overall water splitting and Zn-air batteries

• 3%IrO x /NCNT shows an ultra-low overpotential of 8 mV for HER. • 3%IrO x /NCNT exhibits an ultra-low overpotential of 241 mV for OER. • 3%IrO x /NCNT can deliver overall water splitting current density of 10 mA•cm −2 at 1.487 V. • 3%IrO x /NCNT-based Zn-air battery exhibits a peak power density of 59.3 mW cm −2 . • The cooperation effect between IrO 2 and NCNT promotes these reactions. Abstract Development of high-efficiency multifunctional catalysts is pivotal to cut down the fabricating cost and complicacy of energy conversion and storage devices. Here, we fabricate ultrafine iridium-based nanoparticles onto nitrogen-doped carbon nanotubes (IrO x /NCNT) for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR). As a representative sample, the 3%IrO x /NCNT with 2.82 wt% Ir loading exhibits superior electrocatalytic HER activity, showing ultra-low overpotentials of 8 mV, 35 mV, 44 mV, and 82 mV at 10 mA•cm −2 in 0.5 M H 2 SO 4 , 1 M KOH, 0.1 M KOH, and 1 M PBS (pH =7), respectively. Additionally, it shows outstanding OER performance with low overpotentials of 241 mV, 285 mV, and 376 mV at 10 mA•cm −2 in 1 M KOH, 0.5 M H 2 SO 4 , and 1 M PBS, respectively. Due to excellent multifunctional properties, it can be used for overall water splitting, showing potentials of 1.487 V, 1.523 V, and 1.854 V to reach 10 mA•cm −2 in 0.5 M H 2 SO 4 , 1 M KOH, and 1 M PBS, respectively. In addition, the 3%IrO x /NCNT-based Zn-air battery displays a maximal power density of 59.3 mW cm −2 . The IrO x should be the main active site for HER, OER and ORR, while cooperation mechanisms between IrO x and NCNT facilitate these reactions. TOC Ultrafine iridium oxide supported onto nitrogen-doped carbon nanotubes exhibits trifunctional HER, OER and ORR performance due to the synergistic effect between IrO 2 and NCNT.

Activate Fe3S4 Nanorods by Ni Doping for Efficient Dye-Sensitized Photocatalytic Hydrogen Production.

Developing suitable catalysts capable of receiving injected electrons and possessing active sites for hydrogen evolution reaction (HER) is the key to building an efficient dye-sensitized system for hydrogen production. Fe3S4 is generally regarded as an inferior HER catalyst among the metal sulfide family, mainly due to its weak surface adsorption toward H atoms. In this work, we demonstrate a facile metal-organic framework-derived method to synthesize uniform Fe3S4 nanorods and active them for HER by Ni doping. Our experimental results and theoretical calculations reveal that Ni doping can greatly modify the electronic structure of Fe3S4 nanorods, improving their electron conductivity and optimizing their surface adsorption energy toward H atoms. Sensitized by a commercial organic dye (eosin-Y), 1%Ni-doped Fe3S4 nanorods display a high H2 production rate of 3240 μmol gcat-1 h-1 with an apparent quantum yield of 12% under 500 nm wavelength, which is significantly higher than that of pristine Fe3S4 and even higher than that of 1% Pt-deposited Fe3S4. The working mechanism of this dye-sensitized system is explored, and the effect of Ni-doping concentration has been studied. This work presents a facile strategy to synthesize metal-doped sulfide nanocatalysts with greatly enhanced activity toward photocatalytic H2 production.

Structural and electrochemical properties of carbon ion beam irradiated 12-tungstophosphoric acid

In recent years polyoxometalates (POMs) have attracted significant research interest due to versatile properties. These properties are determined by the size, structure and elemental composition of POMs and hence play an important role in their application. In the present study, the ion beam irradiation (10 keV C+ ions, 5 × 1014–2.5 × 1015 ions/cm2) has been utilized for modification of physicochemical properties of 120 nm-thick layer of 12-tungstophosphoric acid (WPA). Scanning electron microscopy analysis of irradiated films showed change of morphology i.e. an increase of WPA grain size with irradiation and coalescence of grains at the highest fluence. This was accompanied by structural changes. Attenuated total reflectance Fourier transform infrared analysis revealed that vibration bands of Keggin anion became less pronounced as fluence increased, while Raman spectra appeared as strongly modified. The effect of irradiation with 1.25 × 1015 ions/cm2 on the structure of WPA was similar to the effect of thermal treatment at 600 °C. Irradiation of WPA led to decrease of the band gap (from 4.07 to 3.92 eV), which was correlated to transformation Keggin anions into a network of WO6 octahedra and PO4 tetrahedra. This is in line with increased number of W=Od bonds observed by UV–Visible diffuse reflectance spectroscopy. Beside transformation to bronzes a reduction of WPA was observed by X-ray Photoelectron Spectroscopy (shift to lower binding energy) and Raman methods, whereas the Raman spectra of irradiated samples were similar to heteropoly blue. The electrochemical properties of irradiated WPA were also assessed. Cyclic voltammetry measurements showed that at up to 1.25 × 1015 ions/cm2 lithiation capacity of WPA increases and activity for hydrogen evolution reaction (HER) improves. The highest fluence caused interconnection of WO6 octahedra, closing of lithiation pathways and decrease in the number of active sites for HER. Our results provide a novel insight into the effects of ion beam irradiation on WPA and demonstrate high potential for tuning of physicochemical properties of POMs that are relevant in wide range of applications.