Recent development of transition metal doped carbon materials derived from biomass for hydrogen evolution reaction

Achieving high catalytic performance with the lowest cost is critical for hydrogen evolution reduction. In recent years, biomass-derived carbon catalysts have triggered huge interest in catalytic reactions owing to the low cost, high energy conversion efficiency and environmental friendliness. A rapid growth of novel electrocatalysts is witnessed especially those based on non-precious metals, some of which approach the activity of precious metals. Synergistic interactions between metals and heteroatoms can significantly improve the electrocatalytic activity, thus transition metal-decorated biomass-based carbon materials were commonly adopted to improve HER performance. The resulting electrocatalytic activities are introduced and compared to conventional Pt/C-based electrocatalysts in present research. Moreover, the remaining challenges in the development process and future prospects of hydrogen evolution reduction catalysts are discussed.     

Cobalt and cobalt oxide supported on nitrogen-doped porous carbon as electrode materials for hydrogen evolution reaction

A facile method is proposed to prepare cobalt supported on nitrogen-doped porous carbon material with high graphitization degree by using chitosan as carbon source, urea as soft template and poloxamer as dispersant. The prepared cobalt-carbon material (Co@NPC) shows that uniformly distributed cobalt nanoparticles are encapsulated in nitrogen-doped porous carbon bundle with large specific surface area. When Co@NPC is applied as electrode in hydrogen evolution reaction, it exhibits superior electrocatalytic performance with low overpotential (η₁₀ = 259 mV), small Tafel slope (99 mV dec⁻¹) and high stability with 83% of its original current density remained after 6 h electrochemical test in 1 M potassium hydroxide electrolyte.     

Duckweed derived nitrogen self-doped porous carbon materials as cost-effective electrocatalysts for oxygen reduction reaction in microbial fuel cells

Cost-effective metal-free electrocatalysts for oxygen reduction reaction were incredible significance of improvement about microbial fuel cells. In this research, a novel nitrogen self-doped porous carbon material is effectively inferred with KOH activation from a natural and renewable biomass, duckweed. Self-doped nitrogen in carbon matrix of nitrogen-doped porous carbon at 800 °C provides abundant active sites for oxygen reduction and improves the oxygen reduction kinetics significantly. Moreover, the porous structure of nitrogen-doped porous carbon at 800 °C encourages the transition of electrolyte and oxygen molecules throughout the oxygen reduction reaction. Oxygen on the three-phase boundary is reduced to water according to a four-electron pathway on nitrogen-doped porous carbon electrocatalyst. The single-chamber microbial fuel cell with nitrogen-doped porous carbon as electrocatalyst achieves comparable power density (625.9 mW m⁻²) and better stability compared to the commercial Pt/C electrocatalyst. This simple and low-cost approach provides a straightforward strategy to prepare excellent nitrogen-doped electrocatalyst derived from natural and renewable biomass directly as a promising alternate to precious platinum-based catalysts in microbial fuel cells.     

Easily-prepared bimetallic metal phosphides as high-performance electrode materials for asymmetric supercapacitor and hydrogen evolution reaction

Transition metal phosphides are very attractive because of the remarkable performance in energy storage and conversion. Herein, a series of bimetallic phosphides are synthesized through a one-step solid-state reaction. The obtained bimetallic phosphides show outstanding properties as supercapacitor electrode materials. Results show that the incorporation of secondary metal into phosphides tunes composition, electronic structure and then the electrochemical performance. And electrochemical properties are closely associated with the secondary metal content. Notably, the obtained NiCoP shows the best performance with 2011 F g⁻¹ at 1 A g⁻¹. And an asymmetric supercapacitor (ASC) based on NiCoP shows energy density of 47.6 W h kg⁻¹, along with 90.5% of capacitance maintained after 10000 cycles. In addition, the NiCoP also possesses great performance toward hydrogen evolution reaction (HER), which displays the lowest potential of 0.221 V vs. RHE and 0.173 V vs. RHE at 10 mA cm⁻² in 0.5 M H₂SO₄ as well as 1.0 M KOH, respectively. The excellent properties may result from the enhanced electrical conductivity, synergistic effects among metal elements and the increased local electrical dipole. The regulation of electronic structure through introduction of secondary metal atom sheds considerable light on realization and preparation of the bimetallic transition metal compounds as electrode materials.     

