MoS2||CoP heterostructure loaded on N,P-doped carbon as an efficient trifunctional catalyst for oxygen reduction,oxygen evolution,and hydrogen evolution reaction

Exploring multifunctional electrocatalysts is crucial for the development of energy conversion and storage equipments, such as fuel cells, water splitting devices and zinc-air batteries. Herein, we provide a rational design whereby the cobalt phosphide particles are introduced into molybdenum sulfide nanosheets to form a heterostructure (MoS₂||CoP) through the ultrasonic method and calcination. Subsequently, N, P-doped carbon (NPC) is obtained synchronously. The as-prepared MoS₂||CoP/NPC demonstrates highly effective multifunctional catalytic performance for oxygen evolution and hydrogen evolution reaction at lower overpotential, as well as oxygen reduction reaction at high half-wave potential. What this reveals is higher power density and superior stability in zinc-air battery. The excellent electrocatalytic activity of MoS₂||CoP/NPC may be attributed to the presence of the MoS₂||CoP heterostructure, as well as N, P-doped carbon coupled with a high percentage of pyridinic-N. This work proposes a novel and facile strategy to prepare the heterostructure compound and serves as a good reference for constructing efficient and low-cost electrocatalysts.     

Layered double (Ni,Fe) hydroxide grown on nickel foam and modified by nickel carbonyl powder and carbon black as an efficient electrode for water splitting

Developing novel oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts is vital for water splitting. Here, carbon black (CB) and nickel carbonyl powder (NCP) are used as components, and the nonionic surfactant polyvinyl pyrrolidone (PVP) is used as a shape-controlled capping agent to easily prepare layered double (Ni, Fe) hydroxide (NiFe-LDH) electrodes. Scanning electron microscopy observation and X-ray photoelectron spectra analysis show that the Fe²⁺-doped layered double hydroxide is grown in situ on nickel foam (NF). CB (XC-72) and NCP further improve the electrical conductivity. At 10 mA?cm^?2, the overpotentials of the OER and HER are 203 mV and 83 mV, respectively, in 1 M KOH. Only 1.48 V is needed when both electrodes are applied for water splitting, and it has a stability of more than 100 h. This work can be used as a medium to elevate the OER and HER performance of NiFe-LDH-based catalysts.     

Synthesis of MoS2 nanoparticles embedded,N, S co-doped mesoporous carbon via molten salt method as hydrogen evolution electrocatalyst under alkaline and neutral conditions

We developed a salt-template strategy to prepare MoS₂ nanoparticles (NPs) embedded, N, S co-doped carbons via the solid-state process. The addition of the inorganic salt played two main roles in the synthetic proceeding. First, the salts could be utilized as the templates to produce the mesopores, which could be removed by simple washing process. Second, the salts could promote the formation of MoS₂ NPs. The as-received electrocatalyst, K-G4.0T2.0Mo1.0, possessed high BET surface area of 446 m² g^?1, in addition to high double layer capacitance of 24.5 mF cm^?2 in the alkaline media. When evaluated as the electrocatalyst for hydrogen evolution reaction (HER), K-G4.0T2.0Mo1.0 demonstrated excellent performance in the alkaline and neutral medias. In details, K-G4.0T2.0Mo1.0 showed a low overpotential of 173 and 358 mV to afford 10 mA cm^?2 under alkaline and neutral conditions, respectively, as well as outstanding durability.     

High-efficiency synthesis of Co,N-doped carbon nanocages by ball milling-hard template method as an active catalyst for oxygen reduction reaction

A facile and scalable method is developed for the high-efficiency synthesis of Co, N-doped carbon nanocages catalyst for the oxygen reduction reaction (ORR). During the synthesis, the precursors are uniformly distributed on the surface of potassium chloride (KCl) by high-energy ball milling. As evidenced, the N and Co elements are successfully doped and distributed uniformly on the surface of carbon nanocages. Owing to the distinctive nanocage architecture and the synergistic effects of Co, N and Co-N_X coordination, the obtained Co, N–CNC-800 shows efficient ORR catalytic activity with an onset potential of 0.924 V (vs. RHE), and the number of electron transfer (n) is approximately 3.4. Furthermore, its stability and methanol tolerance are far superior to those of commercial 40% Pt/C. This simple and universal synthesis strategy is expected to be widely applied in the preparation of other heteroatom-doped carbon nanocages as catalysts in hydrogen fuel cells.     

