10.1002/anie.202003129
Angewandte Chemie International Edition
RESEARCH ARTICLE
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In summary, we have prepared a “sandwich”-structured CBC/Vr-
ReSe2@CBC/CBC membrane with hydrophobic surface and high
electroactivity. As predicted by the DFT calculation results, the
introduced selenium vacancy could modulate the electronic
structures of ReSe2 nanosheet by positively shifting its d-band
position, which shows poor electrocatalytic selectivity with
simultaneously enhanced NRR and HER processes. As revealed
by the under-electrolyte nitrogen bubble adhesive force and
superhydrophilic measurements, the covered hydrophobic CBC
layer is beneficial to resisting the intimate contact between water
molecules and Vr-ReSe2@CBC nanofibers, and slightly increases
the adhesive force towards nitrogen bubbles. As a result, the
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CBC/Vr-ReSe2@CBC/CBC membrane displayed
a boosted
Faradaic efficiency by ~32% at room temperature. As revealed by
COMSOL Multiphysics stimulations, the porous and hydrophobic
CBC layers could provide special channels for sluggish internal
diffusion of H+ ions, leaving limited water molecules to contact the
electro-active Vr-ReSe2@CBC nanofibers and more unoccupied
active site for nitrogen adsorption and NRR processes. This work
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We are really grateful for the financial support from the National
Natural Science Foundation of China (21674019, 51801075), the
Shanghai Scientific and Technological Innovation Project
(18JC1410600), the Program of Shanghai Academic Research
Leader (17XD1400100), the Engineering and Physical Sciences
Research Council (EPSRC, EP/L015862/1). J.H and J.M.
gratefully acknowledge the financial support of the Flemish
Government through the Moonshot cSBO project P2C
(HBC.2019.0108) and through long-term structural funding
(Methusalem). D.R. gratefully acknowledge the support of
Jiangsu Overseas Visiting Scholar Program for University
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Keywords: ReSe2 • carbon nanofiber • nitrogen reduction
reaction • DFT calculation • COLSOM simulation
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