Three-dimensional hierarchically porous iridium oxide-nitrogen doped carbon hybrid: An efficient bifunctional catalyst for oxygen evolution and hydrogen evolution reaction in acid

Active and durable acid medium electrocatalysts for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are of critical importance for the development of proton exchange membrane (PEM) water electrolyser or Fuel cells. Herein, we report a facile method for the synthesis of 3D-hierarchical porous iridium oxide/N-doped carbon hybrid (3D-IrO₂/N@C) and its superior OER and HER activity in acid. In 0.5 M HClO₄, this catalyst exhibited remarkable activity towards OER with a low overpotential of 280 mV at 10 mA/cm² current density, a low Tafel slope of 45 mV/dec and ∼98% faradaic efficiency. The mass activity (MA) and turnover frequency (TOF) are found to be 833 mA/mg and 0.432 s⁻¹ at overpotential of 350 mV which are ∼32 times higher than commercial (comm.) IrO₂. The HER performance of this 3D-IrO₂/N@C is comparable with comm. Pt/C catalyst in acid. This 3D-IrO₂/N@C catalyst requires only 35 mV overpotential to reach a current density 10 mA/cm² with Tafel slope 31 mV/dec. Most importantly, chronoamperometric stability test confirmed superior stability of this catalyst towards HER and OER in acid. This 3D-IrO₂/N@C catalyst was applied as both cathode and anode for over-all water splitting and required only 1.55 V overpotential to achieve a current density of 10 mA/cm² in acid. The outstanding activity of the 3D-IrO₂/N@C catalyst can be attributed to a unique hierarchical porous network, high surface area, higher electron and mass transportation, synergistic interaction between IrO₂ and carbon support.     

Ni3Mo3N coupled with nitrogen-rich carbon microspheres as an efficient hydrogen evolution reaction catalyst and electrochemical sensor for H2O2 detection

Hydrogen evolution reaction (HER) and electrochemical analysis are two important fields of electrochemical research at present. We found that both HER and some electrochemical analytical reactions relied on the concentration of hydrogen ions (H⁺) in solution, so we intended to develop an electrode material that is sensitive to H⁺ and can be used for both HER and some electrochemical analyses. In this work, we synthesized Ni₃Mo₃N coupled with nitrogen-rich carbon microspheres (Ni₃Mo₃N@NC MSs) as highly efficient electrode material for HER and detection of Hydrogen peroxide (H₂O₂), which plays an important role in physiological processes. Here the aniline was used as the nitrogen and carbon sources to synthesize Ni₃Mo₃N@NC. The Ni₃Mo₃N@NC MSs showed high performance for HER in 1 M KOH solution with a small overpotential of 51 mV at 10 mA cm^?2 and superior stability. For H₂O₂ detection, a detection limit of 1 μM (S/N = 3), sensitivity of 120.3 μA·mM^?1 cm^?2 and linear range of 5 μM–40 mM can be achieved, respectively. This work will open up a low-cost and easy avenue to synthesize transition metal nitrides coupled with N-doped carbon as bifunctional electrode material for HER and electrochemical detection.     