Greatly improved HER electrocatalytic activity by the composite of CoSe2 and N,S-dual doped graphitic carbon

Several composite catalysts were facilely fabricated by hydrothermal supporting CoSe₂ on N, S dual-doped graphitic mesoporous carbon (SDGC) synthesized by pyrolyzing thiocarbamide and in-situ formed phenolic resin. The synthesized CoSe₂/SDGC composites were characterized to have mesoporous structure distributed on the carbon matrix covered with the sphere like aggregates of CoSe₂. Their electrocatalytic performances were evaluated by hydrogen evolution reaction (HER) in 0.5 M H₂SO₄. The results have shown that the as-prepared catalysts exhibited highly improved electrocatalytic activities for HER compared with the pristine CoSe₂ and SDGC. Especially, the composite CoSe₂/SDGC-60 with the optimized ratio of CoSe₂ to SDGC has exhibited the highest electrocatalytic activity. The catalyst has obtained the lowest overpotential and Tafel slope of 203 mV (at 10 mA/cm²) and 58 mV/dec, respectively. It also showed impressive durability against 0.5 M H₂SO₄ and the electrocatalytic activity hardly decreased even after 5000 cycles.     

Fabrication and characterization of NiCoZn-M (M: Ag, Pd and Pt) electrocatalysts as cathode materials for electrochemical hydrogen production

Ag, Pd and Pt-modified alkaline leached NiCoZn composite coatings were prepared on a copper specimen by electrochemical technique. The chemical composition of layers before and after leaching as well as after noble metal modification was determined by energy dispersive X-ray spectroscopy (EDX). The surface morphologies of the composite coatings were examined with the help of scanning electron microscopy (SEM). The hydrogen evolution activity of the electrodes was studied in 1 M KOH solution. For this purpose, cathodic current-potential curves and electrochemical impedance spectroscopy (EIS) techniques were used. Furthermore, the change of hydrogen evolution activity of the electrodes as a function of operation time in alkaline solution was also investigated. Surface morphologies showed that the composite coatings prepared to have compact and porous surface. EDX analysis confirmed the presence of Ag, Pd and Pt metals over the NiCoZn layer. The co-deposition of nickel, cobalt and zinc on copper surface and subsequently alkaline leaching of zinc rendered cathode material very active in hydrogen evolution. The modification of alkaline leached NiCoZn ternary coating by deposition of small amounts of Ag, Pd and Pt can further enhance the hydrogen evolution performance of this Raney-type electrode when compared to NiCoZn individually. The order of hydrogen evolution activity of catalysts studied is Ni < NiCoZn < NiCoZn-Pd < NiCoZn-Ag < NiCoZn-Pt. The long-term electrolysis tests showed that the Pt-modified electrode has the better time stability than the others. The superiority of Pt-modified catalyst explained by well known intrinsic catalytic activity of Pt.     

Self-assembly synthesis of Ru nanoparticles anchored on B,N co-doping carbon support for hydrogen evolution: Electronic state induced by the strong metal-support interactions

The strong metal-support interactions between metal and its support have been considered as an effective way to improve the electrocatalytic activity in heterogeneous catalysis, which can modulate metal d-band's energy level and, consequently, affect the adsorption/desorption of the intermediates on the metal nanoparticle's surface. In this paper, we use a self-assembly strategy for construction nano-sized Ru nanoparticles (NPs) anchored on B, N co-doping carbon nanorod carrier (Ru/BCN) as HER catalyst by using unique boron cluster-organic framework as precursor and self-sacrificing templates. This supramolecular framework forming with cucurbit [6]uril as the host and closo-[B₁₂H₁₂]^2- as the guest can feature unique hexagonal nanorod morphology to confine the Ru NPs into framework through weak reductivity of closo-[B₁₂H₁₂]^2-. After pyrolysis, the strong metal-support interactions between B, N co-doping carbon support (BCN) and Ru NPs have been found due to the synergistic coupling effect of co-dopants B and N, which can increase electron transfer between the metal nanoparticle and support. The overpotentials of 33 mV and 40 mV are required for as-prepared catalyst Ru/BCN to achieve a current density of 10 mA cm^?2 in alkaline and acidic conditions, respectively, which are approximately one third of those of Ru/CN. These findings demonstrate that our synthetic way offers a potential route for fabricating co-doping carbon with B and N atoms to support Ru NPs with enhanced HER performance in pH-independent conditions.     

Design study of an AnSBBR for hydrogen production by co-digestion of whey with glycerin: Interaction effects of organic load,cycle time and feed strategy

An anaerobic sequencing batch biofilm reactor (AnSBBR) treating a mixture of dairy industry wastewater and biodiesel production wastewater (co-digestion of whey with glycerin) was applied to hydrogen production. The influence of fed-batch and batch mode, cycle time and interactions effects between influent concentration and cycle time (2, 3 and 4 h) over the organic loading rate were assessed in order to obtain a sensitivity analysis for important operational variables to the reactor. It was possible to find an optimal cycle time of 3 h with an influent concentration of 7000 mgCOD L^?1 (molar productivity 129.0 molH₂ m^?3 d^?1 and yield 5.4 molH₂ kgCOD^?1). Reactor operation in fed-batch mode allowed higher hydrogen production rates. Increasing the influent concentration (with a constant cycle time) was better for the hydrogen production process than decreasing the cycle length (with a constant influent concentration), which means that these two parameters have different weights in the organic loading rate. The best operational conditions produce hydrogen via acetic, butyric and valeric acids similarly. The system is able to produce 1.3 kJ per gram of COD applied.