Insights into the effect of catalyst loading on methane steam reforming and controlling regime for metallic catalytic monoliths

The influence of Ru/LaAl₂O₃ catalyst loading (100–200 mg) was investigated over high cell density Fecralloy^® monoliths (461 cpsi, 1367 cpsi) for methane steam reforming (SMR). A uniform and well-attached catalyst layer was developed by in-situ washcoating method and the developed catalysts were analyzed by using various physico-chemical characterization techniques. The results confirmed the impact of catalyst loading on the geometric and hydraulic properties of monoliths, and methane conversion was improved by increasing both the catalyst loading and cell density. As per characteristic time analysis, no external and washcoat diffusion regimes were observed and SMR was found to be in kinetic controlling regime. The methane conversion was still limited by the amount of catalyst (200 mg) deposited onto the monoliths (40.9 μm for 461 cpsi, 26.9 μm for 1367 cpsi) which demonstrated the potential to deposit more catalyst up to the transition point of washcoat diffusion limitations. For same washcoat thickness of ～20.6 μm, the higher cell density 1367 cpsi monolith showed better catalytic activity towards SMR as compared to 461 cpsi monolith and this improvement is more prominent at lower temperature with a value of 13.6% higher methane conversion at 600 °C, WHSV = 55 NL h^?1 g_cat^?1 and S/C = 3.0.     

The first catalytic hydrolysis of ethylenediamine bisborane with hydrogel-supported metallic nanoparticles

Ethylene diamine bisborane (EDB) was synthesized in a single step as the hydrogen storage material. The synthesized compound was firstly used in the literature for the production of hydrogen gas by catalytic hydrolysis reaction. Cu, Co and Ni nanoparticles with average sizes of 75–150 nm formed in p(acrylicacid-co-vinylimidazole) hydrogel network structures were used as catalysts for the hydrolysis reaction. The effect of the parameters such as catalyst type, EDB concentration, catalyst concentration, temperature and solvent environment on the catalytic hydrolysis reaction of EDB was investigated. In the activity tests for the catalyst, it was determined that the catalyst had a loss of only 15% in activity even at the end of 5 cycles. The activation energies of hydrolysis reaction were calculated as 39.42 kJmol^–1, 44.77 kJmol^–1 and 47.48 kJmol^–1 for Cu, Co and Ni hydrogel composite catalyst, respectively.     

M (Co,Ni), N and S tridoped carbon nanoplates as multifunctional catalysts for rechargeable Zn-air batteries and water electrolyzers

Exploration of multifunctional non-precious metal catalysts towards oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is very important for many clean energy technologies. Here, two trifunctional catalysts based on M (Co, Ni), N and S tridoped carbon nanoplates (Co/N/S-CNPs and Ni/N/S-CNPs) are reported. Due to the relatively higher catalytic site content, graphitization degree and smaller charge-transfer resistance, the Co/N/S-CNPs catalyst shows higher activity and stability for ORR (onset potential of 0.99 V and half-wave potential of 0.87 V vs. RHE (reversible hydrogen electrode)), OER (overpotential at 10 mA cm^?2 of 0.37 V) and HER than the Ni/N/S-CNPs catalyst. Furthermore, when constructed with the Co/N/S-CNPs and commercial 20 wt% Pt/C + Ir/C cathodes, respectively, Zn-air battery (ZnAB) based on the Co/N/S-CNPs cathode displays better performance, including a higher power density of 96.0 mW cm^?2 and cycling stability at 5 mA cm^?2. In addition, an alkaline electrolyzer assembled with the Co/N/S-CNPs catalyst as a bifunctional catalyst can reach 10 mA cm^?2 at 1.65 V for overall water splitting and maintain excellent stability even after cycling for 12 h. The present work proves the potential of the Co/N/S-CNPs catalyst for many clean energy devices.     