Effect of the thickness of nickel electrode with aligned porous structure on hydrogen evolution reaction

Seven nickel electrodes with aligned porous structure of different thicknesses (i.e., 100, 250, 400, 500, 600, 850, and 1100 μm) were fabricated via freeze casting, and the effect of the electrode thickness on hydrogen evolution reaction (HER) was experimentally studied. The polarization curves of the porous electrodes were obtained by linear sweep voltammetry (LSV) in a 1 M KOH solution. The results show that, in the lower current density zone, the overpotential decreases with the increasing thickness of the aligned porous electrode. At higher current density, the overpotential presents a relative complex variation with the electrode thickness. For a thicker porous electrode, its electrochemically active surface area (ECSA) undoubtedly increases. Nevertheless, its bubble removal ability decreases due to deeper porous channels, which adversely affects the HER performance. It is also found that while the aligned pore orientation of the electrode is parallel to gravity direction, the electrode with a thickness of 400 μm has a trade-off between the ECSA and bubble removal ability and shows optimal performance.     

Electrocatalytic properties of porous Ni-Co-WC composite electrode toward hydrogen evolution reaction in acid medium

Porous Ni-Co-(WC)_x ternary composite electrodes were fabricated by means of electrodeposition on a foam Ni substrate. The surface morphology and microstructure of the electrodes were characterized by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The electrocatalytic properties of porous Ni-Co-(WC)_x electrodes for hydrogen evolution reaction (HER) in 0.5 M H₂SO₄ solution at temperatures from 25 to 50 °C were conducted by means of cathodic polarization, electrochemical impedance spectroscopy (EIS), cyclic voltammetry and chronoamperometry (CA). These Ni-Co-WC electrodes are efficient electrocatalysts for HER. Compared with the porous Ni-Co electrode, the porous Ni-Co-(WC)_x electrode exhibited a lower HER overpotential, a lower electrochemical impedance, a lower apparent activation energy and a higher exchange current density. The apparent exchange current density of porous Ni-Co-(WC)_x (x = 10, 20, 30 and 40 g/l) is 2.01, 3.01, 7.8 and 19.91 times of porous Ni-Co electrode, respectively. With the increase of WC concentration and temperature, the apparent exchange current density of HER was enhanced. With the increase of WC concentration and potential, the HER resistance and the activation energy decreased. The Ni-Co-(WC_)x electrode exhibited superior corrosion resistance and stability for HER.     

Construction and preparation of nitrogen-doped porous carbon material based on waste biomass for lithium-ion batteries

Biomass derived carbon materials have been widely studied as electrodes in energy storage devices due to their renewable nature, low-cost and tunable physical/chemical properties. However, the influences of different treatments for biomass derived carbon materials are still lack of in-depth discussion. In this work, we investigate the effects of the treatment for biomass on the structure and composition of the resulted carbon materials. Especially, the optimal N-doped porous carbon (NPCCS), which was fabricated by H₂SO₄-assisted hydrothermal treatment and subsequent pyrolysis process using corn silk as raw material, shows a unique interconnected layered nanostructure with ultra-high nitrogen content (18.79 at%). As a result, the NPCCS electrode displays excellent cycling stability and outstanding rate performance in lithium-ion half-cell test and shows high first reversible specific capacity of 523.6 mAh g^?1 in full-cell test. This work provides some guidance for preparing biomass derived carbon materials with superior electrochemical performance for the applications in advanced energy storage devices.     

Development and operation of alternative oxygen electrode materials for hydrogen production by high temperature steam electrolysis

High temperature steam electrolysis (HTSE) is one of the most promising ways for hydrogen mass production. To make this technology suitable from an economical point of view, each component of the system has to be optimized, from the balance of plant to the single solid oxide electrolysis cell. At this level, the optimization of the oxygen electrode is of particular interest since it contributes to a large extent to the cell polarization resistance. The present paper is focused on alternative oxygen electrode materials with improved performances compared to the usual ones mainly based on perovskite structure. Two nickelates, with compositions La₂NiO_4+δ and Nd₂NiO_4+δ are investigated and evaluated in HTSE operation at the button cell level. The performances of the Ln₂NiO_4+δ - containing cells (Ln = La, Nd) is improved compared to a cell containing the classical Sr-doped LaMnO₃ (LSM) perovskite oxygen electrode showing that nickelates are promising candidates for HTSE oxygen electrodes, especially for operation below 800 °C. Indeed, current densities determined at 1.3 V are 1.1 times larger for the La₂NiO_4+δ - containing cell and 1.6 times larger for the Nd₂NiO_4+δ one compared to the LSM - containing cell at 850 °C, whereas at 750 °C they are 1.8 and 4.4 times larger, respectively. Thanks to the use of a reference electrode, by coupling impedance spectroscopy and polarization measurements, the overpotential of each working electrode is deconvoluted from the complete cell voltage under HTSE operating conditions.     

