Fe?N4O?C Nanoplates Covalently Bonding on Graphene for Efficient CO2 Electroreduction and Zn?CO2 Batteries (Adv. Funct. Mater. 27/2023)

Electrochemical carbon dioxide (CO₂) reduction into value-added products holds great promise in moving toward carbon neutrality but remains a grand challenge due to lack of efficient electrocatalysts. Herein, the nucleophilic substitution reaction is elaborately harnessed to synthesize carbon nanoplates with a Fe N₄O configuration anchored onto graphene substrate (Fe N₄O C/Gr) through covalent linkages. Density functional theory calculations demonstrate the unique configuration of Fe N₄O with one oxygen (O) atom in the axial direction not only suppresses the competing hydrogen evolution reaction, but also facilitates the desorption of *CO intermediate compared with the commonly planar single-atomic Fe sites. The Fe N₄O C/Gr shows excellent performance in the electroreduction of CO₂ into carbon monoxide (CO) with an impressive Faradaic efficiency of 98.3% at −0.7 V versus reversible hydrogen electrode (RHE) and a high turnover frequency of 3511 h⁻¹. Furthermore, as a cathode catalyst in an aqueous zinc (Zn)-CO₂ battery, the Fe N₄O C/Gr achieves a high CO Faradaic efficiency (≈91%) at a discharge current density of 3 mA cm⁻² and long-term stability over 74 h. This work opens up a new route to simultaneously modulate the geometric and electronic structure of single-atomic catalysts toward efficient CO₂ conversion.     

Fe?N?C Electrocatalysts with Densely Accessible Fe?N4 Sites for Efficient Oxygen Reduction Reaction

The development of iron and nitrogen co-doped carbon (Fe N C) electrocatalysts for the oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells (PEMFCs) is a grand challenge due to the low density of accessible Fe N₄ sites. Here, an in situ trapping strategy using nitrogen-rich molecules (e.g., melamine, MA) is demonstrated to enhance the amount of accessible Fe N₄ sites in Fe N C electrocatalysts. The melamine molecules can participate in the coordination of Fe ions in zeolitic imidazolate frameworks to form Fe N₆ sites within precursors. These Fe N₆ sites are then converted into atomically dispersed Fe N₄ sites during a pyrolytic process. Remarkably, the Fe N C/MA exhibits a high single-atom Fe content (3.5 wt.%), a large surface area (1160 m² g⁻¹), and a high density of accessible FeN₄ sites (45.7 × 10¹⁹ sites g⁻¹). As a result, Fe N C/MA shows a much enhanced ORR activity with a half-wave potential of 0.83 V (vs the reversible hydrogen electrode) in a 0.5 m H₂SO₄ electrolyte solution and a good performance in a PEMFC system with an activity of 80 mA cm⁻² at 0.8 V under 1.0 bar H₂/air. This work offers a promising approach toward high-performance carbon-based ORR electrocatalysts.     

Highly Dispersed NiO Clusters Induced Electron Delocalization of Ni?N?C Catalysts for Enhanced CO2 Electroreduction

Oxygen-regulated Ni-based single-atom catalysts (SACs) show great potential in accelerating the kinetics of electrocatalytic CO₂ reduction reaction (CO₂RR). However, it remains a challenge to precisely control the coordination environment of Ni O moieties and achieve high activity at high overpotentials. Herein, a facile carbonization coupled oxidation strategy is developed to mass produce NiO clusters-decorated Ni N C SACs that exhibit a high Faradaic efficiency of CO (maximum of 96.5%) over a wide potential range (−0.9 to −1.3 V versus reversible hydrogen electrode) and a high turnover frequency for CO production of 10 120 h⁻¹ even at the high overpotential of 1.19 V. Density functional theory calculations reveal that the highly dispersed NiO clusters induce electron delocalization of active sites and reduce the energy barriers for *COOH intermediates formation from CO₂, leading to an enhanced reaction kinetics for CO production. This study opens a new universal pathway for the construction of oxygen-regulated metal-based SACs for various catalytic applications.     

