Electrocatalytic Activity For HER Research Articles

An efficient multifunctional SnS2/g-C3N4 hierarchical nanoflower catalyst for electrocatalytic and photocatalytic applications

The rising energy demand via renewable sources and existence of organic pollutants in water has attracted the world-wide attention to attain sustainable ecosystems. The development of a multi-functional catalyst with significant economic and environmental implications remains a challenge. Herein, we synthesized SnS2/g-C3N4 hierarchical nanoflower using solvothermal method, verified by XRD and FTIR investigations. The surface morphology was analyzed using FESEM, TEM and HRTEM while optical absorption via UV–Vis spectroscopy. SnS2/g-C3N4 displayed outstanding electrocatalytic activity for HER and OER with smaller tafel slope and higher values of current density. The results are in accordance with Cdl and ECSA values, ensuing more active sites and surface area for a catalytic reaction to take place. As-prepared SnS2/g-C3N4 also exhibited 90 % photocatalytic MB deterioration in 90 min upon solar irradiation, following first order kinetics. Type-II mechanism for charge transfer alongwith reactive specie trapping experiment and cyclic stability is also presented. The findings suggests that SnS2/g-C3N4 emerged as proficient catalyst for electrocatalytic and photocatalytic applications.

Heterogeneous Ni-Boride/Phosphide Anchored Amorphous B-C Layer for Overall Water Electrocatalysis.

The rational design of efficient and economical bifunctional electrocatalysts remained a challenge for overall water electrolysis. In this work, the Ni-boride/ phosphide particles anchored amorphous B-doped carbon layer with hierarchical porous characteristics in Ni foam (Ni3P/Ni3B/B-C/NF) was fabricated for overall water splitting. The Boroncarbide (B4C) power was filled and fixed in the NF interspace through the electroplating and electroless plating, and then annealed in vacuum high temperature. The amorphous B-C layer derived from the B4 C not only speeded up the electron transport, but also cooperate with Ni-boride/phosphide to enhance the electrocatalytic activity for HER and OER synergistically. Furthermore, the hierarchical porous architecture of Ni3P/Ni3B/B-C/NF increased space utilization to load more active materials. The self-supported Ni3P/Ni3B/B-C/NF electrode possessed a low overpotential of 212 and 280 mV to deliver 100 mA cm-2 for HER and OER, respectively, and high stability for 48 h. In particular, the electrolyzer constituted with the Ni3P/Ni3B/B-C/NF bifunctional electrocatalyst only required a voltage of 1.59 V at 50 mA cm-2 for water electrocatalysis under alkaline medium, and demonstrated long-term stability for 48 h. This study provides a new technical path for the development of bifunctional of transition metal borides to promote the application of hydrogen production from water splitting.

The electrocatalytic HER activity of MoS2 decorated with adjustable-size ruthenium nanoparticles

MoS2 is a potential electrocatalytic material for its excellent durability and stability. Here, we investigate the electrocatalytic hydrogen evolution reaction performance of MoS2 nanosheets decorated with size-controlled Ru nanoparticles. The MoS2 compounded with 2.46 nm-Ru exhibits the good electrocatalytic performance with overpotential of 53 mV at 10 mA/cm2 in 0.5 M H2SO4 condition. The enhanced electrocatalytic activity of Ru@MoS2 results from accelerated charge migration between the Ru metal and MoS2 semiconductor, as well as the addition of Ru increases the number of active sites on the surface of MoS2. Furthermore, the first-principles calculations demonstrated the ΔGH* of Ru@MoS2 (−0.05 eV) is lower than P–MoS2 (2.04 eV) and the narrowed bandgap facilitates more efficient electron migration. And the theoretical calculations further reveal that the Ru nanoparticles with suitable size at the interface own the ideal ΔGH* by manipulating the D-band center of the Ru.

The dependence of electrocatalytic HER activity of decorated MoS2 with Cu nanoclusters

Molybdenum disulfide is a potential electrocatalytic material for water splitting with excellent stability and durability. Here, the electrocatalytic hydrogen evolution reaction performance of Molybdenum disulfide nanosheets decorated with copper nanoclusters was investigated. The Cu@MoS2–1:10 exhibited remarkable hydrogen evolution reaction activity, with an overpotential as low as 150 mV under acidic conditions. The First-principles calculations further confirmed the superior electrocatalytic performance of Cu@MoS2, with a minimum hydrogen adsorption free energy of -0.10 eV. The improved electrocatalytic activity of Cu@MoS2 arises from the accelerated charge migration at the interface. And the addition of Cu increases the number of active sites on the surface of MoS2. This work could offer insights into the advancement of additional non-precious metals and transition metal dichalcogenides.