Synthesis of lawn-like NiS2 nanowires on carbon fiber paper as bifunctional electrode for water splitting

a low-cost electrode with lawn-like NiS₂ nanowire arrays on flexible carbon fiber paper was synthesized, for the first time, via sulfurization of Ni₂(CO₃)(OH)₂ precursor. And the performance of this electrode as a bifunctional electrocatalyst toward both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) was evaluated. It shows that NiS₂ NWs/CFP requires small overpotentials of 165 mV for HER and 246 mV for OER, respectively, to deliver the current density of 10 mA cm^?2 in 1.0 M KOH. The corresponding symmetric two-electrode alkaline water electrolyzer only needs a cell voltage of 1.59 V to afford 10 mA cm^?2 water-splitting current density.     

Facile synthesis of carbon encapsulated RuO2 nanorods for supercapacitor and electrocatalytic hydrogen evolution reaction

In this work, carbon encapsulated RuO₂ nanorods (RuO₂ NRs/C) has been synthesized by thermolysis of ruthenium chloride and Punica granatum (P. granatum) peel under N₂ atmosphere. The synthesized RuO₂ NRs/C was characterized using Fourier transform infrared (FT-IR) spectroscopy, X-ray diffraction method (XRD), field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HR-TEM) with energy dispersive spectroscopy (EDS) analyses. The FT-IR results suggested that the organic constituents of P. granatum have been carbonized and encapsulated over RuO₂ nanorods (RuO₂ NRs). The XRD pattern of RuO₂ NRs/C revealed its crystalline nature and carbon encapsulation. The synthesized RuO₂ NRs/C has been well dispersed with the average width of 20 nm, exposed from the FE-SEM and HR-TEM images. The EDS results of RuO₂ NRs/C showed the existence of three elements viz., Ru, O and C. Further, the supercapacitor and electrocatalytic hydrogen evolution reaction (HER) activities of RuO₂ NRs/C were studied using standard electrochemical methods. The synthesized RuO₂ NRs/C offered a maximum specific capacitance of 151.3 F g⁻¹ at a scan rate of 5 mV s⁻¹, obtained from the cyclic voltammetry results. The onset over potential and Tafel slope of synthesized RuO₂ NRs/C for HER were −0.099 V_RHE and −99.4 mV dec⁻¹, respectively. The present study revealed that RuO₂ NRs/C as a better candidate for supercapacitor and HER.     

Facile preparation of N,P co-doped molybdenum carbide / porous carbon rough microspheres for efficient electrocatalytic hydrogen evolution

Despite that diverse carbon materials have been designed as framework to anchor molybdenum carbide to efficiently improve catalytic performance for hydrogen evolution reaction (HER), simply and uniformly hybridizing Mo and carbon source to form well-defined heteroatom-doped Mo₂C/carbon nanostructure using suitable precursors to expose the more active sites and optimize electron structure Mo₂C is still great challenge. Herein, we design and fabricate N, P-co-doped molybdenum carbide/porous carbon hybrid rough microspheres by a simple hydrothermal and followed annealing method using red jujube and phosphomolybdic acid as carbon and Mo source, respectively. Benefiting from carbon framework derived from red jujube inhibiting the aggregation of Mo₂C nanoparticles, N, P co-doping changing the electro-structure of the adjacent Mo and C atoms, and rough micro-spherical structure increasing the electrolyte-active materials contact surface, the resulting material exhibits high electrocatalytic performance with a low overpotential of 103 and 80 mV at current densities of 10 mA cm⁻², a small Tafel slope of 57 and 46 mV dec⁻¹, respectively, in acidic and alkaline electrolyte, and excellent stability. The convenient resource, facile preparation and high performance make this material showing great potential in cost effective hydrogen production.     