NiMoO4 Nanosheets Anchored on N?S Doped Carbon Clothes with Hierarchical Structure as a Bidirectional Catalyst toward Accelerating Polysulfides Conversion for Li?S Battery

The serious shuttle effect, sluggish reduction kinetics of polysulfides and the difficult oxidation reaction of Li₂S have hindered Li S battery practical application. Herein, a 3D hierarchical structure composed of NiMoO₄ nanosheets in situ anchored on N S doped carbon clothes (NiMoO₄@NSCC) as the free-standing host is creatively designed and constructed for Li S battery. Dual transitional metal oxide (NiMoO₄) increases the electrons density near the Fermi level due to the contribution of the incorporating molybdenum (Mo), leading to the smaller bandgap, and thus stronger metallic properties compared with NiO. Furthermore, as a bidirectional catalyst, NiMoO₄ is proposed to facilitate reductions of polysulfides through lengthening the S S bond distance of Li₂S₄ and reducing the free energy of polysulfides conversion, meanwhile promote critical oxidation of insulative discharge product (Li₂S) via lengthening Li S bond distance of Li₂S and decreasing Li₂S decomposition barrier. Therefore, after loading sulfur (2 mg cm⁻²), NiMoO₄@NSCC/S as the self-supporting cathode for the Li S battery exhibits impressive long cycle stability. This study proposes a concept of a bidirectional catalyst with dual metal oxides, which would supply a novel vision to construct the high-performance Li S battery.     

Highly Efficient Green Zn?Ag?In?S/Zn?In?S/ZnS QDs by a Strong Exothermic Reaction for Down‐Converted Green and Tripackage White LEDs

Highly efficient bright green‐emitting Zn? Ag? In? S (ZAIS)/Zn? In? S (ZIS)/ZnS alloy core/inner‐shell/shell quantum dots (QDs) are synthesized using a multistep hot injection method with a highly concentrated zinc acetate dihydrate precursor. ZAIS/ZIS/ZnS QD growth is realized via five sequential steps: a core growth process, a two‐step alloying–shelling process, and a two‐step shelling process. To enhance the photoluminescence quantum yield (PLQY), a ZIS inner‐shell is synthesized and added with a band gap located between the ZAIS alloy‐core and ZnS shell using a strong exothermic reaction. The synthesized ZAIS/ZIS/ZnS QDs shows a high PLQY of 87% with peak wavelength of 501 nm. Tripackage white down‐converted light‐emitting diodes (DC‐LEDs) are realized using an InGaN blue (B) LED, a green (G) ZAIS/ZIS/ZS QD‐based DC‐LED, and a red (R) Zn? Cu? In? S/ZnS QD‐based DC‐LED with correlated color temperature from 2700 to 10 000 K. The red, green, and blue tripackage white DC‐LEDs exhibit high luminous efficacy of 72 lm W^?1 and excellent color qualities (color rendering index (CRI, R _a) = 95 and the special CRI for red (R ₉) = 93) at 2700 K.     

Rh?MoS2 Nanocomposite Catalysts with Pt‐Like Activity for Hydrogen Evolution Reaction

High overpotentials and low efficiency are two main factors that restrict the practical application for MoS₂, the most promising candidate for hydrogen evolution catalysis. Here, Rh? MoS₂ nanocomposites, the addition of a small amount of Rh (5.2 wt%), exhibit the superior electrochemical hydrogen evolution performance with low overpotentials, small Tafel slope (24 mV dec^?1), and long term of stability. Experimental results reveal that 5.2 wt% Rh? MoS₂ nanocomposite, even exceeding the commercial 20 wt% Pt/C when the potential is less than ?0.18 V, exhibits an excellent mass activity of 13.87 A mg_metal^?1 at ?0.25 V, four times as large as that of the commercial 20 wt% Pt/C catalyst. The hydrogen yield of 5.2 wt% Rh? MoS₂ nanocomposite is 26.3% larger than that of the commercial 20 wt% Pt/C at the potential of ?0.25 V. The dramatically improved electrocatalytic performance of Rh? MoS₂ nanocomposites may be attributed to the hydrogen spillover from Rh to MoS₂.     

Hierarchical Ni?Mo?S and Ni?Fe?S Nanosheets with Ultrahigh Energy Density for Flexible All Solid‐State Supercapacitors

Highly flexible supercapacitors (SCs) have great potential in modern electronics such as wearable and portable devices. However, ultralow specific capacity and low operating potential window limit their practical applications. Herein, a new strategy for the fabrication of free‐standing Ni? Mo? S and Ni? Fe? S nanosheets (NSs) for high‐performance flexible asymmetric SC (ASC) through hydrothermal and subsequent sulfurization technique is reported. The effect of Ni²⁺ is optimized to attain hierarchical Ni? Mo? S and Ni? Fe? S NS architectures with high electrical conductivity, large surface area, and exclusive porous networks. Electrochemical properties of Ni? Mo? S and Ni? Fe? S NS electrodes exhibit that both have ultrahigh specific capacities (≈312 and 246 mAh g^?1 at 1 mA cm^?2), exceptional rate capabilities (78.85% and 78.46% capacity retention even at 50 mA cm^?2, respectively), and superior cycling stabilities. Most importantly, a flexible Ni? Mo? S NS//Ni? Fe? S NS ASC delivers a high volumetric capacity of ≈1.9 mAh cm^?3, excellent energy density of ≈82.13 Wh kg^?1 at 0.561 kW kg^?1, exceptional power density (≈13.103 kW kg^?1 at 61.51 Wh kg^?1) and an outstanding cycling stability, retaining ≈95.86% of initial capacity after 10 000 cycles. This study emphasizes the potential importance of compositional tunability of the NS architecture as a novel strategy for enhancing the charge storage properties of active electrodes.     