Electrocatalytic hydrogen evolution by cobalt(Ⅲ) triphenyl corrole bearing different number of trifluoromethyl groups

Hydrogen production from electrolyzing water is known as the most promising hydrogen production method. To further understand the effect of steric hindrance and electron-withdrawing groups on catalysts, four cobalt triphenyl corroles bearing different number of ortho-trifluoromethyls (1, 2, 3, 4) had been synthesized and used as hydrogen evolution electrocatalysts. These cobalt corroles showed effective electrocatalytic hydrogen evolution activity in organic medium and neutral aqueous medium, with turnover frequency ranging from 100 s−1 to 220 s−1 using 32 equivalents of trifluoroacetic acid proton source in DMF. The electrocatalytic HER goes via competitive ECEC or EECC pathway depending on the used proton source. The electrocatalytic HER activity varies obviously with the number of the peripheral ortho- groups. This work is helpful for the design of new metal corrole HER electrocatalyst.

Modulating the electronic structure of VS2via Ru decoration for an efficient pH-universal electrocatalytic hydrogen evolution reaction.

High-efficiency water electrolysis over a broad pH range is desirable but challenging. Herein, Ru-decorated VS2 on carbon cloth (Ru-VS2/CC) has been in situ synthesized, which features the regulated electronic structure of VS2 by introducing Ru. It is remarkable that the optimal Ru-VS2/CC displays excellent electrocatalytic hydrogen evolution activity with overpotentials of 89 and 87 mV at -10 mA cm-2 in 0.5 M H2SO4 and 1.0 M KOH, respectively. Theoretical calculations and electrocatalytic measurements have demonstrated that introducing Ru induces an enhanced charge density around the Fermi level, facilitating charge transfer and speeding up the electrocatalytic HER kinetics. The Gibbs free energy of the hydrogen intermediate (ΔGH*) of Ru-VS2/CC (0.23 eV) is much closer to zero than that of pure VS2 (0.51 eV) and Ru (-0.37 eV), demonstrating an easier hydrogen adsorption and desorption process for Ru-VS2/CC. The more favorable ΔGH*, differential charge density and the d-band center endow Ru-VS2 with enhanced intrinsic electrocatalytic activity. This study presents a feasible strategy for enhancing electrocatalytic HER activity by the regulation of the electronic structure and the rational integration of dual active components.

Decoding Electrocatalysis: Transforming Aluminum-Clad TLC Plates into Potash Alum for Hydrogen Evolution Exploration

This work deals with using a waste aluminum-based TLC plate to prepare crystalline potash alum, which is subsequently activated for the study of hydrogen evolution reaction in alkaline KOH. The structural and morphological characterization of the synthesized potash alum (PA) has been assessed with powder X-ray diffraction and thermogravimetry analysis. Scanning electron micrographs reveal the morphology of the activated potash alum. The heterogeneous electrocatalytic HER activity in 1 M KOH attributes a moderate electrocatalytic efficiency for activated potash alum (APA) in the light of onset potentials, Faradic efficiency, double-layer capacitance, electrochemically activated surface area, and number of active sites. However, the electrocatalyst APA is a pre-catalyst as it undergoes a significant structural transformation under the electrochemical operation, leading to Al2O3 nanoparticles being the active catalyst for hydrogen production. Possibly, the chemical inertness of the Al2O3 induces a limitation in the local vicinity for the synergistic effect for facile electron transport in alkaline KOH.

Hierarchical Porous Activated Carbon from Wheat Bran Agro-Waste: Applications in Carbon Dioxide Capture, Dye Removal, Oxygen and Hydrogen Evolution Reactions.

