Polymer‐Mediated Electron Tunneling Towards Solar Water Oxidation

Abstract

Exploiting emerging artificial photosystems with regulated vectorial charge transfer pathways is retarded by the difficulties in precise interface modulation at the nanoscale level, deficiency of suitable assembly methodologies, and ultra-short charge lifetime. Herein, it is first conceptually demonstrated the general design of transition metal chalcogenides quantum dots (TMCs QDs)insulating polymer-metal oxides (MOs) electron-tunneling photo systems, wherein TMCs QDs are controllably layer-by-layer self-assembled on the MOs substrates assisted by an ultrathin insulating polymer interim layer. It is ascertained that electrons photoexcited over TMCs QDs in spatially highly ordered MOs/(TMCs QDs/polymer) n multilayered heterostructures can be unidirectionally extracted and tunneled to the MOs substrates across the intermediate insulating polymer layer by engendering the tandem charge transfer to accelerate the interfacial charge migration kinetics, thereby triggering the significantly boosted net efficiency of solar-driven photoelectrochemical water oxidation. This study would spark new inspirations for designing novel electron-tunneling photosystems for fine carrier modulation towards solar energy harvesting and conversion.

Charge modulation over atomically precise metal nanoclusters via non-conjugated polymers for photoelectrochemical water oxidation

“…3d, T(Au x P) 8 exhibits the smallest semicircle arc radius compared with T(Ag x P) 8 , T(Au 25 P) 8 , TP 8 , and TNTAs, implying its most efficient interfacial charge separation efficiency. 21,49 As summarized in Table S3, † T(Au x P) 8 demonstrates the lowest charge transfer resistance (3290 U) with respect to other photoelectrodes, that is, T(Ag x P) 8 (3375 U), T(Au 25 P) 8 (4233 U), TP 8 (11 170 U), and TNTAs (11 510 U), implying that cooperativity of Au x NCs and PAH is advantageous to boost the interfacial charge transport efficiency. The results are consistent with the LSV and I-t results.…”

Surface engineering of nanoporous silicon photocathodes for enhanced photoelectrochemical hydrogen production

“…[7][8][9][10][11][12] To enable the practical sunlightdriven water splitting, an ideal PEC cell needs to have high solar-to-hydrogen (STH) efficiency, low-cost and long-term stability, which strictly limits the selection of semiconductor materials. [13][14][15][16][17][18][19][20] In the past decades, n-type semiconductors have been widely studied in the photoanode configuration for water oxidation. [21][22][23][24][25][26][27][28][29][30][31][32] However, there are relatively fewer efficient, stable and low-cost p-type candidates to produce hydrogen fuel from water.…”

Photosensitization Efficiency Modulation of Atomically Precise Silver Nanoclusters for Photoelectrocatalysis

“…On the other hand, a large variety of metal oxides (MOs, e.g., TiO 2 , WO 3 , Fe 2 O 3 , etc.) function as high-efficiency photoanodes for PEC water oxidation owing to favorable valence band potential, good photostability, and environmentally friendly advantages . Nonetheless, developments of MO-based photoanodes are still impeded by the confined light absorption range and the rapid carrier recombination rate. , The advantages of Ag x NCs in light-harvesting capability and conversion lead us to consider that their photosensitization effect would perfectly compensate for the drawbacks of MO-based photoanodes by constructing MOs/Ag x NC heterostructured photoanodes by smartly harnessing the generic photosensitization effect and enriched catalytically active sites of atomically precise Ag x NCs.…”

“…function as highefficiency photoanodes for PEC water oxidation owing to favorable valence band potential, good photostability, and environmentally friendly advantages. 27…”