Large‐Scale Li?O2 Pouch Type Cells for Practical Evaluation and Applications

Due to their high theoretical specific capacity and energy density, Li? O₂ batteries are considered as candidates for next‐generation battery systems in place of conventional Li‐ion batteries for advanced applications such as electric vehicles. However, low energy efficiency, poor cycle life, and Li‐metal safety issues make the use of Li? O₂ batteries yet impractical. In addition, actual cell capacities are very low, and since only small‐scale electrodes are currently tested, it is hard to predict the properties of large‐size electrodes and cells, thus evaluating and judging real practical challenges related to this battery technology. In this work, the behavior of pouch‐type Li? O₂ cells using 3 × 5 cm² sized electrodes is investigated and it is confirmed that Li‐metal is a key issue for the upscale of Li? O₂ cells. This study can help to determine which parameters are the most important for developing practical Li? O₂ batteries.     

Mg?Si?As: An Unexplored System with Promising Nonlinear Optical Properties

Two new non‐centrosymmetric ternary compounds, MgSiAs₂ and Mg₃Si₆As₈, are discovered via metal flux and solid‐state synthetic methods. MgSiAs₂ belongs to the well‐known II‐IV‐V₂ family, which is extensively studied experimentally and computationally for their optical properties. MgSiAs₂ is computationally predicted but not experimentally known prior to this work. Mg₃Si₆As₈ crystallizes in a new non‐centrosymmetric cubic chiral structure type with the Pearson symbol cP68. The syntheses, crystal structure, thermal and chemical stabilities, electronic structures, and optical properties of these two new compounds are investigated in this work. Optical absorption measurements and electronic structure calculations reveal the two compounds to be direct or pseudo‐direct bandgap semiconductors (1.8–2 eV). The crystal structures of both compounds are non‐centrosymmetric, though Mg₃Si₆As₈ belongs to the 432 chiral crystal class, which is optically active but does not exhibit second harmonic generation (SHG) behavior. The SHG response of MgSiAs₂ is 60% of that for AgGaS₂, but MgSiAs₂ exhibits a higher laser damage threshold than AgGaS₂ at 33.2 MW cm^?2.     

Carbon Black-Supported Single-Atom Co?N?C as an Efficient Oxygen Reduction Electrocatalyst for H2O2 Production in Acidic Media and Microbial Fuel Cell in Neutral Media

Single metal atom isolated in nitrogen-doped carbon materials (M N C) are effective electrocatalysts for oxygen reduction reaction (ORR), which produces H₂O₂ or H₂O via 2-electron or 4-electron process. However, most of M N C catalysts can only present high selectivity for one product, and the selectivity is usually regulated by complicated structure design. Herein, a carbon black-supported Co N C catalyst (CB@Co N C) is synthesized. Tunable 2-electron/4-electron behavior is realized on CB@Co-N-C by utilizing its H₂O₂ yield dependence on electrolyte pH and catalyst loading. In acidic media with low catalyst loading, CB@Co N C presents excellent mass activity and high selectivity for H₂O₂ production. In flow cell with gas diffusion electrode, a H₂O₂ production rate of 5.04 mol h⁻¹ g⁻¹ is achieved by CB@Co N C on electrolyte circulation mode, and a long-term H₂O₂ production of 200 h is demonstrated on electrolyte non-circulation mode. Meanwhile, CB@Co N C exhibits a dominant 4-electron ORR pathway with high activity and durability in pH neutral media with high catalyst loading. The microbial fuel cell using CB@Co N C as the cathode catalyst shows a peak power density close to that of benchmark Pt/C catalyst.     

