| 1. |
- Li, Fusheng, 1985-, et al.
(author)
-
Electroless Plating of NiFeP Alloy on the Surface of Silicon Photoanode for Efficient Photoelectrochemical Water Oxidation
- 2020
-
In: ACS Applied Materials and Interfaces. - : American Chemical Society (ACS). - 1944-8244 .- 1944-8252. ; 12:10, s. 11479-11488
-
Journal article (peer-reviewed)abstract
- N- type silicon is a kind of semiconductor with a narrow band gap that has been reported as an outstanding light-harvesting material for photoelectrochemical (PEC) reactions. Decorating a thin catalyst layer on the n-type silicon surface can provide a direct and effective route toward PEC water oxidation. However, most of catalyst immobilization methods for reported n-type silicon photoanodes have been based on energetically demanding, time-consuming, and high-cost processes. Herein, a high-performance NiFeP alloy (NiFeP)-decorated n-type micro-pyramid silicon array (n-Si) photoanode (NiFeP/n-Si) was prepared by a fast and low-cost electroless deposition method for light-driven water oxidation reaction. The saturated photocurrent density of NiFeP/n-Si can reach up to similar to 40 mA cm(-2) and a photocurrent density of 15.5 mA cm(-2) can be achieved at 1.23 V-RHE under light illumination (100 mW cm(-2), AM1.5 filter), which is one of the most promising silicon-based photoanodes to date. The kinetic studies showed that the NiFeP on the silicon photoanodes could significantly decrease the interfacial charge recombination between the n-type silicon surface and electrolyte.
|
|
| 2. |
- Daniel, Quentin, et al.
(author)
-
Rearranging from 6-to 7-coordination initiates the catalytic activity : An EPR study on a Ru-bda water oxidation catalyst
- 2017
-
In: Coordination chemistry reviews. - : Elsevier. - 0010-8545 .- 1873-3840. ; 346, s. 206-215
-
Journal article (peer-reviewed)abstract
- The coordination of a substrate water molecule on a metal centered catalyst for water oxidation is a crucial step involving the reorganization of the ligand sphere. This process can occur by substituting a coordinated ligand with a water molecule or via a direct coordination of water onto an open site. In 2009, we reported an efficient ruthenium-based molecular catalyst, Ru-bda, for water oxidation. Despite the impressive improvement in catalytic activity of this type of catalyst over the past years, a lack of understanding of the water coordination still remains. Herein, we report our EPR and DFT studies on Ru-bda (triethylammonium 3-pyridine sulfonate)(2) (1) at its Ru-III oxidation state, which is the initial state in the catalytic cycle for the O-O bond formation. Our investigation suggests that at this III-state, there is already a rearrangement in the ligand sphere where the coordination of a water molecule at the 7th position (open site) takes place under acidic conditions (pH = 1.0) to form a rare 7-coordinated Ru-III species.
|
|
| 3. |
- Daniel, Quentin, et al.
(author)
-
Water Oxidation Initiated by In Situ Dimerization of the Molecular Ru(pdc) Catalyst
- 2018
-
In: ACS Catalysis. - : AMER CHEMICAL SOC. - 2155-5435. ; 8:5, s. 4375-4382
-
Journal article (peer-reviewed)abstract
- The mononuclear ruthenium complex [Ru(pdc)L-3] (H(2)pdc = 2,6-pyridinedicarboxylic acid, L = N-heterocycles such as 4-picoline) has previously shown promising catalytic efficiency toward water oxidation, both in homogeneous solutions and anchored on electrode surfaces. However, the detailed water oxidation mechanism catalyzed by this type of complex has remained unclear. In order to deepen understanding of this type of catalyst, in the present study, [Ru(pdc)(py)(3)] (py = pyridine) has been synthesized, and the detailed catalytic mechanism has been studied by electrochemistry, UV-vis, NMR, MS, and X-ray crystallography. Interestingly, it was found that once having reached the Ru-IV state, this complex promptly formed a stable ruthenium dimer [Ru-III(pdc)(py)(2)-O-Ru-IV(pdc)(py)(2)](+). Further investigations suggested that the present dimer, after one pyridine ligand exchange with water to form [Ru-III(pdc)(py)(2)-O-Ru-IV(pdc)(py)(H2O)](+), was the true active species to catalyze water oxidation in homogeneous solutions.
|
|
| 4. |
- Li, Fusheng, 1985-, et al.