Carbon nanofibers decorated SiC foam monoliths as the support of anti-sintering Ni catalyst for methane dry reforming

A silicon carbide (SiC) foam monolith decorated with a carbon nanofibers (CNFs) layer was employed as the catalyst support for Ni-based catalyst preparation, used for the CO₂ dry reforming of methane (DRM) reaction. The loading amount of CNFs on the SiC foam monolith was 6.6 wt.%, which obviously increased the surface area of the pristine SiC foam from 4 m²/g to 24 m²/g. The prepared CNFs layer strongly attached to the pristine SiC surface and was considerably stable even after 100 h time on stream (TOS) DRM reaction. The CNFs decorated SiC composite support provided more anchorage sites for improving the dispersion of the Ni particles and enhanced the metal-support interaction compared to the pristine SiC support. Compared with other catalysts such as Ni/SiC and Ni/CNFs, the Ni/CNFs-SiC catalyst exhibited not only the highest activity but also remarkable stability during DRM reaction. The XPS and SEM-EDS results showed that the carbon deposition over the nickel surface of Ni/CNFs-SiC catalyst was much less than those of Ni/SiC and Ni/CNFs catalysts. In addition, the XRD analysis verified that almost no sintering of nickel particle was detected over the Ni/CNFs-SiC catalyst, which was prepared with CNFs-SiC composite as catalyst support, even after 100 h TOS DRM reaction at 750 °C.     

Structural transformations of highly porous nickel catalysts during ethanol conversion towards hydrogen

In this work, we report a liquid-phase reduction method to prepare porous non-supported amorphous nickel catalysts with high surface areas (65–250 m²/g). A highly crystalline face center cubic Ni (fcc-Ni) catalyst with 110 m²/g surface area was also prepared by frontal crystallization of the amorphous nickel catalyst. The catalytic activity and stability of these catalysts for ethanol decomposition was investigated at different time on stream (TOS) to understand structural transformations occurring at the early stages of catalyst activation-deactivation. Activity vs. TOS results obtained at 473 K show that on the amorphous catalysts the conversion increases from about 50% to 60–75% reaching a steady value at ～30 h TOS, which remains constant during the observed 96 h of TOS. The fcc-Ni catalyst initially exhibits a higher conversion (～85%), however, it quickly deactivates to a conversion in the similar range as the amorphous catalysts. It is also shown that BET surface areas of amorphous catalysts decreases during hydrogen pretreatment at 473 K due to crystallization, grain growth, and sintering. The structure of amorphous catalysts continuously refines to form a combination of fcc-Ni and hexagonal close-packed nickel (hpc-Ni) phases, as well as nickel carbide (Ni₃C) and carbon layers that stabilize catalytic activity. The structure of the fcc-Ni catalyst remains unchanged during the 96 h TOS experiment indicating that carbon deposition might cause its initial deactivation. At 523 K, the amorphous catalyst shows 100% conversion, which remains constant during 96 h of TOS, while the fcc-Ni crystalline catalyst initially exhibits 95% conversion and then slowly deactivates to ～80% at 96 h TOS. Thus at 523K the stabilized amorphous catalyst does not deactivate under the same TOS compared to the crystalline fcc-Ni catalyst, showing that the active sites on these catalysts are different. The findings of this work suggest that the liquid-phase reduction method can be used to prepare active and stable catalysts for reactions involving decomposition of alcohols and hydrocarbons to produce hydrogen.     

Production of hydrogen from methanol steam reforming using CuPd/ZrO2 catalysts – Influence of the catalytic surface on methanol conversion and CO selectivity

Electricity generation for mobile applications by proton exchange membrane fuel cells (PEMFCs) is typically hindered by the low volumetric energy density of hydrogen. Nevertheless, nearly pure hydrogen can be generated in-situ from methanol steam reforming (MSR), with Cu-based catalysts being the most common MSR catalysts. Cu-based catalysts display high catalytic performance, even at low temperatures (ca. 250 °C), but are easily deactivated. On the other hand, Pd-based catalysts are very stable but show poor MSR selectivity, producing high concentrations of CO as by-product. This work studies bimetallic catalysts where Cu was added as a promoter to increase MSR selectivity of Pd. Specifically, the surface composition was tuned by different sequences of Cu and Pd impregnation on a monoclinic ZrO₂ support. Both methanol conversion and MSR selectivity were higher for the catalyst with a CuPd-rich surface compared to the catalyst with a Pd-rich surface. Characterization analysis indicate that the higher MSR selectivity results from a strong interaction between the two metals when Pd is impregnated first (likely an alloy). This sequence also resulted in better metallic dispersion on the support, leading to higher methanol conversion. A H₂ production rate of 86.3 mmol h^?1 g^?1 was achieved at low temperature (220 °C) for the best performing catalyst.     