Mechanochemical Post-Synthesis of Metal–Organic Framework-Based Pre-Electrocatalysts with Surface Fe?O?Ni/Co Bonding for Highly Efficient Oxygen Evolution

Rational surface engineering of metal–organic frameworks (MOFs) provide potential opportunities to address the sluggish kinetics of oxygen evolution reaction (OER). However, the development of MOF-based materials with low overpotentials remains a great challenge. Herein, a post-synthesis strategy to prepare highly efficient MOF-based pre-electrocatalysts via all-solid-phase mechanochemistry is demonstrated. The surface of a Fe-based MOF (MIL-53) can be reconstructed and anchored with atomically dispersed Ni/Co sites. As expected, the optimized M-NiA-CoN exhibits a very low overpotential of 180 mV at 10 mA cm⁻² and a small Tafel slope of 41 mV dec⁻¹ in 1 m KOH electrolyte. The superior electrocatalytic OER activity is mainly due to the formation of surface Fe O Ni/Co bonding. Furthermore, density functional theory calculations reveal that the transformation from ^*OH to ^*O is the rate-determining step and the electrocatalytic OER activity trend at different metal sites is Co > Ni≈Fe.     

Single-Atom Cadmium-N4 Sites for Rechargeable Li–CO2 Batteries with High Capacity and Ultra-Long Lifetime

The rechargeable Li–CO₂ battery shows great potential in civil, military, and aerospace fields due to its high theoretical energy density and CO₂ capture capability. To facilitate the practical application of Li–CO₂ battery, the design of efficient, low-cost, and robust non-noble metal cathodes to boost CO₂ reduction/evolution kinetics is highly desirable yet remains a challenge. Herein, single-atom cadmium is reported with a Cd-N₄ coordination structure enable rapid kinetics of both the discharge and recharge process when employed as a cathode catalyst, and thus facilitates exceptional rate performance in a Li–CO₂ battery, even up to 10 A g⁻¹, and remains stable at a high current density (100 A g⁻¹). An unprecedented discharge capacity of 160045 mAh g⁻¹ is attained at 500 mA g⁻¹. Excellent cycling stability is maintained for 1685 and 669 cycles at 1 A g⁻¹ and capacities of 0.5 and 1 Ah g⁻¹, respectively. Density functional theory calculations reveal low energy barriers for both Li₂CO₃ formation and decomposition reactions during the respective discharge and recharge process, evidencing the high catalytic activity of single Cd sites. This study provides a simple and effective avenue for developing highly active and stable single-atom non-precious metal cathode catalysts for advanced Li–CO₂ batteries.     

Regulating Fe Aggregation State via Unique Fe?N?V Pre-Coordination to Optimize the Adsorption-Catalysis Effect in High-Performance Lithium-Sulfur Batteries

Lithium-sulfur batteries (LSBs) suffer from uncontrollable shuttling behavior of lithium polysulfides (LiPSs: Li₂S_x, 4 ≤ x ≤8) and the sluggish reaction kinetics of bidirectional liquid-solid transformations, which are commonly coped through a comprehensive adsorption-catalysis strategy. Herein, a unique Fe N V pre-coordination is introduced to regulate the content of “dissociative Fe³⁺” in liquid phase, realizing the successful construction of N-doped micro-mesoporous “urchin-like” hollow carbon nanospheres decorated with single atom Fe-N₄ sites and VN nanoparticles (denoted as SA-Fe/VN@NMC). The strong chemisorption ability toward LiPSs and catalyzed Li₂S decomposition behavior on VN, along with the boosted reaction kinetics for sulfur reduction on SA-Fe sites are experimentally and theoretically evidenced. Moreover, the nanoscale-neighborhood distribution of VN and SA-Fe active sites presents synergistic effect for the anchoring-reduction-decomposition process of sulfur species. Thus SA-Fe/VN@NMC presents an optimized adsorption-catalysis effect for the whole sulfur conversion. Therefore, the SA-Fe/VN@NMC based Li-S cells exhibit high cyclic stability (a low decay of 0.024% per cycle over 700 cycles at 1 C, sulfur content: 70 wt%) and considerable rate performance (683.2 mAh g⁻¹ at 4 C). Besides, a high areal capacity of 5.06 mAh cm⁻² is retained after 100 cycles under the high sulfur loading of 5.6 mg cm⁻². This work provides a new perspective to design the integrated electrocatalysts comprising hetero-formed bimetals in LSBs.     