Hierarchically porous carbon from biomass tar as sustainable electrode material for high-performance supercapacitors

The byproduct tar from biomass gasification process had seriously impeded development and applications of this technology, thus novel path for biomass tar valorization is had been continuously pursued. Given its high carbon content, this work attempted to convert biomass tar into hierarchically porous carbon by thermal activation with acetate potassium. The optimal product produced with mass ratio of biomass tar to acetate potassium of 1:3 and activation temperature at 800 °C was revealed as excellent electrode material for high-performance supercapacitor, which demonstrated electrochemical capacitance up to 310.4 F/g at 0.2 A/g, whilst preserved 91% of initial capacitance after 5000 charge-discharge circles at current density of 5 A/g. These excellent properties had arisen from the open and hierarchical porosity and large surface area. This work disclosed the great potential of biomass tar as sustainable and competent candidate for fabricating high-performance electrode material for electrochemical energy devices, and may bring up new opportunities to development of biomass gasification technologies.     

One-step electrodeposition of cauliflower-like CozNiySx@polypyrrole electrocatalysts on carbon fiber paper for hydrogen evolution reaction

Transition-metal chalcogenides as the promising alternatives to noble-metal-based electrocatalysts for hydrogen evolution reaction (HER) with high activity and durability in water splitting have attracted extensive attention in recent years. Herein, Co_zNi_yS_x@PPy composites with three-dimensional (3D) cauliflower-like were firstly prepared on carbon fiber paper (CFP) via a simple and efficient electrochemical reduction of elemental sulfur in the precursor of S@PPy composite coated on CFP to react with Co and Ni ions in the electrolyte. The optimum electrode, i.e., Co_zNi_yS_x@PPy/CFP-6 (A-6) prepared by using an electrolyte with a Co/Ni molar ratio of 0/6, showed excellent catalytic activity (with an overpotential of 185 mV@10 mA cm⁻² and a small Tafel slope of 78.13 mV dec⁻¹) as well as long-term stability (at least 100 h) in 1 M KOH solutions. This work provides a novel way to fabricate effective and non-noble-metal electrodes for HER in water splitting.     

Simulation and characterization of hydrogen evolution reaction on porous NiCu electrode using surface response methodology

In this study, porous NiCu coating was applied on Ni foam and electrocatalytic activity for hydrogen evolution reaction was studied using the simulation method. In order to optimize the electrocatalytic activity of the fabricated coating on the Ni foam, the experiment was designed using the response surface methodology (RSM). The results demonstrated that in the optimal condition, the porous NiCu electrode requires only 203 and 310 mV vs. RHE overpotentials at the current densities of 10 and 100 mA cm⁻², respectively. In addition, the Tafel slope was 88.2 mV dec⁻¹ and the electrochemically active surface area was about 1790 cm². Moreover, the porous NiCu catalyst depicted favorable electrocatalytic durability and affords long-term electrolysis without activity degradation. This high electrocatalytic activity and stability of coating can be attributed to the active surface area due to porous structure growth, rapid separation of hydrogen gas bubbles and the synergistic effect between Ni and Cu. This study offers an effective fabrication method for three-dimensional electrodes for renewable energy resources.     

