ABSTRACT
Electrocatalytic hydrogen evolution reaction (HER) is regarded as a sustainable and green way for H2 generation, which faces a great challenge in designing highly active, stable electrocatalysts to replace the state-of-art noble metal-platinum catalysts. 1T MoS2 is highly promising in this regard, but the synthesis and stability of this is a particularly pressing task. Here, a phase engineering strategy has been proposed to achieve a stable, high-percentage (88%) 1T MoS2 /chlorophyll-a hetero-nanostructure, through a photo-induced donation of anti-bonding electrons from chlorophyll-a (CHL-a) highest occupied molecular orbital to 2H MoS2 lowest unoccupied molecular orbital. The resultant catalyst has abundant binding sites provided by the coordination of magnesium atom in the CHL-a macro-cycle, featuring higher binding strength and low Gibbs-free energy. This metal-free heterostructure exhibits excellent stability via band renormalization of Mo 4d orbital which creates the pseudogap-like structure by lifting the degeneracy of projected density of state with 4S in 1T MoS2 . It shows extremely low overpotential, toward the acidic HER (68 mV at the current density of 10 mA cm-2 ), very close to the Pt/C catalyst (53 mV). The high electrochemical-surface-area and electrochemical turnover frequency support enhanced active sites along with near zero Gibbs free energy. Such a surface-reconstruction strategy provides a new avenue toward the production of efficient non-noble-metal-catalysts for the HER with the aim of green-hydrogen production.
ABSTRACT
Self-assembly of chlorophyll-a (Chl-a) molecules within a protein environment serves as the key factor behind controlled and efficient light energy harvesting in natural photosystems. Long-range ordering among supramolecular structures in terms of spin-orbit coupling and edge effect helps in untrapping of excitons in the disordered energy landscape. Mimicking the photosynthetic machinery would give a new paradigm for organic photovoltaic material design where a large amount of disorder exists. In this paper, we report the experimental evidence of room temperature magnetic domain wall formation and edge effect along with spin flop canting in self-assembled Chl-a within hydrogel matrix via SQUID magnetometry. This was further correlated with intermolecular coupling and exciton delocalization through specific arrangements of self-assembly as evident from NMR spectral and photophysical characteristics. The data cumulatively suggest electronic backscattering protection which is also substantiated by the ferroelectric behavior coming from coexisting symmetry lowering. Here the polarization evolves through primary distribution of π electronic density along with a photoresponsive IV loop, similar to the photoprotection of photosynthesis. This work thus proposes a promising design principle for room temperature Chl-a based biomimetic systems efficient in photoharnessing.
ABSTRACT
Biomimetic photo harvesting architecture has been proposed as an alternative for existing solar conversion systems. This fact led us to the successful realization of non-coherent electron hopping [hopping rate 4.28 ns(-1)] through excitonically coupled Chlorophyll-a (Chl-a) molecules within chitosan hydrogel matrix via TCSPC (Time Correlated Single Photon Count) and fluorescence anisotropy measurements. Chl-a molecules remain stable within the hydrogel matrix up to 3 months, as evidenced from UV-vis spectroscopy. The mono-exponential decay parameter with 78 picoseconds time scale, high initial anisotropy data [r0 = 0.33] and with reduced TCSPC lifetime [1.311 ns] of 23° in plane aligned Chl-a macrocycles, indicate that hopping excitonic cascade is prominent among chlorophyll molecules. From the Raman Spectra, it can be postulated that they form a highly co-ordinated closely packed structure via water molecules within chitosan hydrogel due to 6th co-ordination through central Mg of porphyrin macrocycle. All these data predict that this chlorophyll-chitosan hydrogel can be an active component in artificial light harvesting systems.
