Deeper Insights into the Morphology Effect of Na2Ti3O7 Nanoarrays on Sodium-Ion Storage.

Na2Ti3O7-based anodes show great promise for Na+ storage in sodium-ion batteries (SIBs), though the effect of Na2Ti3O7 morphology on battery performance remains poorly understood. Herein, hydrothermal syntheses is used to prepare free-standing Na2Ti3O7 nanosheets or Na2Ti3O7 nanotubes on Ti foil substrates, with the structural and electrochemical properties of the resulting electrodes explored in detail. Results show that the Na2Ti3O7 nanosheet electrode (NTO NSs) delivered superior performance in terms of reversible capacity, rate capability, and especially long-term durability in SIBs compared to its nanotube counterpart (NTO NTs). Electrochemical impedance spectroscopy (EIS) and scanning electron microscopy (SEM) investigations, combined with density functional theory calculations, demonstrated that the flexible 2D Na2Ti3O7 nanosheets are mechanically more robust than the rigid Na2Ti3O7 nanotube arrays during prolonged battery cycling, explaining the superior durability of the NTO NSs electrode. This work prompts the use of anodes based on Na2Ti3O7 nanosheets in the future development of high-performance SIBs.

Insightful Understanding of Synergistic Oxygen Reduction on PtCo3(111) Toward Zinc-Air Batteries.

Theory-guided materials design is an effective strategy for designing catalysts with high intrinsic activity whilst minimizing the usage of expensive metals like platinum. As proof-of-concept, herein it demonstrates that using density functional theory (DFT) calculations and experimental validation that intermetallic PtCo3 alloy nanoparticles offer enhanced electrocatatalytic performance for the oxygen reduction reaction (ORR) compared to Pt nanoparticles. DFT calculations established that PtCo3(111) surfaces possess better intrinsic ORR activity compared to Pt(111) surfaces, owing to the synergistic action of adjacent Pt and Co active sites which optimizes the binding strength of ORR intermediates to boost overall ORR kinetics. With this understanding, a PtCo3/NC catalyst, comprising PtCo3 nanoparticles exposing predominantly (111) facets dispersed on an N-doped carbon support, is successfully fabricated. PtCo3/NC demonstrates a high specific activity (3.4 mA cm-2 mgPt -1), mass activity (0.67 A mgPt -1), and cycling stability for the ORR in 0.1 M KOH, significantly outperforming a commercial 20 wt.% Pt/C catalyst. Moreover, a zinc-air battery (ZAB) assembled with PtCo3/NC as the air-electrode catalyst delivered an open-circuit voltage of 1.47 V, a specific capacity of 775.1 mAh gZn -1 and excellent operation durability after 200 discharge/charge cycles, vastly superior performance to a ZAB built using commercial Pt/C+IrO2 as the air-electrode catalyst.

Iron-Cobalt Phosphide Encapsulated in a N-Doped Carbon Framework as a Promising Low-Cost Oxygen Reduction Electrocatalyst for Zinc-Air Batteries.

The oxygen reduction reaction (ORR) plays a vital role in many next-generation electrochemical energy conversion and storage devices, motivating the search for low-cost ORR electrocatalysts possessing high activity and excellent durability. In this work, we demonstrate that iron-cobalt phosphide (FeCoP) nanoparticles encapsulated in a N-doped carbon framework (FeCoP@NC) represent a very promising catalyst for the ORR in alkaline media. The core-shell structured FeCoP@NC catalyst offered outstanding ORR activity with a half-wave potential (E1/2) of 0.86 V vs reversible hydrogen electrode (RHE) and excellent stability in a 0.1 M KOH electrolyte, outperforming commercial Pt/C and many recently reported noble-metal-free ORR electrocatalysts. The superiority of FeCoP@NC as an ORR electrocatalyst relative to Pt/C was further verified in prototype zinc-air batteries (ZABs), with the aqueous and flexible ZABs prepared using FeCoP@NC offering excellent stability, impressive open circuit voltages (1.56 and 1.44 V, respectively), and high maximum power densities (183.5 and 69.7 mW cm-2, respectively). Density functional theory calculations revealed that encapsulating FeCoP nanoparticles in N-doped carbon shells resulted in favorable electron penetration effects, which synergistically regulated the adsorption/desorption of ORR intermediates for optimal ORR performance while also boosting the electronic conductivity. Our findings offer valuable new insights for rational design of transition metal phosphide-based catalysts for the ORR and other electrochemical applications.

Simultaneous Generation of H2 O2 and Formate by Co-Electrolysis of Water and CO2 over Bifunctional Zn/SnO2 Nanodots.

Hydrogen peroxide (H2 O2 ) and formate are important chemicals used in various chemical manufacturing industries. One promising approach for the simultaneous production of these chemicals is coupling anodic two-electron water oxidation with cathodic CO2 reduction in an electrolyzer using nonprecious bifunctional electrocatalysts. Herein, we report an innovative hybrid electrosynthesis strategy using Zn-doped SnO2 (Zn/SnO2 ) nanodots as bifunctional redox electrocatalysts to achieve Faradaic efficiencies of 80.6 % and 92.2 % for H2 O2 and formate coproduction, respectively, along with excellent stability for at least 60 h at a current density of ≈150 mA cm-2 . Through a combination of physicochemical characterizations, including operando attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), isotope labeling mass spectrometry (MS)/1 H NMR and quasi-in situ electron paramagnetic resonance (EPR), with density functional theory (DFT) calculations, we discovered that the Zn dopant facilitates the coupling of *OH intermediates to promote H2 O2 production and optimizes the adsorption of *OCHO intermediates to accelerate formate formation. Our findings offer new insights into designing more efficient bifunctional electrocatalyst-based pair-electrosynthesis system for the coproduction of H2 O2 and formate feedstocks.