Novel Ni–Co–B hollow nanospheres promote hydrogen generation from the hydrolysis of sodium borohydride

Ni–Co–B hollow nanospheres were synthesized by the galvanic replacement reaction using a Co–B amorphous alloy and a NiCl₂ solution as the template and additional reagent, respectively. The Ni–Co–B hollow nanospheres that were synthesized in 60 min (Ni–Co–B-60) showed the best catalytic activity at 303 K, with a hydrogen production rate of 6400 mL_hydrogenmin^?1g_catalyst^?1 and activation energy of 33.1 kJ/mol for the NaBH₄ hydrolysis reaction. The high catalytic activity was attributed to the high surface area of the hollow structure and the electronic effect. The transfer of an electron from B to Co resulted in higher electron density at Co sites. It was also found that Ni was dispersed on the Co–B alloy surface as result of the galvanic replacement reaction. This, in turn, facilitated an efficient hydrolysis reaction to enhance the hydrogen production rate. The parameters that influenced the hydrolysis of NaBH₄ over Ni–Co–B hollow nanospheres (e.g., NaOH concentration, reaction temperature, and catalyst loading) were investigated. The reusability test results show that the catalyst is active, even after the fifth run. Thus, the Ni–Co–B hollow nanospheres are a practical material for the generation of hydrogen from chemical hydrides.     

Study of coking and catalyst stability over CaO promoted Ni-based MCF synthesized by different methods for CH4/CO2 reforming reaction

CaO doped Ni/MCF catalysts were prepared by conventional incipient wetness impregnation and sol-gel methods for the study of methane dry reforming reaction. The fresh and used catalysts were characterized using H₂ temperature programmed reduction (H₂-TPR), X-ray diffraction (XRD), Fourier transform infra-red spectroscopy (FTIR), thermogravimetry (TG), differential scanning calorimetry (DSC) and O₂ temperature-programmed oxidation (O₂-TPO). XRD exhibited that CaO and Ni particles are dispersed on the surface of catalyst. The Ni:CaO ratio was adjusted for the improvement of pore textural properties on behalf of enhancement of metal particle dispersion for increased catalytic performance and anti-coking. The catalytic performance and stability of the catalysts for methane dry reforming reaction were studied at 700–750 °C at atmospheric pressure with GHSV of 24000 mL g^?1h^?1 having same feed ratio of CH₄:CO₂ = 1. Experimental results exhibited that catalyst prepared by a sol-gel method showed superior catalytic activity, stability and resisted carbon deposition than catalyst prepared incipient wetness impregnation method. Among all tested catalysts 9CaO 9Ni/MCF catalyst remained the best for catalytic performance and anti-coking activity due to higher metal dispersion with small metal particles, as well as the synergetic effect between CaO and Ni. During 75 h stability test over the catalyst 9CaO 9Ni/MCF the CH₄ and CO₂ conversion remained 91% and 99% respectively.     

Highly efficient and reactivated electrocatalyst of ruthenium electrodeposited on nickel foam for hydrogen evolution from NaBH4 alkaline solution

Cyclic life of catalyst for hydrolysis of sodium borohydride is one of the key issues, which hinder commercialization of hydrogen generation from sodium borohydride (NaBH₄) solution. This paper is aimed at promoting the cyclic life of Ru/Ni foam catalysts by employing an electro-deposition method. The effect of hydrolysis parameters on hydrolysis of sodium borohydride was studied for improving the catalytic performance. It is found that the hydrogen generation rate (HGR) of the hydrolysis reaction catalyzed by Ru/Ni foam catalyst can reach as high as 23.03 L min^?1 g^?1 (Ru). The Ru/Ni foam catalyst shows good catalytic activity after a cycleability test of 100 cycles by rinsing with HCl, which is considered as more effective method than rinsing with water for recovering the performance of Ru/Ni foam catalyst.     

Syngas production by steam and oxy-steam reforming of biogas on monolith-supported CeO2-based catalysts

