Project description:Water is the only available fossil-free source of hydrogen. Splitting water electrochemically is among the most used techniques, however, it accounts for only 4% of global hydrogen production. One of the reasons is the high cost and low performance of catalysts promoting the oxygen evolution reaction (OER). Here, we report a highly efficient catalyst in acid, that is, solid-solution Ru‒Ir nanosized-coral (RuIr-NC) consisting of 3 nm-thick sheets with only 6 at.% Ir. Among OER catalysts, RuIr-NC shows the highest intrinsic activity and stability. A home-made overall water splitting cell using RuIr-NC as both electrodes can reach 10 mA cm-2geo at 1.485 V for 120 h without noticeable degradation, which outperforms known cells. Operando spectroscopy and atomic-resolution electron microscopy indicate that the high-performance results from the ability of the preferentially exposed {0001} facets to resist the formation of dissolvable metal oxides and to transform ephemeral Ru into a long-lived catalyst.
Project description:The development of high-performance and cost-effective earth-abundant transition metal-based electrocatalysts is of major interest for several key energy technologies, including water splitting. Herein, we report the synthesis of ultrathin CoMoP nanosheets through a simple ion etching and phosphorization method. The obtained catalyst exhibits outstanding electrocatalytic activity and stability towards oxygen and hydrogen evolution reactions (OER and HER), with overpotentials down to 273 and 89 mV at 10 mA cm-2, respectively. The produced CoMoP nanosheets are also characterized by very small Tafel slopes, 54.9 and 69.7 mV dec-1 for OER and HER, respectively. When used as both cathode and anode electrocatalyst in the overall water splitting reaction, CoMoP-based cells require just 1.56 V to reach 10 mA cm-2 in alkaline media. This outstanding performance is attributed to the proper composition, weak crystallinity and two-dimensional nanosheet structure of the electrocatalyst.
Project description:Electrochemical water splitting is one of the potential commercial techniques to produce clean hydrogen energy because of the high efficiency and environmental friendliness. However, development of low-cost bifunctional electrocatalysts that can replace Pt-based catalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is challenging. Herein, Co nanoparticles (NPs) are anchored on MoO2 nanosheets (Co/MoO2) by thermal reduction of the CoMoO4 nanosheet array in Ar/H2. The uniformly distributed Co NPs improve the electron transfer capability and modulate the surface states of the MoO2 nanosheets to enhance hydrogen desorption and HER kinetics. Moreover, the Co/MoO2 composite is beneficial to the interfacial structure and the MoO2 nanosheets prevent aggregation of Co NPs to improve the intrinsic OER characteristics in the alkaline electrolyte. As a result, the Co/MoO2 electrocatalyst shows low HER and OER overpotentials of 178 and 318 mV at a current density of 10 mA cm-2 in 1 M KOH. The electrolytic cell consisting of the bifunctional Co/MoO2 electrodes shows a small voltage of 1.72 V for a current density of 10 mA cm-2 in overall water splitting.
Project description:While dye-sensitized metal oxides are good candidates as H2 evolution photocatalysts for solar-driven Z-scheme water splitting, their solar-to-hydrogen (STH) energy conversion efficiencies remain low because of uncontrolled charge recombination reactions. Here, we show that modification of Ru dye-sensitized, Pt-intercalated HCa2Nb3O10 nanosheets (Ru/Pt/HCa2Nb3O10) with both amorphous Al2O3 and poly(styrenesulfonate) (PSS) improves the STH efficiency of Z-scheme overall water splitting by a factor of ~100, when the nanosheets are used in combination with a WO3-based O2 evolution photocatalyst and an I3-/I- redox mediator, relative to an analogous system that uses unmodified Ru/Pt/HCa2Nb3O10. By using the optimized photocatalyst, PSS/Ru/Al2O3/Pt/HCa2Nb3O10, a maximum STH of 0.12% and an apparent quantum yield of 4.1% at 420 nm were obtained, by far the highest among dye-sensitized water splitting systems and comparable to conventional semiconductor-based suspended particulate photocatalyst systems.
Project description:Designing and constructing bifunctional electrocatalysts is vital for water splitting. Particularly, the rational interface engineering can effectively modify the active sites and promote the electronic transfer, leading to the improved splitting efficiency. Herein, free-standing and defect-rich heterogeneous MoS2/NiS2 nanosheets for overall water splitting are designed. The abundant heterogeneous interfaces in MoS2/NiS2 can not only provide rich electroactive sites but also facilitate the electron transfer, which further cooperate synergistically toward electrocatalytic reactions. Consequently, the optimal MoS2/NiS2 nanosheets show the enhanced electrocatalytic performances as bifunctional electrocatalysts for overall water splitting. This study may open up a new route for rationally constructing heterogeneous interfaces to maximize their electrochemical performances, which may help to accelerate the development of nonprecious electrocatalysts for overall water splitting.