Embedding Co2P nanoparticles into N&P co-doped carbon fibers for hydrogen evolution reaction and supercapacitor

The demands for highly efficient and low-cost electrochemically active materials are still urgent needs for the fields of electro-catalysis and supercapacitor. Herein, a facile strategy for preparing high-efficient bi-functional electrode material was reported. The electrode material was prepared through embedding Co₂P nanoparticles in the binary co-doped carbon nanofibers (Co₂P@N&P-CNFs). This unique structure can effectively prevent the Co₂P from detaching and provide abundant active sites. Materials prepared in this work showed the superior hydrogen evolution reaction (HER) performance with overpotential of 192 mV at a current density of 10 mA cm^?2 and remarkable stability for 20 h. Moreover, the asymmetric supercapacitor (ASC) was fabricated using the Co₂P@N&P-CNFs as the positive electrode material and carbon nanofibers (CNFs) as the negative electrode material, which shows an outstanding cycle stability (91.5% of the initial capacitance is retained throughout 10,000 charge-discharge tests) and a high E of 22.31 Wh kg^?1 at the P of 225.02 W kg^?1 at 0.3 A g^?1. This work offers an effective route in designing bi-functional active materials for HER and supercapacitor.     

Walnut shell-derived hierarchical porous carbon with high performances for electrocatalytic hydrogen evolution and symmetry supercapacitors

Walnut Shell-derived hierarchical porous carbon has been successfully synthesized by the efficient KOH activation process. The hierarchical porous carbon material activated at 600 °C, has the specific micropore area of 1037.31 m² g⁻¹ and micropore volume of 0.51 cm³ g⁻¹, which leads to have electrochemical performances of the hydrogen evolution reaction (HER) and supercapacitors. Specifically, as the hydrogen evolution reaction electrocatalyst, the walnut shell-derived carbon material activated at 600 °C exhibits a lower onset potential of 6.00 mV, a smaller Tafel slope of 69.76 mV dec⁻¹ and outstanding stability above long-term cycling. As a supercapacitor electrode material, the sample possesses specific capacitance of 262.74 F g⁻¹ at 0.5 A g⁻¹, the remarkable rate capability of 224.60 F g⁻¹ at even 10 A g⁻¹ and good long-term stability. A symmetric supercapacitor shows the highly energy density of 7.97 Wh kg⁻¹ at a power density of 180.80 W kg⁻¹. This novel and low-cost biomass material is very promising for the electrocatalytic water splitting and supercapacitors.     

Electrochemical behaviour of single walled carbon nanotubes – Hydrogen storage and hydrogen evolution reaction

The electrochemical behaviour of single walled carbon nanotubes (SWCNT) related to the mechanism involved in the hydrogen electrode reaction applying electrochemical and spectroscopic techniques is studied. Cyclic voltammetry applied to electrodes containing different percentages of SWCNT demonstrates that this material can behave as efficient capacitor and that the hydrogen electrode reaction develops through the H-electrosorption followed by the formation of molecular H₂ and its evolution. Also, SWCNT are able to storage hydrogen within their porous structure. This is confirmed through the galvanostatic charge and discharge experiments. Electrochemical impedance spectroscopy allowed calculating the real area that takes part in the electrode reaction and the main and valuable conclusion is that the hydrogen electrode reaction consists of a simple charge transfer reaction and that the H adatom relaxation or diffusion processes can be disregarded. Furthermore, a model proposed for their structure which was validated through impedance experiments confirms those conclusions. Results of Raman spectra allowed identifying the nature of the electrodes confirming that after purification the material is composed of single walled carbon nanotubes.     

Effect of pore orientation on the catalytic performance of porous NiMo electrode for hydrogen evolution in alkaline solutions

Porous NiMo alloys with Mo content of 5 at.% were fabricated by freezing casting method. The pores are elongated, and the media pore size is 8.1 μm. The electrocatalytic activity of the synthesized NiMo alloy foam as cathodes for hydrogen evolution reaction (HER) in 6.0 M potassium hydroxide solution was investigated. Results show that the electrodes which pore orientation is parallel to the hydrogen overflow direction present higher electrocatalytic activity than the electrodes with pore orientation perpendicular to the hydrogen overflow direction. The Tafel slope is 94 and 117 mV dec⁻¹, respectively at a current density of 10 mA/cm² at room temperature.