Project description:Platinum-based alloys with low cost transition metals have been considered as promising electrocatalysts in the field of sustainable energy conversion and storage. Herein, chloroplatinic acid, cobalt chloride, and carbon nanotubes are used as platinum, cobalt precursors, and carriers, respectively, to prepare rich Pt dealloying PtCo nanoparticles (SD-PtCo/CNT) via co-liquid phase reduction and chemical dealloying methods. The characterization and test results confirm that PtCo alloy nanoparticles are evenly dispersed on carbon nanotubes, further dealloying and resulting in the partial dissolving of cobalt, simultaneously generating a rich Pt layer and roughly active surface. Benefiting from the unique structure, the SD-PtCo/CNT catalyst displays obviously enhanced HER activity in both acidic and alkaline conditions. In 1.0 M KOH, SD-PtCo/CNT exhibits a low overpotential of 78 mV at 10 mA/cm2 and a small tafel slope (38.28 mV/dec). In 0.5 M H2SO4, SD-PtCo/CNT still shows the superior performance compared with un-dealloying PtCo/CNT, with an overpotential of 17 mV at 10 mA/cm2 and corresponding tafel slope of 21.35 mV/dec. The high HER activity of SD-PtCo/CNT can be attributed to the formation of a platinum rich layer and the uniformly dispersed PtCo nanoparticles supported on superior conductive carbon nanotubes, suggesting its great potential for hydrogen generation via water splitting.
Project description:The oxygen evolution reaction (OER) underpins many aspects of energy storage and conversion in modern industry and technology, but which still be suffering from the dilemma of sluggish reaction kinetics and poor electrochemical performance. Different from the viewpoint of nanostructuring, this work focuses on an intriguing dynamic orbital hybridization approach to renormalize the disordering spin configuration in porous noble-metal-free metal-organic frameworks (MOFs) to accelerate the spin-dependent reaction kinetics in OER. Herein, we propose an extraordinary super-exchange interaction to reconfigure the domain direction of spin nets at porous MOFs through temporarily bonding with dynamic magnetic ions in electrolytes under alternating electromagnetic field stimulation, in which the spin renormalization from disordering low-spin state to high-spin state facilitates rapid water dissociation and optimal carrier migration, leading to a spin-dependent reaction pathway. Therefore, the spin-renormalized MOFs demonstrate a mass activity of 2,095.1 A gmetal-1 at an overpotential of 0.33 V, which is about 5.9 time of pristine ones. Our findings provide a insight into reconfiguring spin-related catalysts with ordering domain directions to accelerate the oxygen reaction kinetics.
Project description:Single-atom-catalysts (SACs) afford a fascinating activity with respect to other nanomaterials for hydrogen evolution reaction (HER), yet the simplicity of single-atom center limits its further modification and utilization. Obtaining bimetallic single-atom-dimer (SAD) structures can reform the electronic structure of SACs with added atomic-level synergistic effect, further improving HER kinetics beyond SACs. However, the synthesis and identification of such SAD structure remains conceptually challenging. Herein, systematic first-principle screening reveals that the synergistic interaction at the NiCo-SAD atomic interface can upshift the d-band center, thereby, facilitate rapid water-dissociation and optimal proton adsorption, accelerating alkaline/acidic HER kinetics. Inspired by theoretical predictions, we develop a facile strategy to obtain NiCo-SAD on N-doped carbon (NiCo-SAD-NC) via in-situ trapping of metal ions followed by pyrolysis with precisely controlled N-moieties. X-ray absorption spectroscopy indicates the emergence of Ni-Co coordination at the atomic-level. The obtained NiCo-SAD-NC exhibits exceptional pH-universal HER-activity, demanding only 54.7 and 61 mV overpotentials at -10 mA cm-2 in acidic and alkaline media, respectively. This work provides a facile synthetic strategy for SAD catalysts and sheds light on the fundamentals of structure-activity relationships for future applications.
Project description:Silicon photocathodes coated with drop-casted {Mo3S4}-based polyoxothiometalate assemblies are demonstrated to be effective for sunlight-driven hydrogen evolution reaction (HER) in acid conditions. These photocathodes are catalytically more efficient than that coated with the parent thiomolybdate incorporating an organic ligand, as supported by a higher onset potential and a lower overvoltage at 10 mA cm-2. At pH 7.3, the trend is inversed and the beneficial effect of the polyoxometalate for the HER is not observed. Moreover, the polyoxothiometalate-modified photocathode is found to be also more stable under acid conditions and can be operated at the light-limited catalytic current for more than 40 h. Furthermore, X-ray photoelectron spectroscopy and atomic force microscopy measurements indicate that the cathodic polarization of both photocathodes leads to the release of a large amount of the deposited material into the electrolyte solution concomitantly with the formation of mixed valence species {Mo(IV)3-x Mo(III) x O4-n S n }(4-x)+ resulting from the replacement of S2- sulfido ligands in the cluster by oxo O2- groups; these combined effects are shown to be beneficial for the photoelectrocatalysis.
Project description:Interface confined reactions, which can modulate the bonding of reactants with catalytic centres and influence the rate of the mass transport from bulk solution, have emerged as a viable strategy for achieving highly stable and selective catalysis. Here we demonstrate that 1T'-enriched lithiated molybdenum disulfide is a highly powerful reducing agent, which can be exploited for the in-situ reduction of metal ions within the inner planes of lithiated molybdenum disulfide to form a zero valent metal-intercalated molybdenum disulfide. The confinement of platinum nanoparticles within the molybdenum disulfide layered structure leads to enhanced hydrogen evolution reaction activity and stability compared to catalysts dispersed on carbon support. In particular, the inner platinum surface is accessible to charged species like proton and metal ions, while blocking poisoning by larger sized pollutants or neutral molecules. This points a way forward for using bulk intercalated compounds for energy related applications.
