Regulating the Electronic Structure of Bismuth Nanosheets by Titanium Doping to Boost CO2 Electroreduction and Zn–CO2 Batteries

The electrochemical carbon dioxide reduction reaction (E-CO₂RR) to formate is a promising strategy for mitigating greenhouse gas emissions and addressing the global energy crisis. Developing low-cost and environmentally friendly electrocatalysts with high selectivity and industrial current densities for formate production is an ideal but challenging goal in the field of electrocatalysis. Herein, novel titanium-doped bismuth nanosheets (Ti Bi NSs) with enhanced E-CO₂RR performance are synthesized through one-step electrochemical reduction of bismuth titanate (Bi₄Ti₃O₁₂). We comprehensively evaluated Ti Bi NSs using in situ Raman spectra, finite element method, and density functional theory. The results indicate that the ultrathin nanosheet structure of Ti Bi NSs can accelerate mass transfer, while the electron-rich properties can accelerate the production of *CO₂⁻ and enhance the adsorption strength of *OCHO intermediate. The Ti Bi NSs deliver a high formate Faradaic efficiency (FE_formate) of 96.3% and a formate production rate of 4032 µmol h⁻¹ cm⁻² at −1.01 V versus RHE. An ultra-high current density of −338.3 mA cm⁻² is achieved at −1.25 versus RHE, and simultaneously FE_formate still reaches more than 90%. Furthermore, the rechargeable Zn–CO₂ battery using Ti Bi NSs as a cathode catalyst achieves a maximum power density of 1.05 mW cm⁻² and excellent charging/discharging stability of 27 h.     

An Iron-Decorated Carbon Aerogel for Rechargeable Flow and Flexible Zn–Air Batteries

Mechanically stable and foldable air cathodes with exceptional oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activities are key components of wearable metal–air batteries. Herein, a directional freeze-casting and annealing approach is reported for the construction of a 3D honeycomb nanostructured, N,P-doped carbon aerogel incorporating in situ grown FeP/Fe₂O₃ nanoparticles as the cathode in a flexible Zn–air battery (ZAB). The aqueous rechargeable Zn–air batteries assembled with this carbon aerogel exhibit a remarkable specific capacity of 648 mAh g⁻¹ at a current density of 20 mA cm⁻² with a good long-term durability, outperforming those assembled with commercial Pt/C+RuO₂ catalyst. Furthermore, such a foldable carbon aerogel with directional channels can serve as a freestanding air cathode for flexible solid-state Zn–air batteries without the use of carbon paper/cloth and additives, giving a specific capacity of 676 mAh g⁻¹ and an energy density of 517 Wh kg⁻¹ at 5 mA cm⁻² together with good cycling stability. This work offers a new strategy to design and synthesize highly effective bifunctional air cathodes to be applied in electrochemical energy devices.     

1T-WS2 Nanosheet-Modified Biomass Carbon as Sulfur Host for High-Performance Lithium–Sulfur Batteries

The sluggish sulfur reaction kinetics and fast capacity attenuation still pose great challenges to lithium–sulfur (Li–S) batteries. Herein, tubular carbonl (HPOC) is obtained by carbonization of the cattail fiber. 1T-WS₂@HPOC is prepared by solvothermal method, and their sulfur composite, 1T-WS₂@HPOC/S and HPOC/S as sulfur host composite, is obtained by sulfur melting. The composite materials are characterized by scanning electron microscopy, X-ray diffraction, thermogravimetry, X-ray photoelectron spectroscopy, etc. Results show that 1T-WS₂ grows uniformly on the HPOC substrate and has abundant active sites, which can effectively improve the physicochemical adsorption capacity of S-fixation (76 wt%) and polysulfide. Battery assembly and electrochemical performance tests are conducted for the HPOC/S and 1T-WS₂@HPOC/S composites. Results show that the initial discharge capacity of the 1T-WS₂@HPOC/S positive electrode is 1272 mAh g⁻¹ at 0.1 C, higher than the HPOC/S positive electrode (1025 mAh g⁻¹). 1T-WS₂@HPOC/S maintains a discharge capacity of 695 mAh g⁻¹ after 500 cycles at 0.5 C, with a capacity decay rate of only 0.054% per cycle. With a discharge capacity of 504 mAh g⁻¹ after 400 cycles at 1 C, the Coulomb efficiency is 98.9%. The 1T-WS₂@HPOC/S composites with unique structure and excellent electrochemical performance have broad application prospects in the field of Li–S batteries.     

