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Adv Mater ; 32(8): e1906806, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31950562


Oxygen evolution reaction (OER) catalysts that function efficiently in pH-neutral electrolyte are of interest for biohybrid fuel and chemical production. The low concentration of reactant in neutral electrolyte mandates that OER catalysts provide both the water adsorption and dissociation steps. Here it is shown, using density functional theory simulations, that the addition of hydrated metal cations into a Ni-Fe framework contributes water adsorption functionality proximate to the active sites. Hydration-effect-promoting (HEP) metal cations such as Mg2+ and hydration-effect-limiting Ba2+ into Ni-Fe frameworks using a room-temperature sol-gel process are incorporated. The Ni-Fe-Mg catalysts exhibit an overpotential of 310 mV at 10 mA cm-2 in pH-neutral electrolytes and thus outperform iridium oxide (IrO2 ) electrocatalyst by a margin of 40 mV. The catalysts are stable over 900 h of continuous operation. Experimental studies and computational simulations reveal that HEP catalysts favor the molecular adsorption of water and its dissociation in pH-neutral electrolyte, indicating a strategy to enhance OER catalytic activity.

Angew Chem Int Ed Engl ; 59(6): 2273-2278, 2020 Feb 03.
Artigo em Inglês | MEDLINE | ID: mdl-31743581


Rechargeable aqueous zinc-ion batteries are attractive because of their inherent safety, low cost, and high energy density. However, viable cathode materials (such as vanadium oxides) suffer from strong Coulombic ion-lattice interactions with divalent Zn2+ , thereby limiting stability when cycled at a high charge/discharge depth with high capacity. A synthetic strategy is reported for an oxygen-deficient vanadium oxide cathode in which facilitated Zn2+ reaction kinetic enhance capacity and Zn2+ pathways for high reversibility. The benefits for the robust cathode are evident in its performance metrics; the aqueous Zn battery shows an unprecedented stability over 200 cycles with a high specific capacity of approximately 400 mAh g-1 , achieving 95 % utilization of its theoretical capacity, and a long cycle life up to 2 000 cycles at a high cathode utilization efficiency of 67 %. This work opens up a new avenue for synthesis of novel cathode materials with an oxygen-deficient structure for use in advanced batteries.

Small ; 15(52): e1905903, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31769588


Metal anodes, such as zinc and bismuth have been regarded as ideal materials for aqueous batteries due to high gravimetrical capacity, high abundance, low toxicity, and intrinsic safety. However, their translation into practical applications are hindered by the low mass loading (≈1 mg cm-2 ) of active materials. Here, the multiscale integrated structural engineering of 3D scaffold and active material, i.e., bismuth is in situ intercalated in reduced graphene oxide (rGO) wall of network, are reported. Tailoring the rapid charge transport on rGO 3D network and facile access to nano- and microscale bismuth, the rGO/Bi hybrid anode shows high utilization efficiency of 91.4% at effective high load density of ≈40 mg cm-2 , high areal capacity of 3.51 mAh cm-2 at the current density of 2 mA cm-2 and high reversibility of >10 000 cycles. The resulting Ni-Bi full battery exhibits high areal capacity of 3.13 mAh cm-2 at the current density of 2 mA cm-2 , far outperforming the other counterpart batteries. It represents a general and efficient strategy in enhancing the battery performance by designing hierarchically networked structure.

Angew Chem Int Ed Engl ; 58(47): 16820-16825, 2019 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-31535447


The electrocatalytic urea oxidation reaction (UOR) provides more economic electrons than water oxidation for various renewable energy-related systems owing to its lower thermodynamic barriers. However, it is limited by sluggish reaction kinetics, especially by CO2 desorption steps, masking its energetic advantage compared with water oxidation. Now, a lattice-oxygen-involved UOR mechanism on Ni4+ active sites is reported that has significantly faster reaction kinetics than the conventional UOR mechanisms. Combined DFT, 18 O isotope-labeling mass spectrometry, and in situ IR spectroscopy show that lattice oxygen is directly involved in transforming *CO to CO2 and accelerating the UOR rate. The resultant Ni4+ catalyst on a glassy carbon electrode exhibits a high current density (264 mA cm-2 at 1.6 V versus RHE), outperforming the state-of-the-art catalysts, and the turnover frequency of Ni4+ active sites towards UOR is 5 times higher than that of Ni3+ active sites.

Angew Chem Int Ed Engl ; 57(49): 16114-16119, 2018 Dec 03.
Artigo em Inglês | MEDLINE | ID: mdl-30315718


Enhancing the p-orbital delocalization of a Bi catalyst (termed as POD-Bi) via layer coupling of the short inter-layer Bi-Bi bond facilitates the adsorption of intermediate *OCHO of CO2 and thus boosts the CO2 reduction reaction (CO2 RR) rate to formate. X-ray absorption fine spectroscopy shows that the POD-Bi catalyst has a shortened inter-layer bond after the catalysts are electrochemically reduced in situ from original BiOCl nanosheets. The catalyst on a glassy carbon electrode exhibits a record current density of 57 mA cm-2 (twice the state-of-the-art catalyst) at -1.16 V vs. RHE with an excellent formate Faradic efficiency (FE) of 95 %. The catalyst has a record half-cell formate power conversion efficiency of 79 % at a current density of 100 mA cm-2 with 93 % formate FE when applied in a flow-cell system. The highest rate of the CO2 RR production reported (391 mg h-1 cm2 ) was achieved at a current density of 500 mA cm-2 with formate FE of 91 % at high CO2 pressure.

ACS Appl Mater Interfaces ; 10(4): 3624-3633, 2018 Jan 31.
Artigo em Inglês | MEDLINE | ID: mdl-29308871


For photoelectrochemical (PEC) water splitting, the interface interactions among semiconductors, electrocatalysts, and electrolytes affect the charge separation and catalysis in turn. Here, through the changing of the bath temperature, Co-based oxygen evolution catalysts (OEC) with different crystallinities were electrochemically deposited on Ti-doped Fe2O3 (Ti-Fe2O3) photoanodes. We found: (1) the OEC with low crystallinity is highly ion-permeable, decreasing the interactions between OEC and photoanode due to the intimate interaction between semiconductor and electrolyte; (2) the OEC with high crystallinity is nearly ion-impermeable, is beneficial to form a constant buried junction with semiconductor, and exhibits the low OEC catalytic activity; and (3) the OEC with moderate crystallinity is partially electrolyte-screened, thus contributing to the formation of ideal band bending underneath surface of semiconductor for charge separation and the highly electrocatalytic activity of OEC for lowering over-potentials of water oxidation. Our results demonstrate that to balance the water oxidation activity of OEC and OEC-semiconductor interface energetics is crucial for highly efficient solar energy conversion; in particular, the energy transducer is a semiconductor with a shallow or moderate valence-band level.