Project description:Hot electrons generated on metal catalysts influence atomic and molecular processes, leading to hot electron-driven catalytic reactions. Here, we show the acceleration of electrocatalytic hydrogen evolution caused by internal injection of hot electrons on Pt/Si metal-semiconductor electrodes. When a forward bias voltage is applied to the Pt/Si contact, hot electrons are injected. The excess energy of these electrons allows them to reach the Pt/electrolyte interface and reduce the adsorbed hydrogen ions to form H2 (2H+ + 2e-→H2). We show that the onset potential of the hydrogen evolution reaction shifts positively by 160 mV while the cathodic current exhibits an 8-fold increase in the presence of hot electrons. The effect disappears when the thickness of the Pt film exceeds the mean free path of the hot electrons. The concept of a hot electron-driven reaction can lead to the development of a novel mechanism for controlling reactivity at liquid-solid interfaces.
Project description:Developing advanced catalysts with rapid hydrogen evolution reaction (HER) kinetics in alkaline media is vital for hydrogen production. Through the d-p orbital hybridization effect, the electronic structure and H* adsorption can be optimized on metal species. Herein, a N-doped hollow carbon (H-NPC)-supported Ru cluster (c-Ru@H-NPC) catalyst was constructed via carbonization of well-defined hollow metal-organic frameworks, followed by etching and anchoring of Ru clusters. The hollow structure could not alter the coordination number of Ru while exhibiting higher-level electron transfer, thereby strengthening the orbital hybridization. Additionally, finite element simulations indicated the acceleration of H2 diffusion for hollow structures. Furthermore, the N-doping strengthened the electron interaction of Ru-C by the d-p hybridization effect, which was confirmed by theoretical calculations and in situ Raman spectroscopy. Therefore, in alkaline/alkaline seawater media, c-Ru@H-NPC needed only 10/12 mV overpotentials and 1.52/1.55 V cell voltages to drive the HER and overall water splitting, respectively, at a current density of 10 mA cm-2, exhibiting outstanding catalytic activity. Meanwhile, the attenuation of current density was very small towards successive stability tests for >55 h at 10 mA cm-2. This work permits new insights into the design of high-performance metal cluster catalysts for the HER and other conversion reactions.
Project description:Exploring the economical, powerful, and durable electrocatalysts for hydrogen evolution reaction (HER) is highly required for practical application. Herein, nanoclusters-decorated ruthenium, cobalt nanoparticles, and nitrogen codoped porous carbon (Ru-pCo@NC) are prepared with bimetallic zeolite imidazole frameworks (ZnCo-ZIF) as the precursor. Thus, the prepared Ru-pCo@NC catalyst with a low Ru loading of 3.13 wt% exhibits impressive HER catalytic behavior in 1 M KOH, with an overpotential of only 30 mV at the current density of 10 mA cm-2, Tafel slope as low as 32.1 mV dec-1, and superior stability for long-time running with a commercial 20 wt% Pt/C. The excellent electrocatalytic properties are primarily by virtue of the highly specific surface area and porosity of carbon support, uniformly dispersed Ru active species, and rapid reaction kinetics of the interaction between Ru and O.
Project description:Seawater splitting represents an inexpensive and attractive route for producing hydrogen, which does not require a desalination process. Highly active and durable electrocatalysts are required to sustain seawater splitting. Herein we report the phosphidation-based synthesis of a cobalt-iron-phosphate ((Co,Fe)PO4) electrocatalyst for hydrogen evolution reaction (HER) toward alkaline seawater splitting. (Co,Fe)PO4 demonstrates high HER activity and durability in alkaline natural seawater (1 M KOH + seawater), delivering a current density of 10 mA/cm2 at an overpotential of 137 mV. Furthermore, the measured potential of the electrocatalyst ((Co,Fe)PO4) at a constant current density of -100 mA/cm2 remains very stable without noticeable degradation for 72 h during the continuous operation in alkaline natural seawater, demonstrating its suitability for seawater applications. Furthermore, an alkaline seawater electrolyzer employing the non-precious-metal catalysts demonstrates better performance (1.625 V at 10 mA/cm2) than one employing precious metal ones (1.653 V at 10 mA/cm2). The non-precious-metal-based alkaline seawater electrolyzer exhibits a high solar-to-hydrogen (STH) efficiency (12.8%) in a commercial silicon solar cell.
Project description:Photocatalytic hydrogen production from water is a promising way to fulfill energy demands and attain carbon emission reduction goals effectively. In this study, a loop photoreactor with a total volume of around 500 mL is presented for the photocatalytic hydrogen evolution using a Pt-loaded polymeric carbon nitride photocatalyst under 365 nm irradiation in the presence of sacrificial reducing agents. The fluid flow pattern of the developed photoreactor was characterized experimentally and the photon flux incident to the loop photoreactor was measured by chemical actinometry. The system displayed exceptional stability, with operation sustained over 70 hours. A design of experiment (DOE) analysis was used to systematically investigate the influence of key parameters - photon flux, photocatalyst loading, stirring speed, and inert gas flow rate - on the hydrogen generation rate. Linear relationships were found between hydrogen evolution rate and photon flux as well as inert gas flow rate. Photocatalyst loading and stirring speed also showed linear correlations, but could not be correctly described by DOE analysis. Instead, linear single parameter correlations could be applied. Notably, the loop photoreactor demonstrated an external photon efficiency up to 17 times higher than reported in literature studies, while scaling the reactor size by a factor of 10.