This work reports an efficient method for facile synthesis of hierarchically porous carbon (WB-AC) utilizing wheat bran waste. Obtained carbon showed 2.47 mmol g-1 CO2 capture capacity with good CO2 /N2 selectivity and 27.35 to 29.90 kJ mol-1 isosteric heat of adsorption. Rapid removal of MO dye was observed with a capacity of ~555 mg g-1 . Moreover, WB-AC demonstrated a good OER activity with 0.35 V low overpotential at 5 mA cm-2 and a Tafel slope of 115 mV dec-1 . It also exhibited high electrocatalytic HER activity with 57 mV overpotential at 10 mA cm-2 and a Tafel slope of 82.6 mV dec-1 . The large SSA (757 m2 g-1 ) and total pore volume (0.3696 cm3 g-1 ) result from N2 activation contributing to selective CO2 uptake, high and rapid dye removal capacity and superior electrochemical activity (OER/HER), suggesting the use of WB-AC as cost effective adsorbent and metal free electrocatalyst.

Photocatalytic and electrocatalytic hydrogen production promoted by Nd/La substituted cobalt–nickel magnetic nanomaterials

The current work concentrates on the design of Nd/La doped Co0.7Ni0.3Fe2O4 nanocatalysts for the green, clean, and sustainable generation of hydrogen through overall photocatalytic and electrocatalytic water splitting routes using sol-gel auto-combustion route. The spinel symmetry with a Fd3m geometry and cubic polycrystalline nature was observed for the developed catalysts. Spherical formed agglomerated nanoparticles having average grain size of 127.10 and 120.08 nm was confirmed for the produced Co0.7Ni0.3Fe2O4 and Co0.7Ni0.3Nd0.02La0.02Fe1.96O4 catalysts through the FESEM results. Maximum saturation magnetization (Ms) of 64.81 emu/g and coercivity (Hc) of 1234.54 Oe were attained by undoped Co0.7Ni0.3Fe2O4 catalyst. This shows the superior magnetic behaviour of our prepared catalysts, for magnetic recording applications. The estimation of photocatalytic hydrogen production for the prepared photo nanocatalysts was conducted under ambient conditions, with an irradiation from a UV-visible light having wavelength range of 200–2400 nm. The prepared Co0.7Ni0.3Nd0.03La0.03Fe1.94O4 photocatalyst shows the maximum photocatalytic activity of 12.57 mmol gcat−1. Also, the photocatalytic hydrogen evolution, repeatability, and stability of all the prepared catalysts were analyzed at three successive cycles. The third cycle showed a little drop in photocatalytic hydrogen evolution to 11.26 mmol gcat−1 as compared to the first cycle. On the other hand, the electrocatalytic activity of produced electrocatalysts were determined towards the electrocatalytic HER via a three-electrode system in 0.5 M H2SO4 electrolyte. The produced Co0.7Ni0.3Nd0.03La0.03Fe1.94O4 nanocatalyst shows excellent electrocatalytic HER activity as compared to other samples. Hence, with photocatalytic/electrocatalytic water splitting traits, the prepared nanocatalysts are highly efficient and suitable for the production of clean and green hydrogen energy sources.

In‐Situ Growth of Cu2S‐MoS2 Bimetallic Electrocatalyst on Carbon Cloth for Hydrogen Evolution Reaction

AbstractHydrogen evolution reaction (HER) is one of prospective methods to produce hydrogen energy, and the key technology of which lies in the preparation of electrocatalysts. Preparations of catalysts with high efficiency, low price and good stability are expected. In this work, a new polyoxometalate‐based copper‐organic framework, [{CuII(C10N6H7)4(H2O)2}H6(PMo12O40)2] ⋅ 12H2O (1) [C10N6H7: 3‐(1H‐pyrazol‐4‐yl)‐5‐(pyridin‐4‐yl)‐1,2,4‐triazole], was synthesized as an electrocatalyst precursor, and confirmed by infrared spectroscopy (IR), single‐crystal X‐ray diffraction (SXRD) and X‐ray powder diffraction (PXRD). A new electrocatalyst (Cu2S‐MoS2@CC‐1) was synthesized from 1, thiourea (TU) and carbon cloth (CC) by a one‐pot hydrothermal method. Due to the synergistic effects between Cu2S and MoS2, the Cu2S‐MoS2@CC‐1 catalyst exhibits high electrocatalytic HER activity and good stability in 0.5 M H2SO4. Namely, Cu2S‐MoS2@CC‐1 shows low overpotential of 150 mV@10 mA cm−2 vs reversible hydrogen electrode (RHE) and small Tafel slope of 61 mV dec−1, and remains good stability at least 94 h and over 1000 catalytic cycles. This method provides a promising strategy for development of non‐noble metal catalysts.