(author)
-
Control the O-O bond formation pathways by immobilizing molecular catalysts on glassy carbon via electrochemical polymerization
-
Other publication (other academic/artistic)abstract
- Molecular water oxidation catalysts Ru-bda (1) and Ru-pda (2) are electrochemically polymerized on glassy carbon (GC) electrodes. Reaction orders and kinetic isotope effects (KIE) of the corresponding electrodes are studied. Results indicate that poly-1@GC goes through a radical coupling pathway. By adding poly-styrene (PSt) as a “blocking unit” in the poly-1, the radical coupling process of Ru-bda is blocked, and poly-1+PSt@GC catalyzes water oxidation through the water nucleophilic attack pathway. In comparison, catalyst 2, which oxidizes water via water nucleophilic attack path in homogeneous systems, goes through a radical coupling pathway as well when 2 is polymerized on glassy carbon (poly-2@GC).
|
|
| 5. |
- Li, Fusheng, 1985-
(author)
-
Design of Water Splitting Devices via Molecular Engineering
- 2016
-
Doctoral thesis (other academic/artistic)abstract
- Converting solar energyto fuels such as hydrogen by the reaction of water splitting is a promising solution for the future sustainable energy systems. The theme of this thesis is to design water splitting devices via molecular engineering; it concerns the studies of both electrochemical-driven and photo-electrochemical driven molecular functional devices for water splitting.The first chapter presents a general introduction about Solar Fuel Conversion. It concerns molecular water splitting catalysts, light harvesting materials and fabrication methods of water splitting devices.The second chapter describes an electrode by immobilizing a molecular water oxidation catalyston carbon nanotubes through the hydrophobic interaction. This fabrication method is corresponding to the question: “How to employ catalysts in functional devices without affecting their performances?”In the third chapter, molecular water oxidation catalysts were successfully immobilized on glassy carbon electrode surface via electrochemical polymerization method. The O-O bond formation pathways of catalysts on electrode surfaces were studied. This kinetic studyis corresponding to the question: “How to get kinetic information of RDS whena catalyst is immobilized on the electrode surface?” Chapter four explores molecular water oxidation catalysts immobilized on dye-sensitized TiO2 electrodeand Fe2O3 semiconductor electrode via different fabrication methods. The reasons of photocurrent decay are discussed and two potential solutions are provided. These studies are corresponding to the question: “How to improvethe stability of photo-electrodes?”Finally, in the last chapter, two novel Pt-free Z-schemed molecular photo-electrochemical cells with both photoactive cathode and photoactive anode for visible light driven water splitting driven were demonstrated. These studies are corresponding to the question: “How to utilizethe concept of Z-schemein photosynthesis to fabricate Pt-free molecular based PEC cells?
|
|
| 6. |
- Zhang, Peili, et al.
(author)
-
Gas-templating of hierarchically structured Ni-Co-P for efficient electrocatalytic hydrogen evolution
- 2017
-
In: Journal of Materials Chemistry A. - : ROYAL SOC CHEMISTRY. - 2050-7488 .- 2050-7496. ; 5:16, s. 7564-7570
-
Journal article (peer-reviewed)abstract
- One of the grand challenges for developing scalable and sustainable hydrogen producing systems is the lack of efficient and robust earth-abundant element based catalysts for the hydrogen evolution reaction (HER). Herein, a hierarchically structured Ni-Co-P film was fabricated via a gas templating electro-deposition method. This film exhibits remarkably high catalytic performance for the HER in 1 M KOH with respective current densities of -10 and -500 mA cm(-2) at the overpotentials of -30 and -185 mV with a Tafel slope of 41 mV dec(-1). A controlled potential electrolysis experiment demonstrates that the as-prepared Ni-Co-P film is an efficient and robust catalyst with a faradaic efficiency close to 100%. Systematic characterization suggests that the unique hierarchical structure and the mutual participation of nano-sized Ni/Co based components are responsible for the high HER catalytic activity.
|
|