In this study, the syngas production by steam reforming (SR) and oxy-steam reforming (OSR) of clean biogas over cordierite monoliths (400 cpsi) lined with Ni, Rh, or Pt on CeO₂ catalyst was deeply investigated. Structured catalysts were prepared by using an alternative method to traditional washcoating based on the combination of the solution combustion synthesis (SCS) with the wetness impregnation (WI) technique. TEM and SEM analysis were used to study the morphology of the catalytic layer and to determine its thickness, while the quality of the coating in terms of adhesion on the monolith was evaluated by ultrasonic treatment in isopropyl alcohol solution. The performance and the stability of the structured catalysts were investigated at different process parameters, namely temperature (700–900 °C), steam-to-carbon (S/C = 1–5) and oxygen-to-carbon (O/C = 0.1–0.2) molar ratios, and weight space velocity (WSV = 30,000–250,000 NmL g_cat^?1 h^?1). The SCS + WI deposition method allowed obtaining a uniform and thin coated layer with high mechanical strength. The following order of activity was exploited: Rh > Pt > Ni for biogas SR and Rh > Pt ≈ Ni for biogas OSR. The Rh-based catalyst exhibited higher activity and long-lasting stability towards biogas SR and OSR reactions for syngas production.     

Heteroatom-doped carbon nanospheres derived from cuttlefish ink: A bifunctional electrocatalyst for oxygen reduction and evolution

The development of efficient bifunctional catalysts for both oxygen reduction and oxygen evolution reactions is highly desirable but challenging in energy conversion and storage systems. Here, a simple yet cost-effective strategy is developed to produce heteroatom-doped carbon nanospheres using natural cuttlefish ink as the precursor. For the oxygen reduction reaction, the catalyst exhibits more positive onset-potential and larger diffusion limiting current density compared with benchmark platinum catalyst in alkaline medium. Moreover, the as synthesized catalyst shows low onset-potential for oxygen evolution reaction, indicating its outstanding catalytic activity. The catalyst shows a potential gap of 0.75 V between the oxygen evolution reaction potential at a current density of 10 mA cm^?2 and the oxygen reduction reaction potential at the half-wave potential, outperforming most of other noble metal-free carbon catalysts in the current state of research. The remarkable catalytic performance can be assigned to heteroatoms doping, full exposure of the active sites, large surface area and enrichment of pores for sufficient contact and rapid transportation of the reactants. This study offers a new approach for the synthesis of metal-free carbon nanomaterials from natural resources, and broadens the design for the fabrication of bifunctional oxygen reduction and oxygen evolution catalysts.     

Catalytic combustion of hydrogen—II. An experimental investigation of fundamental conditions for burner design

The performance of catalysts in different forms was investigated for the design of a catalytic combustor with hydrogen fuel. The catalysts tested had dimensions of 150 × 150 mm, and consisted of a ceramic honeycomb impregnated with Pt, two Ni metal foams coated with Pd powder which differed from each other in pore size, and a ceramic foam coated with Co-Mn-Ag oxide powder. In the diffusive mode of operation, the Pd-coated Ni foam with larger pores exhibited the highest combustion efficiency. The ceramic foam with the oxide coating also provided smooth hydrogen combustion in the range 0.2–1.0 kcal cm^?2 h^?1. Combustion efficiency was improved by increasing the amount of premixed air and totally supplied air. Spot measurements of surface temperature and gas composition were carried out over the catalyst surface and the characteristic features of each catalyst were compared and discussed.     

Experimental studies on the catalytic behavior of alloy and core-shell supported Co-Ni bimetallic nano-catalysts for hydrogen generation by hydrolysis of sodium borohydride

Monometallic (Co) and bimetallic (Co-Ni and Co-Cu) oxides catalysts supported on the almond based activated carbon (AC) were prepared by the heterogeneous deposition-precipitation method. The activity of these catalysts was evaluated as a function of reaction temperature, NaOH, and NaBH₄ concentration. Several analysis methods including XRD, XPS, FTIR, TEM, FESEM, ICP-OES, and BET were applied to characterize the structure of prepared samples. Well-dispersed supported bimetallic nano-catalysts with the size of particles below 20 nm were formed by using nickel and copper oxides as a promoter which was confirmed by XRD and TEM techniques. Surface composition of alloy and core-shell cobalt-nickel oxides catalysts was analyzed by ICP-OES which was in a good agreement with nominal content during catalyst preparation. The performance of bimetallic cobalt-nickel oxides catalysts indicated the synergic effect between cobalt and nickel in comparison with monometallic and bimetallic cobalt-copper samples for hydrogen production. Maximum hydrogen generation rate was measured for the supported core-shell catalyst as named Ni1/Co3/AC. The reaction rate increased with increasing the temperature of the alkaline solution as a significant parameter while other operating conditions were kept constant. The optimal values for NaOH and NaBH₄ content were calculated to be 10 wt % for both variables at 30 °C. Hydrogen production rates were calculated to be 252.0, 310.8 and 658.8 mL min^?1.g^?1 by applying Co3/Ni1/AC, Co3-Ni1/AC (alloy) and Ni1/Co3/AC at 30 °C in 5 wt % NaBH₄ and 5 wt % NaOH solutions, respectively. Obtained activation energy (50 kJ mol^?1) illustrated that the suitable catalysts were synthesized for hydrogen generation. The experimental study showed that the hydrolysis of NaBH₄ was a zero-order type reaction with the respect to the sodium borohydride concentration. A semi empirical kinetic model was derived at the various temperatures and NaOH concentrations.     