Biomass-Derived Bifunctional Cathode Electrocatalyst and Multiadaptive Gel Electrolyte for High-Performance Flexible Zn–Air Batteries in Wide Temperature Range

High-efficiency and low-cost bifunctional electrocatalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER), as well as gel electrolytes with high thermal and mechanical adaptability are required for the development of flexible batteries. Herein, abundant Setaria Viridis (SV) biomass is selected as the precursor to prepare porous N-doped carbon tubes with high specific surface area and the 900 °C calcination product of SV (SV-900) shows the optimum ORR/OER activities with a small E_OER–E_ORR of 0.734 V. Meanwhile, a new multifunctional gel electrolyte named C20E2G5 is prepared using cellulose extracted from another widely distributed biomass named flax as the skeleton, epichlorohydrin as the cross-linker and glycerol as the antifreezing agent. C20E2G5 possesses high ionic conductivity from −40 to + 60 °C, excellent tensile and compressive resistance, high adhesion, strong freezing and heat resistance. Moreover, the symmetrical cell assembled with C20E2G5 can significantly inhibit Zn dendrite growth. Finally, flexible solid-state Zn–air batteries assembled with SV-900 and C20E2G5 show high open circuit voltage, large energy density, and long-term operation stability between −40 and + 60 °C. This biomass-based approach is generic and can be used for the development of diverse next-generation electrochemical energy conversion and storage devices.     

High-Performance Gas Sensing of CO: Comparative Tests for Semiconducting (SnO(2)-Based) and for Amperometric Gas Sensors

A comparison of the stability and sensitivity for two different sensor types (semiconductor SnO(2) devices, amperometric electrochemical sensors) has been performed. Sensitivities and drifts in the signal and in the background for various concentrations of CO have been studied for thick-film SnO(2) sensors (Pt and Pd doped) for a period in excess of 8 months. Similar performance data have been recorded for commercial amperometric sensors for a period in excess of 4 years. The two different sensor types investigated here were also compared to the well-known commercial Figaro TGS 822 sensor at similar concentrations. An objective approach for comparing different types of sensors has been developed using the "analytical sensitivity".     

Mo2N–ZrO2 Heterostructure Engineering in Freestanding Carbon Nanofibers for Upgrading Cycling Stability and Energy Efficiency of Li–CO2 Batteries

Li–CO₂ batteries have attracted considerable attention for their advantages of CO₂ fixation and high energy density. However, the sluggish dynamics of CO₂ reduction/evolution reactions restrict the practical application of Li–CO₂ batteries. Herein, a dual-functional Mo₂N–ZrO₂ heterostructure engineering in conductive freestanding carbon nanofibers (Mo₂N–ZrO₂@NCNF) is reported. The integration of Mo₂N–ZrO₂ heterostructure in porous carbons provides the opportunity to simultaneously accelerate electron transport, boost CO₂ conversion, and stabilize intermediate discharge product Li₂C₂O₄. Benefiting from the synchronous advantages, the Mo₂N–ZrO₂@NCNF catalyst endows the Li–CO₂ batteries with excellent cycle stability, good rate capability, and high energy efficiency even under high current densities. The designed cathodes exhibit an ultrahigh energy efficiency of 89.8% and a low charging voltage below 3.3 V with a potential gap of 0.32 V. Remarkably, stable operation over 400 cycles can be achieved even at high current densities of 50 µA cm⁻². This work provides valuable guidance for developing multifunctional heterostructured catalysts to upgrade longevity and energy efficiency of Li–CO₂ batteries.     

High-Performance,Long-Life,Rechargeable Li–CO2 Batteries based on a 3D Holey Graphene Cathode Implanted with Single Iron Atoms

A highly efficient cathode catalyst for rechargeable Li–CO₂ batteries is successfully synthesized by implanting single iron atoms into 3D porous carbon architectures, consisting of interconnected N,S-codoped holey graphene (HG) sheets. The unique porous 3D hierarchical architecture of the catalyst with a large surface area and sufficient space within the interconnected HG framework can not only facilitate electron transport and CO₂/Li⁺ diffusion, but also allow for a high uptake of Li₂CO₃ to ensure a high capacity. Consequently, the resultant rechargeable Li–CO₂ batteries exhibit a low potential gap of ≈1.17 V at 100 mA g⁻¹ and can be repeatedly charged and discharged for over 200 cycles with a cut-off capacity of 1000 mAh g⁻¹ at a high current density of 1 A g⁻¹. Density functional theory calculations are performed and the observed appealing catalytic performance is correlated with the hierarchical structure of the carbon catalyst. This work provides an effective approach to the development of highly efficient cathode catalysts for metal–CO₂ batteries and beyond.     