Project description:The oriented two-dimensional porous nitrogen-doped carbon embedded with CoS2 and MoS2 nanosheets is a highly efficient bifunctional electrocatalyst. The hierarchical structure ensures fast mass transfer capacity in improving the electrocatalytic activity. And the greatly increased specific surface area is beneficial to expose more electrocatalytically active atoms. For oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) tests in 1 mol/L KOH solution, only 194 and 140 mV overpotential are required to achieve a current density of 10 mA/cm2, respectively. Our research provides an effective strategy for synergizing the individual components in nanostructures for a wide range of electrocatalytic reactions.
Project description:The exploration of low-cost and efficient bifunctional electrocatalysts for oxygen evolution reaction and hydrogen evolution reaction through tuning the chemical composition is strongly required for sustainable resources. Herein, we developed a bimetallic cobalt-manganese sulfide supported on Ni foam (CMS/Ni) via a solvothermal method. It has discovered that after combining with the pure Co9S8 and MnS, the morphologies of CMS/Ni have modulated. The obtained three-dimensionally hexagram-like CMS/Ni nanosheets have a significant increase in electrochemical active surface area and charge transport ability. More than that, the synergetic effect of Co and Mn has also presented in this composite. Benefiting from these, the CMS/Ni electrode shows great performance toward hydrogen evolution reaction and oxygen evolution reaction in basic medium, comparing favorably to that of the pure Co9S8/Ni and MnS/Ni. More importantly, this versatile CMS/Ni can catalyze the water splitting in a two-electrode system at a potential of 1.47 V, and this electrolyzer can be efficiently driven by a 1.50 V commercial dry battery.
Project description:A nanoscale core-shell NiO@CoO composite is prepared on flexible carbon cloth for electrodes in supercapacitors and overall water splitting. The needle-like CoO nanowires with NiO nanosheets as the active materials improve the elemental constituents as well as surface area. The NiO@CoO electrode boasts a capacity of 2.87 F cm-2 (1024.05 F g-1) at 1 A g-1 current density, and even at a large current density of 20 A g-1 the retention ratio is 80.9% after 5000 cycles. The excellent specific capacity with high rate capability can be ascribed to the unique structure which increases the area of the liquid-solid interface and facilitates electron and ion transport, improving the utilization efficiency of active materials. The asymmetric hybrid supercapacitor prepared with the core-shell electrode shows the energy output of 40.3 W h kg-1 at 750 W kg-1 with a better retention (71.7%) of specific capacitance after 15 000 cycles. In addition, linear sweep voltammetry is performed to assess the performance of the electrode in water splitting and the electrode shows excellent activity in the OER as manifested by a Tafel slope of 88.04 mV dec-1. Our results show that the bifunctional structure and design strategy have large potential in energy applications.
Project description:Unique metal sulfide (MS) clusters embedded ultrathin nanosheets of Fe/Ni metal-organic framework (MOF) are grown on nickel foam (NiFe-MS/MOF@NF) as a highly efficient bifunctional electrocatalyst for overall water splitting. It exhibits remarkable catalytic activity and stability toward both the oxygen evolution reaction (OER, ? = 230 mV at 50 mA cm-2) and hydrogen evolution reaction (HER, ? = 156 mV at 50 mA cm-2) in alkaline media, and bi-functionally catalyzes overall alkaline water splitting at a current density of 50 mA cm-2 by 1.74 V cell voltage without iR compensation. The enhancement mechanism is ascribed to the impregnated metal sulfide clusters in the nanosheets, which not only promote the formation of ultrathin nanosheet to greatly enlarge the reaction surface area while offering high electric conductivity, but more importantly, efficiently modulate the electronic structure of the catalytically active atom sites to an electron-rich state via strong electronic interaction and strengthen the adsorption of oxygenate intermediate to facilitate fast electrochemical reactions. This work reports a highly efficient HER/OER bifunctional electrocatalyst and may shed light on the rational design and synthesis of uniquely structured MOF-derived catalysts.
Project description:Engineering surface structure of catalysts is an efficient way towards high catalytic performance. Here, we report on the synthesis of regular iridium nanospheres (Ir NSs), with abundant atomic steps prepared by a laser ablation technique. Atomic steps, consisting of one-atom level covering the surface of such Ir NSs, were observed by aberration-corrected high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM). The prepared Ir NSs exhibited remarkably enhanced activity both for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in acidic medium. As a bifunctional catalyst for overall water splitting, they achieved a cell voltage of 1.535 V @ 10 mA/cm2, which is much lower than that of Pt/C-Ir/C couple (1.630 V @ 10 mA/cm2).