Development of new atom transfer radical polymerization system by iron (III)-metal salts without using any external initiator and reducing agent.

Atom transfer radical polymerization (ATRP) catalyzed by high oxidation state metal salts of FeX3 is developed for the first time in the absence of both external initiator and reducing agent. Methyl methacrylate (MMA) and styrene are polymerized successfully using FeX3 /Phosphorous ligands with well-controlled molecular weight distributions (=1.5). The molecular weight of the polymers increases with monomer consumption with the progress of time and the polymerization behaviors show a decent ATRP trend. Activators and initiators are suggested to generate in situ by the addition reaction of MMA and one equivalent of FeX3 . The PMMA synthesized from without-initiator system is characterized by (1) H, (13) C and DEPT (distortionless enhancement by polarization transfer nuclear magnetic resonance) nuclear magnetic resonance spectroscopy. Chain extension and copolymerization experiments prove the livingness of the obtained polymer.

Nanostructure Engineering and Electronic Modulation of a PtNi Alloy Catalyst for Enhanced Oxygen Reduction Electrocatalysis in Zinc-Air Batteries.

PtNi nanoalloys have demonstrated electrocatalysis superior to that of benchmark Pt/C catalysts for the oxygen reduction reaction (ORR), yet the underlying mechanisms remain underexplored. Herein, a PtNi/NC catalyst comprising PtNi nanoparticles (∼5.2 nm in size) dispersed on N-doped carbon frameworks was prepared using a simple pyrolysis strategy. Benefiting from the individual components and a hierarchical structure, the PtNi/NC catalyst exhibited outstanding ORR activity and stability (E1/2 = 0.82 V vs RHE and 8 mV negative shift after 20000 cycles), outperforming a commercial 20 wt % Pt/C catalyst (E1/2 = 0.81 V and 32 mV negative shift). A prototype zinc-air battery constructed using PtNi/NC as the air electrode catalyst achieved highly enhanced electrochemical performance, outperforming a battery constructed using Pt/C as the ORR catalyst. Density functional theory calculations revealed that the improved ORR activity of the PtNi nanoalloys originated from charge redistribution with a suitable metal d-band center to promote the formation of the ORR intermediates.

Sodium Tartrate-Assisted Synthesis of High-Purity NiFe2O4 Nano-Microrods Supported by Porous Ketjenblack Carbon for Efficient Alkaline Oxygen Evolution.

Herein, a simple two-step synthetic method was developed for the synthesis of NiFe2O4 nano-microrods supported on Ketjenblack carbon (NiFe2O4/KB). A sodium tartrate-assisted hydrothermal method was employed for the synthesis of a NiFe-MOF/KB precursor, which was then pyrolyzed under N2 at 500 °C to yield NiFe2O4/KB. Benefiting from the presence of high-valence Ni3+ and Fe3+, high conductivity, and a large electrochemically active surface area, NiFe2O4/KB delivered outstanding OER electrocatalytic performance under alkaline conditions, including a very low overpotential of 258 mV (vs RHE) at 10 mA cm-2, a small Tafel slope of 43.01 mV dec-1, and excellent durability in 1.0 M KOH. Density functional theory calculations verified the superior alkaline OER electrocatalytic activity of NiFe2O4 to IrO2. While both catalysts possessed a similar metallic ground state, NiFe2O4 offered a lower energy barrier in the rate-determining OER step (*OOH → O2) compared to IrO2, resulting in faster OER kinetics.

A Hybrid of the Fe4N-Fe Heterojunction Supported on N-Doped Carbon Nanobelts and Ketjen Black Carbon as a Robust High-Performance Electrocatalyst.

Herein, an extremely simple l-alanine-assisted pyrolysis method was proposed for the construction of a novel hierarchically porous hybrid of Fe4N-Fe supported on N-doped carbon nanobelts and Ketjen black carbon (denoted as Fe4N-Fe@N-C/N-KB). It has been found that the participation of l-alanine in pyrolysis can dramatically increase the total pyridinic-N/graphitic-N content in Fe4N-Fe@N-C/N-KB, which is peculiarly conducive to the enhancement of ORR performance. The in-site formation of the Fe4N-Fe heterojunction via the thermal reduction and decomposition of Fe3N as well as the introduction of cheap KB can significantly improve the ORR performance. As a result, the activity, durability, and methanol tolerance of this hybrid are comprehensively better than those of commercial 20 wt % Pt/C, promising future applications in practical devices. Density functional theory calculations disclose that the highly improved ORR activity of Fe4N-Fe@N-C/N-KB also benefits from the favorable electron penetration and excellent electronic conductivity between the Fe4N nanoparticles and the N-incorporated carbon frameworks.