Effect of La2O3 replacement on γ-Al2O3 supported nickel catalysts for acetic acid steam reforming

The effect of replacement of γ-Al₂O₃ by La₂O₃ was studied on Ni catalysts for hydrogen production via acetic acid steam reforming. The La/(La + Al) weight ratio ranged from 0 to 1 in the catalyst support prepared by co-precipitation method. Over the Ni/La-3Al catalyst (the La/(La + Al) weight ratio at 0.25), the carbon conversion and hydrogen yield reached 100% and 72.72%, respectively, which was obviously higher than other catalysts at 700 °C, S/C = 1 and LHSV = 10 h^?1. The effect of S/C, LHSV and stability test were studied in detail over Ni/La-3Al catalyst, whose high activity maintained for more than 30 h.     

Enhanced activity of CO2 methanation over mesoporous nanocrystalline Ni–Al2O3 catalysts prepared by ultrasound-assisted co-precipitation method

The ultrasound-assisted co-precipitation method was employed for the synthesis of the Ni–Al₂O₃ catalysts with different metal loadings for the CO₂ methanation reaction. This study indicated that increasing the Ni loading up to 25 wt.% enhanced the surface area, decreased the crystallinity and improved the reducibility of the catalysts, while further raise in Ni loading adversely influenced the surface area. Improvements in catalytic performance were obtained with the raise in Ni content because of enhancing the BET area. The results confirmed that the 25Ni–Al₂O₃ catalyst with the highest BET area (188 m² g^?1) and dispersion of Ni has the highest catalytic activity in CO₂ methanation and reached to 74% CO₂ conversion and 99% CH₄ selectivity at 350 °C. In addition, this catalyst exhibited a great stability after 10 h time-on-stream.     

Finding a suitable catalyst for on-board ethanol reforming using exhaust heat from an internal combustion engine

Ethanol steam reforming with pure ethanol and commercial bioethanol (S/C = 3) was carried out inside the housing of the exhaust gas pipe of a gasoline internal combustion engine (ICE) by using exhaust heat (610–620 °C). Various catalytic honeycombs loaded with potassium-promoted cobalt hydrotalcite and with ceria-based rhodium–palladium catalysts were tested under different reactant loads. The hydrogen yield obtained over the cobalt-based catalytic honeycomb at low load (F/W < 25 mL_liq·g_cat^?1·h^?1, GHSV = 4·10² h^?1) was remarkably high, whereas that obtained over the noble metal-based catalytic honeycombs was much superior at high loads (F/W = 25–150 mL_liq·g_cat^?1·h^?1, GHSV = 4·10²–2.4·10³ h^?1). At higher reactant loads the overall hydrogen production was limited by heat transfer from the exhaust heat to the reformer inside the housing of the exhaust gas pipe of the ICE. Extensive carbon deposition occurred over the cobalt-based honeycomb, making its use impractical. In contrast, stability runs (>200 h) at high load (F/W = 150 mL_liq·g_cat^?1·h^?1, GHSV = 2.4·10³ h^?1) showed that promotion of the ceria-supported noble metal catalyst with alumina and zirconia is a key element for practical application using commercial bioethanol. HRTEM analysis of post mortem honeycombs loaded with RhPd/Ce_0.5Zr_0.5O₂–Al₂O₃ showed no carbon formation and no metal agglomeration.     