Temperature controlled phase selective facile synthesis of tin sulfides and their electrochemical HER activity

Tin sulfide based semiconductors act as a promising candidate in photo/electro catalysis and solar cell applications owing to its suitable band gap and environment friendly nature. In this article we demonstrate a one-step synthesis of tin sulfides (SnS, SnS2, Sn2S3) via facile gas–solid reaction method. XRD, SEM and XPS analysis were carried out to characterize the samples for phase formation, morphology and valence states of the elements respectively. Bulk layered SnS and Sn2S3 micro-rods were obtained at the operating temperature of 700 °C and 600 °C respectively. Hexagonal nanoplate SnS2 was also obtained as a minor product during the synthesis of SnS. Furthermore, the electrocatalytic HER activity of the ballmilled SnS and Sn2S3 samples showed a considerable reduction in the overpotential of 171 mV and 126 mV respectively. The enhanced HER activity is attributed to the exposed catalytic active sites of the ballmilled samples.

Interface engineering of bifunctional nickel hydroxide/ nickel phosphide heterostructure for efficient intermittent hydrazine-assisted water splitting

Hydrazine oxidation reaction (HzOR) has been proposed to replace the sluggish oxygen evolution reaction (OER) for energy-saving hydrogen generation. However, the rational design of bifunctional electrocatalysts that can simultaneously accelerate HER/HzOR kinetics and the source of the hydrazine chemical substrate are still challenging. Herein, interfacial heterogeneous nickel hydroxide/nickel phosphide microstructures are in-situ grown on nickel foam (Ni(OH)2/Ni2P/NF) via a combined electrodeposition-phosphorization-electrodeposition strategy. After Ni(OH)2 modification, a charge redistribution is triggered between Ni(OH)2 and Ni2P, reducing the charge-transfer resistance and optimizing the adsorption energy of reaction intermediates. Ni(OH)2/Ni2P/NF thus yields an impressive bifunctional electrocatalytic activity for HER and HzOR with potentials of −72 and −14 mV at 10 mA cm−2, respectively. When using Ni(OH)2/Ni2P/NF as both electrodes, decreased cell voltage of 0.357 V is required to drive a current density of 100 mA cm−2 in 0.5 M hydrazine-containing alkaline electrolyte. Furthermore, an intermittent hydrazine-assisted water electrolysis system is proposed to make the combination of hydrazine sewage purification and energy-saving hydrogen production realistic.

Fabricating Ru single atoms and clusters on CoP for boosted hydrogen evolution reaction

Single atom catalysts (SATs) process the highest utilization efficiency of noble metals. The synergistic effect of noble single atoms and clusters, however, is insufficiently explored. In this work, Ru single atoms and clusters are fabricated on CoP substrate simultaneously, using a facile synchronous phosphorization method, with pre-prepared CoOOH and RuCl3 mixture as the raw materials. It is demonstrated that strong charge transfer is established between Co and Ru elements, which leads to electron-sufficient Ru sites. As a result, the Ru species decorated CoP exhibits excellent electrocatalytic activity for HER, with an overpotential of 32 mV to afford a current density of 10 mA/cm2 and a Tafel slope of 37.6 mV/dec, much better than the pure CoP counterpart. This work provides insights into the exploration of synergistic effect of noble metal single atoms and clusters fabricated on transition metal phosphide substrate.

A Double Atomic‐Tuned RuBi SAA/Bi@OG Nanostructure with Optimum Charge Redistribution for Efficient Hydrogen Evolution

AbstractCharge redistribution on surface of Ru nanoparticle can significantly affect electrocatalytic HER activity. Herein, a double atomic‐tuned RuBi SAA/Bi@OG nanostructure that features RuBi single‐atom alloy nanoparticle supported by Bi−O single‐site‐doped graphene was successfully developed by one‐step pyrolysis method. The alloyed Bi single atom and adjacent Bi−O single site in RuBi SAA/Bi@OG can synergistically manipulate electron transfer on Ru surface leading to optimum charge redistribution. Thus, the resulting RuBi SAA/Bi@OG exhibits superior alkaline HER activity. Its mass activity is up to 65000 mA mg−1 at an overpotential of 150 mV, which is 72.2 times as much as that of commercial Pt/C. DFT calculations reveal that the RuBi SAA/Bi@OG possesses the optimum charge redistribution, which is most beneficial to strengthen adsorption of water and weaken hydrogen‐adsorption free energy in HER process. This double atomic‐tuned strategy on surface charge redistribution of Ru nanoparticle opens a new way to develop highly efficient electrocatalysts.

