RESUMEN
Oxygen reduction reaction via the two-electron pathway (2e- ORR) offers a sustainable opportunity for hydrogen peroxide (H2O2) production, but suffers from low selectivity. In this work, indium oxide with oxygen vacancies (In2O3-x) exhibits a H2O2 selectivity close to 98% at 0.6 V vs. RHE. Further, a Faradaic efficiency (FE) of around 95% at 0.4-0.6 V vs. RHE and a H2O2 productivity of 3.7 mol gcatalyst-1 h-1 are reached in a flow cell. In situ Raman spectra indicate that In2O3-x promotes the adsorption and activation of O2 and stabilizes oxygen intermediates. This work provides an insight into improving H2O2 selectivity for 2e- ORR catalysts.
RESUMEN
Due to the slow dynamics of mass and charge transfer at Zn|electrolyte interface, the stable operation of Zn-air batteries (ZABs) is challenging, especially at low temperature. Herein, inspired by cell membrane, a hydrophilic-hydrophobic dual modulated Zn|electrolyte interface is constructed. This amphiphilic design enables the quasi-solid-state (QSS) ZABs to display a long-term cyclability of 180 h@50 mA cm-2 at 25 °C. Moreover, a record-long time of 173 h@4 mA cm-2 at -60 °C is also achieved, which is almost threefolds of untreated QSS ZABs. Control experiments and (in situ) characterization reveal that the growth of insulating ZnO passivation layers is largely inhibited by tuned hydrophilic-hydrophobic behavior. Thus, the enhanced transfer dynamic of Zn2+ at Zn|electrolyte interface from 25 to -60 °C is attained. As an extension, the QSS Al-air batteries (AABs) with bioinspired interface also show unprecedented discharge stability of 420 h@1 mA cm-2 at -40 °C, which is about two times of untreated QSS AABs. This bioinspired-hydrophilic-hydrophobic dual modulation strategy may provide a reference for energy transform and storage devices with broad temperature adaptability.
RESUMEN
The bifunctional oxygen electrocatalyst is the Achilles' heel of achieving robust reversible Zn-air batteries (ZABs). Herein, durable bifunctional oxygen electrocatalysis in alkaline media is realized on atomic Fe-N4-C sites reinforced by NixCo3-xO4 (NixCo3-xO4@Fe1/NC). Compared with that of pristine Fe1/NC, the stability of the oxygen evolution reaction (OER) is increased 10 times and the oxygen reduction reaction (ORR) performance is also improved. The steric hindrance alters the valence electron at the Fe-N4-C sites, resulting in a shorter Fe-N bond and enhanced stability of the Fe-N4-C sites. The corresponding solid-state ZABs exhibit an ultralong lifespan (>460 h at 5 mA cm-2) and high rate performance (from 2 to 50 mA cm-2). Furthermore, the structural evolution of NixCo3-xO4@Fe1/NC before and after the OER and ORR as well as charge-discharge cycling is explored. This work develops an efficient strategy for improving bifunctional oxygen electrocatalysis and possibly other processes.
RESUMEN
The unsatisfactory adsorption and activation of CO2 suppress electrochemical reduction over a wide potential window. Herein, the built-in electric field (BIEF) at the CeO2/In2O3 n-n heterostructure realizes the C1 (CO and HCOO-) selectivity over 90.0% in a broad range of potentials from -0.7 to -1.1 V with a maximum value of 98.7 ± 0.3% at -0.8 V. In addition, the C1 current density (-1.1 V) of the CeO2/In2O3 heterostructure with a BIEF is about 2.0- and 3.2-fold that of In2O3 and a physically mixed sample, respectively. The experimental and theoretical calculation results indicate that the introduction of CeO2 triggered the charge redistribution and formed the BIEF at the interfaces, which enhanced the interfacial adsorption and activation of CO2 at low overpotentials. Furthermore, the promoting effect was also extended to CeO2/In2S3. This work gives a deep understanding of BIEF engineering for highly efficient CO2 electroreduction over a wide potential window.
RESUMEN
It is an urgent need to improve the depth of discharge (DOD) of Zn-air batteries (ZABs), considering that most reported ZABs with long cycle life are realized at low DOD (<1%). In this work, our solid-state ZABs achieved a long cycle life of more than 220 h at 3.2% DOD (the discharge capacity of 10 mA h cm-2 per cycle). Moreover, benefiting from excellent bifunctional oxygen electrocatalysts (Fe@BNC) and robust Zn|electrolyte interface, the ZABs displayed a long cycle life of 120 h even at high DOD of 23.4% and large discharge capacity of 72 mA h cm-2. Additionally, the impact of Zn|electrolyte interface on the cycle time at different DODs is analysed and discussed. The unstable interface exacerbated the dendrite growth and uneven deposition of Zn at high DOD, leading to the decay of the cycle life. The work gives insights into the mechanism of the effect of DOD on the cycle life of the batteries.
RESUMEN
Electrochemical CO2 reduction (ECO2R) with renewable electricity is an advanced carbon conversion technology. At present, copper is the only metal to selectively convert CO2 into multicarbon (C2+) products. Among them, atomically dispersed (AD) Cu catalysts have received great attention due to the relatively single chemical environment, which are able to minimize the negative impact of morphology, valence state, and crystallographic properties, etc. on product selectivity. Furthermore, the completely exposed atomic Cu sites not only provide space and bonding electrons for the adsorption of reactants in favor of better catalytic activity but also provide an ideal platform for studying its reaction mechanism. This review summarizes the recent progress of AD Cu catalysts as a chemically tunable platform for ECO2R, including the atomic Cu sites dynamic evolution, the catalytic performance, and mechanism. Furthermore, the prospects and challenges of AD Cu catalysts for ECO2R are carefully discussed. We sincerely hope that this review can contribute to the rational design of AD Cu catalysts with enhanced performance for ECO2R.
RESUMEN
Electrocatalytic CO2 reduction has received great attention for alleviating environmental problems and energy crisis. SnO2-based catalysts are attractive candidates, but they still face problems such as high overpotentials and small current density due to their low intrinsic electrical conductivity and weak activation for CO2. Here, superior selectivity and activity for C1 products (HCOO- and CO) were obtained using In-doped SnO2. The maximum faradaic efficiency was 96.46% at -0.75 V and the partial current density reached -20.12 mA cm-2 at -0.95 V for C1 products. Furthermore, the selectivity for C1 products was over 90% from -0.5 to -1.0 V with a current density of -166.2 mA cm-2 at -1.0 V in flow cells. In ion doping induced electron transfer from Sn species to In and simultaneously generated oxygen vacancies, which improved electrical conductivity and regulated the oxidation state of Sn active sites and provided more active sites. This work emphasizes the role of enhanced electron transfer of catalysts in CO2 electroreduction.