Monodisperse nickel nanoparticles supported on multi-walls carbon nanotubes as an effective catalyst for the electro-oxidation of urea

Monodisperse nickel nanoparticles (NPs) were synthesized by reduction of nickel acetylacetonate with oleylamine in 1-octadecene, and uniformly dispersed on multi-walls carbon nanotubes via sonication. The electro-oxidation activity and stability of the catalyst were investigated by cyclic voltammetry and chronoamperometry respectively. Characterization results indicate that the 80%Ni/MWCNT (80% represent the wt% of Ni) catalyst shows the highest electro-oxidation activity (1866 mA cm^?2 mg^?1) and stability for urea electro-oxidation, which is higher than most reported Ni-based catalysts. In addition, the urea electro-oxidation process is a mixed control of diffusion and kinetic limitation, as demonstrated by the effects of scan rate on the peak current density and peak potential. Subsequently, the impact of diffusion for the different catalysts varies with the change of Ni loading, which is verified by experiments.     

One-pot sol–gel synthesis of Ni/TiO2 catalysts for methane decomposition into COx free hydrogen and multiwalled carbon nanotubes

A series of mesoporous Ni/TiO₂ catalysts with different loadings of nickel from 10 to 50 wt% was successfully prepared via a facile one-pot sol–gel route; characterized for its structural, textural and redox properties; and tested for the non-oxidative thermocatalytic decomposition of undiluted methane for the first time. The characterization results reveal the presence of both NiO and NiTiO₃ and metallic nickel as active metal phase in the fresh and reduced catalysts, respectively. Spherical catalyst particles were found to be highly inter-aggregated and to provide a porous texture to the catalyst. All of the prepared catalysts exhibited high catalytic activity and stability for methane decomposition. It is due to the fine dispersion of active nickel nanoparticles on the surface of the TiO₂ support with proper metal-support interaction. Moreover, with increasing nickel loading and reaction temperature, the yields of hydrogen and nanocarbon were found to be significantly increased. A maximum hydrogen yield of 56% and a final carbon yield of 1544% were obtained for the 50% Ni/TiO₂ catalyst at 700 °C with an undiluted methane feed of 150 ml/min for 360 min of time on stream. The catalyst showed high catalyst stability, for a period of 960 min of time on stream and ～24% hydrogen yield was observed at the end of long-term run using the 50% Ni/TiO₂ catalyst. Moreover, irrespective of the nickel loading involved, bulk amount of multiwalled carbon nanotubes were deposited on the surface of the catalyst. XRD and Raman analyses of the spent catalysts showed that the crystallinity of nanocarbon increased with increasing nickel loadings, whereas the graphitization degree remained unaffected, with an I_D/I_G value of 0.88.     

Nickle-cobalt composite catalyst-modified activated carbon anode for direct glucose alkaline fuel cell

Glucose is the most abundant monosaccharide in nature and has great potential as high-density hydrogen carrier for fuel cells. However, the practical application of direct glucose alkaline fuel cell (DGAFC) is hampered by lack of cost-effective anode catalyst. In this study, nickel-cobalt composite catalysts were prepared by NaBH₄ reduction method and electrochemical, morphological and chemical properties of catalysts were characterized by LSV, EIS, SEM, TEM, XRD and XPS techniques. The nickel-cobalt composite catalyst and modified activated carbon anode was evaluated in one-chamber DGAFC. Our results demonstrated that the DGAFC performance was greatly improved with the addition of Ni-Co composite catalyst in the anode. Fuel cell achieved the peak power density of 23.97 W m^?2 under the condition of 1 M glucose, 3 M KOH and ambient temperature. The enhancement of the anode performance could be attributed to the synergic effect of two reversible redox systems, Ni(II)/Ni(III) and Co(II)/Co(III), which improved interfacial charge-transfer kinetics. Our study may facilitate the development of cost-effective renewable energy devices.     

Defect-rich MoS2 nanosheets vertically grown on graphene-protected Ni foams for high efficient electrocatalytic hydrogen evolution

Defect-rich MoS₂ nanosheets are vertically grown on graphene-protected Ni foam by a facial hydrothermal route. The vertically aligned MoS₂ nanosheets with defects such as cracks, amorphousness and oxygen-incorporated disorders endow these as-synthesized catalysts with rich active sites, high conductivity and good stability. The graphene deposited on Ni foam increases its stability in acid. The optimized catalyst exhibits high activity for hydrogen evolution with a quite low overpotential of 140 mV at 10 mA cm^?2, a small Tafel slope of 42 mV decade^?1, and a large exchange current density of 63 μA/cm², as well as excellent stability. This performance is superior to most of its analogue MoS₂ and many transition metal sulfides. This work will broaden the vision to improve the activity of self-supported electrocatalysts by carefully designing the anchored catalysts.