A Double Atomic-Tuned RuBi SAA/Bi@OG Nanostructure with Optimum Charge Redistribution for Efficient Hydrogen Evolution.

Charge redistribution on surface of Ru nanoparticle can significantly affect electrocatalytic HER activity. Herein, a double atomic-tuned RuBi SAA/Bi@OG nanostructure that features RuBi single-atom alloy nanoparticle supported by Bi-O single-site-doped graphene was successfully developed by one-step pyrolysis method. The alloyed Bi single atom and adjacent Bi-O single site in RuBi SAA/Bi@OG can synergistically manipulate electron transfer on Ru surface leading to optimum charge redistribution. Thus, the resulting RuBi SAA/Bi@OG exhibits superior alkaline HER activity. Its mass activity is up to 65000 mA mg-1 at an overpotential of 150 mV, which is 72.2 times as much as that of commercial Pt/C. DFT calculations reveal that the RuBi SAA/Bi@OG possesses the optimum charge redistribution, which is most beneficial to strengthen adsorption of water and weaken hydrogen-adsorption free energy in HER process. This double atomic-tuned strategy on surface charge redistribution of Ru nanoparticle opens a new way to develop highly efficient electrocatalysts.

Chlorocobaloxime containing N-(4-pyridylmethyl)-1,8-naphthalamide peripheral ligands: synthesis, characterization and enhanced electrochemical hydrogen evolution in alkaline medium.

Two new discrete cobaloxime based complexes with the general formula [ClCo(dioxime)2L] (1 and 2), L1 = N-(4-pyridylmethyl)-1,8-naphthalamide, L2 = 4-bromo-N-(4-pyridylmethyl)-1,8-naphthalamide have been synthesized and characterized by various spectroscopic techniques such as FT-IR, 1H, 13C{1H} NMR and PXRD. The molecular structures of both complexes have also been determined using single crystal X-ray crystallography. The solid state molecular structures revealed distorted octahedral geometry around the Co(III) central metal ion with two dioximes in the equatorial plane and axial positions are occupied by chloro and pyridine nitrogen of N-(4-pyridylmethyl)-1,8-naphthalamide ligands. Both complexes exhibit weaker non-covalent interactions (C-H⋯O, C-H⋯Cl and C-H⋯π(Centroid) in complex 1 whereas C-H⋯O and C-H⋯Br in complex 2) resulting in the formation of dimeric and 1D supramolecular structures. Furthermore, these complexes are immobilized onto the surface of activated carbon cloth (CC) and their electrocatalytic performance for the hydrogen evolution reaction (HER) has been investigated in alkaline and acidic media as well as buffer solution. In alkaline medium, we found that complex 2 exhibited impressive electrocatalytic HER activity and produced a current density of -10 mA cm-2 at an overpotential of 260 mV, whereas complex 1 produced the same current density at an overpotential of 334 mV. An electrochemical impedance spectroscopy (EIS) spectral study revealed the faster charge transfer kinetics of complex 2 than that of complex 1. Similarly, the low Tafel slope (100 mV dec-1) for the HER with complex 2 indicates faster HER kinetics compared to complex 1. The chronoamperometric study showed that complex 2 is stable under electrocatalytic HER conditions for 5 h without losing the initial current density and it has also been established that the complex structure is retained after electrocatalysis.

Synthesis, characterisation, electrocatalytic HER activity, and electrical resistivity of 3R-NbS2 nanosheets

3R-NbS2 nanosheets were obtained at high temperature by decomposing of the Nb–HDA complex with H2S gas in a N2 atmosphere. The temperature-dependent electrical resistivity and electrochemical HER activity of 3R-NbS2 were measured.