Preferentially Engineering FeN4 Edge Sites onto Graphitic Nanosheets for Highly Active and Durable Oxygen Electrocatalysis in Rechargeable Zn–Air Batteries

Single-atom FeN₄ sites at the edges of carbon substrates are considered more active for oxygen electrocatalysis than those in plane; however, the conventional high-temperature pyrolysis process does not allow for precisely engineering the location of the active site down to atomic level. Enlightened by theoretical prediction, herein, a self-sacrificed templating approach is developed to obtain edge-enriched FeN₄ sites integrated in the highly graphitic nanosheet architecture. The in situ formed Fe clusters are intentionally introduced to catalyze the growth of graphitic carbon, induce porous structure formation, and most importantly, facilitate the preferential anchoring of FeN₄ to its close approximation. Due to these attributes, the as-resulted catalyst (denoted as Fe/N-G-SAC) demonstrates unprecedented catalytic activity and stability for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) by showing an impressive half-wave potential of 0.89 V for the ORR and a small overpotential of 370 mV at 10 mA cm⁻² for the OER. Moreover, the Fe/N-G-SAC cathode displays encouraging performance in a rechargeable Zn–air battery prototype with a low charge–discharge voltage gap of 0.78 V and long-term cyclability for over 240 cycles, outperforming the noble metal benchmarks.     

A General “In Situ Etch-Adsorption-Phosphatization” Strategy for the Fabrication of Metal Phosphides/Hollow Carbon Composite for High Performance Liquid/Flexible Zn–Air Batteries

Benefiting from the admirable energy density (1086 Wh kg⁻¹), overwhelming security, and low environmental impact, rechargeable zinc–air batteries (ZABs) are deemed to be attractive candidates for lithium-ion batteries. The exploration of novel oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) bifunctional catalysts is the key to promoting the development of zinc–air batteries. Transitional metal phosphides (TMPs) especially Fe-based TMPs are deemed to be a rational type of catalyst, however, their catalytic performance still needs to be further improved. Considering Fe (heme) and Cu (copper terminal oxidases) are nature's options for ORR catalysis in many forms of life from bacteria to humans. Herein, a general “in situ etch-adsorption-phosphatization” strategy is designed for the fabrication of hollow FeP/Fe₂P/Cu₃P-N, P codoped carbon (Fe P/Cu₃P-NPC) catalyst as the cathode of liquid and flexible ZABs. The liquid ZABs manifest a high peak power density of 158.5 mW cm⁻² and outstanding long-term cycling performance (≈1100 cycles at 2 mA cm⁻²). Similarly, the flexible ZABs deliver superior cycling stability of 81 h at 2 mA cm⁻² without bending and 26 h with different bending angles.     

Single-Site Metal–Organic Framework and Copper Foil Tandem Catalyst for Highly Selective CO2 Electroreduction to C2H4

Tandem catalysis is a promising way to break the limitation of linear scaling relationship for enhancing efficiency, and the desired tandem catalysts for electrochemical CO₂ reduction reaction (CO₂RR) are urgent to be developed. Here, a tandem electrocatalyst created by combining Cu foil (CF) with a single-site Cu(II) metal–organic framework (MOF), named as Cu–MOF–CF, to realize improved electrochemical CO₂RR performance, is reported. The Cu–MOF–CF shows suppression of CH₄, great increase in C₂H₄ selectivity (48.6%), and partial current density of C₂H₄ at −1.11 V versus reversible hydrogen electrode. The outstanding performance of Cu–MOF–CF for CO₂RR results from the improved microenvironment of the Cu active sites that inhibits CH₄ production, more CO intermediate produced by single-site Cu–MOF in situ for CF, and the enlarged active surface area by porous Cu–MOF. This work provides a strategy to combine MOFs with copper-based electrocatalysts to establish high-efficiency electrocatalytic CO₂RR.     

A Freestanding 3D Heterostructure Film Stitched by MOF-Derived Carbon Nanotube Microsphere Superstructure and Reduced Graphene Oxide Sheets: A Superior Multifunctional Electrode for Overall Water Splitting and Zn–Air Batteries

Developing a scalable approach to construct efficient and multifunctional electrodes for the hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) is an urgent need for overall water splitting and zinc–air batteries. In this work, a freestanding 3D heterostructure film is synthesized from a Ni-centered metal−organic framework (MOF)/graphene oxide. During the pyrolysis process, 1D carbon nanotubes formed from the MOF link with the 2D reduced graphene oxide sheets to stitch the 3D freestanding film. The results of the experiments and theoretical calculations show that the synergistic effect of the N-doped carbon shell and Ni nanoparticles leads to an optimized film with excellent electrocatalytic activity. Low overpotentials of 95 and 260 mV are merely needed for HER and OER, respectively, to reach a current density of 10 mA cm⁻². In addition, a high half-wave potential of 0.875 V is obtained for the ORR, which is comparable to that of Pt/RuO₂ and ranks among the top of non-noble-metal catalysts. The use of an “all-in-one” film as the electrode leads to excellent performance of the homemade water electrolyzer and zinc–air battery, indicating the potential of the film for practical applications.