We develop a host-guest strategy to construct an electrocatalyst with Fe-Co dual sites embedded on N-doped porous carbon and demonstrate its activity for oxygen reduction reaction in acidic electrolyte. Our catalyst exhibits superior oxygen reduction reaction performance, with comparable onset potential (E, 1.06 vs 1.03 V) and half-wave potential (E, 0.863 vs 0.858 V) than commercial Pt/C. The fuel cell test reveals (Fe,Co)/N-C outperforms most reported Pt-free catalysts in H/O and H/air. In addition, this cathode catalyst with dual metal sites is stable in a long-term operation with 50 000 cycles for electrode measurement and 100 h for H/air single cell operation. Density functional theory calculations reveal the dual sites is favored for activation of O-O, crucial for four-electron oxygen reduction.
Identification on catalytic sites of heterogeneous catalysts at atomic level is important to understand catalytic mechanism. Surface engineering on defects of metal oxides can construct new active sites and regulate catalytic activity and selectivity. Here we outline the strategy by controlling surface defects of nanoceria to create the solid frustrated Lewis pair (FLP) metal oxide for efficient hydrogenation of alkenes and alkynes. Porous nanorods of ceria (PN-CeO2) with a high concentration of surface defects construct new Lewis acidic sites by two adjacent surface Ce3+. The neighbouring surface lattice oxygen as Lewis base and constructed Lewis acid create solid FLP site due to the rigid lattice of ceria, which can easily dissociate H–H bond with low activation energy of 0.17 eV.
Sub-nanometric Pd clusters on porous nanorods of CeO2 (PN-CeO2) with a high Pd dispersion of 73.6% exhibit the highest catalytic activity and best chemoselectivity for hydrogenation of nitroarenes to date. For hydrogenation of 4-nitrophenol, the catalysts yield a TOF of ∼44059 h(-1) and a chemoselectivity to 4-aminophenol of >99.9%. The superior catalytic performance can be attributed to a cooperative effect between the highly dispersed sub-nanometric Pd clusters for hydrogen activation and unique surface sites of PN-CeO2 with a high concentration of oxygen vacancy for an energetically and geometrically preferential adsorption of nitroarenes via nitro group. The high concentration of surface defects of PN-CeO2 and large Pd dispersion contribute to the enhanced catalytic activity for the hydrogenation reactions. The high chemoselectivity is mainly governed by the high Pd dispersion on the support. The catalysts also deliver high catalytic activity and selectivity for nitroaromatics with various reducible substituents into the corresponding aminoarenes.
Synchrotron x-ray reflectivity is used to study the interface between bulk water and bulk n-alkanes with carbon numbers 6 through 10, 12, 16, and 22. For all interfaces, except the water-hexane interface, the interfacial width disagrees with the prediction from capillary-wave theory. The variation of interfacial width with carbon number can be described by combining the capillary-wave prediction for the width with a contribution from intrinsic structure. This intrinsic structure is determined by the gyration radius for the shorter alkanes and by the bulk correlation length for the longer alkanes.
The
development of heterogeneous frustrated-Lewis-pair (FLP) catalysts
from homogeneous FLP conception is of great promise in practical applications.
While our recent discovery has shown that all-solid FLPs can be created
on ceria via surface oxygen vacancy regulation (
Zhang
Zhang
Nat. Commun.2017815266),
a sound understanding of the intrinsic property and reactivity of
the solid FLPs is still expected. Here we present a comprehensive
theoretical study on the FLPs (Ce···O) constructed
on CeO2(110) and (100) surfaces by using density functional
theory calculations. We find that the creation of surface oxygen vacancy
can enhance both the acidity of FLP-acid site and the basicity of
FLP-base site. The enhanced acidity and basicity of Lewis sites together
with the elongated distance of Lewis pairs (Ce···O)
contribute to the high activity of solid FLPs. The dissociative activation
of H2 on FLPs experiences a heterolytic pathway (H2 → Hδ+ + Hδ−) with a low activation energy of 0.07 eV on CeO2(110)
and 0.08 eV on CeO2(100). Unlike the phenomenon on stoichiometric
CeO2 surfaces that the dissociated hydride (Hδ−) adsorbed at Ce sites is prone to transfer to more stable O sites,
the hydride on FLPs can be stabilized at Ce sites and thus benefits
the hydrogenation of acetylene via an easier pathway. The rate-determining
barriers of acetylene hydrogenation on FLP-CeO2(110) and
FLP-CeO2(100) are calculated to be 0.58 and 0.88 eV, respectively.
These results could help to understand the nature of solid FLPs and
pave the way for rational design of heterogeneous FLP catalysts.
Searching the high‐efficient, stable, and earth‐abundant electrocatalysts to replace the precious noble metals holds the promise for practical utilizations of hydrogen and oxygen evolution reactions (HER and OER). Here, a series of highly active and robust Co‐doped nickel phosphides (Ni2−xCoxP) catalysts and their hybrids with reduced graphene oxide (rGO) are developed as bifunctional catalysts for both HER and OER. The Co‐doping in Ni2P and their hybridization with rGO effectively regulate the catalytic activity of the surface active sites, accelerate the charge transfer, and boost their superior catalytic activity. Density functional theory calculations show that the Co‐doped catalysts deliver the moderate trapping of atomic hydrogen and facile desorption of the generated H2 due to the H‐poisoned surface active sites of Ni2−xCoxP under the real catalytic process. Electrochemical measurements reveal the high HER efficiency and durability of the NiCoP/rGO hybrids in electrolytes with pH 0–14. Coupled with the remarkable and robust OER activity of the NiCoP/rGO hybrids, the practical utilization of the NiCoP/rGO‖NiCoP/rGO for overall water splitting yields a catalytic current density of 10 mA cm−2 at 1.59 V over 75 h without an obvious degradation and Faradic efficiency of ≈100% in a two‐electrode configuration and 1.0 m KOH.
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