Iron-induced lattice distortion generally boots the graphene-supported nickel phosphide nanoparticles catalysis for efficient overall water splitting

Rational design of high-efficient, low-cost and stable bifunctional electrocatalysts is necessary but challenging for water electrolysis. Transition metal phosphides (TMPs) with rich redox properties are considered to be the most promising substitutes for noble-metal materials but with aggregation and poor intrinsic electrical conductivity. Herein, we report an ultra-fast and controllable microwave strategy for synthesizing Fe-doped nickel phosphide on reduced graphene oxide (Fe-Ni12P5/rGO) as a highly active bifunctional electrocatalyst for both hydrogen and oxygen evolution reactions (HER and OER). It is noteworthy that Fe introduction can significantly cause the lattice distortion of Ni12P5 and lead to the increase of electrocatalytic active sites and modulation of the electronic structure of each catalytic center. Benefiting from the highly active Fe-Ni12P5 nanoparticles and two-dimensional graphene conductive network, the as-fabricated Fe-Ni12P5/rGO shows excellent electrocatalytic activity for HER and OER with good stability. In addition, an overall water splitting device with Fe-Ni12P5/rGO as both the cathode and anode electrocatalysts requires only an extremely low cell voltage of 1.57 V to reach 10 mA cm−2, which is attractive among the latest research. This work provides a facile and effective approach for the design of high-performance transition metal-based electrocatalysts.

General Synthesis of MOF Nanotubes via Hydrogen-Bonded Organic Frameworks toward Efficient Hydrogen Evolution Electrocatalysts.

The application scope of metal-organic frameworks (MOFs) can be extended by rationally designing the architecture and components of MOFs, which can be achieved via a metal-containing solid templated strategy. However, this strategy suffers from low efficiency and provides only one specific MOF from one template. Herein, we present a versatile templated strategy in which organic ligands are weaved into hydrogen-bonded organic frameworks (HOFs) for the controllable and scalable synthesis of MOF nanotubes. HOF nanowires assembled from benzene-1,3,5-tricarboxylic acid and melamine via a simple sonochemical approach serve as both the template and precursor to produce MOF nanotubes with varied metal compositions. Hybrid nanotubes containing nanometal crystals and N-doped graphene prepared through a carbonization process show that the optimized NiRuIr alloy@NG nanotube exhibits excellent electrocatalytic HER activity and durability in alkaline media, outperforming most reported catalysts. The strategy proposed here demonstrates a pioneering study of combination of HOF and MOF, which shows great potential in the design of other nanosized MOFs with various architectures and compositions for potential applications.

Type-II CuFe2O4/Graphitic Carbon Nitride Heterojunctions for High-Efficiency Photocatalytic and Electrocatalytic Hydrogen Generation.

Solar water splitting has emerged as an urgent imperative as hydrogen emerges as an increasingly important form of energy storage. g-C3N4 is an ideal candidate for photocatalytic water splitting as a result of the excellent alignment of its band edges with water redox potentials. To mitigate electron-hole recombination that has limited the performance of g-C3N4, we have developed a semiconductor heterostructure of g-C3N4 with CuFe2O4 nanoparticles (NPs) as a highly efficient photocatalyst. Visible-light-driven photocatalytic properties of CuFe2O4/g-C3N4 heterostructures with different CuFe2O4 loadings have been examined with two sacrificial agents. An up to 2.5-fold enhancement in catalytic efficiency is observed for CuFe2O4/g-C3N4 heterostructures over g-C3N4 nanosheets alone with the apparent quantum yield of H2 production approaching 25%. The improved photocatalytic activity of the heterostructures suggests that introducing CuFe2O4 NPs provides more active sites and reduces electron-hole recombination. The g-C3N4/CuFe2O4 heterostructures furthermore show enhanced electrocatalytic HER activity as compared to the individual components as a result of which by making heterostructures g-C3N4 with CuFe2O4 increased the active catalytic surface for the electrocatalytic water splitting reaction. The enhanced faradaic efficiency of the prepared heterostructures makes it a potential candidate for efficient hydrogen generation. Nevertheless, the designed heterostructure materials exhibited significant photo- and electrocatalytic activity toward the HER, which demonstrates a method for methodically enhancing catalytic performance by creating heterostructures with the best energetic offsets.