Efficient Electrocatalytic Reduction of CO2 to Ethanol Enhanced by Spacing Effect of Cu?Cu in Cu2-xSe Nanosheets

It is highly desired yet challenging to strategically steer carbon dioxide (CO₂) electroreduction reaction (CO₂ER) toward ethanol (EtOH) with high activity, which provides a promising way for intermittent renewable energy reservation. Controlling spatial distance between the adjoining active centers and promoting the C C coupling progress are crucial to realize this purpose. Herein, ultrathin 2D Cu_2-xSe is prepared with abundant Se vacancies, where the spatial distance between the Cu Cu around the Se vacancies is effectively shortened because of the lattice stress. Besides, the moderate spatial distance induced by Se vacancies can significantly decrease the Gibbs free energy of asymmetric *CO *CHO coupling progress, effectively change the local charge distribution, decrease the valence state of Cu atoms and increase the electron-donating capacity of the dual active sites. Combining experimental observations and density functional theory   simulations, the Cu Cu dual sites with spatial distance of 2.51 Å in V_Se-Cu_2-xSe sample can catalyze CO₂ER to EtOH with high selectivity in a potential range from −0.4 to −1.6 V, and reach the highest faradaic efficiency of 68.1% at −0.8 V. This work reveals the influence of spacing effect on ethanol selectivity, and provides a new idea for future design of catalysts with chain elongation reaction, which can bring extensive attention.     

Evaluation of Zn?Sn?O buffer layers for CuIn0.5Ga0.5Se2 solar cells

Thin Zn Sn O films are evaluated as new buffer layer material for Cu(In,Ga)Se₂‐based solar cell devices. A maximum conversion efficiency of 13.8% (V_oc = 691 mV, J_sc(QE) = 27.9 mA/cm², and FF = 71.6%) is reached for a solar cell using the Zn Sn O buffer layer which is comparable to the efficiency of 13.5% (V_oc = 706 mV, J_sc(QE) = 26.3 mA/cm², and FF = 72.9%) for a cell using the standard reference CdS buffer layer. The open circuit voltage (V_oc) and the fill factor (FF) are found to increase with increasing tin content until an optimum in both parameters is reached for Sn/(Zn + Sn) values around 0.3–0.4. Copyright © 2010 John Wiley & Sons, Ltd.     

Sieve Tube-Inspired Polysulfide Cathode with Long-Range Ordered Channels and Localized Capture-Catalysis Microenvironments for Efficient Li–S Batteries

Accelerating the conversion of soluble lithium polysulfides (LiPSs) to solid Li₂S₂/Li₂S through single-atom cathodes has emerged as a promising strategy for realizing high-performance lithium–sulfur batteries. However, rationally optimizing the conversion effects and spatial capture abilities of LiPSs intermediates on the atomic catalytic sites is extremely required but still faces enormous challenges. Here, inspired by the delicate structure of sieve tubes in plants, Fe single-atom cathode (channel-Fe_SAC) equipped with long-range ordered channels and localized capture-catalysis microenvironments towards efficient LiPSs conversion is reported on designing. Benefiting from the individual and stable catalytic areal for localized capture and migration inhibition abilities on LiPSs and fully confined triple-phase boundaries between atomic catalytic centers, conductive carbon, and electrolytes, the channel-Fe_SAC can effectively convert polysulfides, thus eliminating the shuttle effects and generation of inactive LiPSs. It is also elucidated that the channel-Fe_SAC exhibits superior migration inhibition of polysulfide and accelerates Li₂S deposition/conversion kinetics compared with bowl-Fe_SAC and flat-Fe_SAC. The outstanding areal capacity and cycling stability under high sulfur loading and low electrolyte/sulfur ratio verify that the channel-Fe_SAC holds great potential as cathodes for high-performance cathodes. This work offers vital insights into the essential roles of bioinspired fully confined channels and catalytic microenvironments in polysulfide catalysis for efficient lithium–sulfur batteries.     

Dual-Phasic Carbon with Co Single Atoms and Nanoparticles as a Bifunctional Oxygen Electrocatalyst for Rechargeable Zn–Air Batteries

The great interest in rechargeable Zn–air batteries (ZABs) arouses extensive research on low-cost, high-active, and durable bifunctional electrocatalysts to boost the sluggish oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). It remains a great challenge to simultaneously host high-active and independent ORR and OER sites in a single catalyst. Herein a dual-phasic carbon nanoarchitecture consisting of a single-atom phase for the ORR and nanosized phase for the OER is proposed. Specifically, single Co atoms supported on carbon nanotubes (single-atom phase) and nanosized Co encapsulated in zeolitic-imidazole-framework-derived carbon polyhedron (nanosized phase) are integrated together via carbon nanotube bridges. The obtained dual-phasic carbon catalyst shows a small overpotential difference of 0.74 V between OER potential at 10 mA cm⁻² and ORR half-wave potential. The ZAB based on the bifunctional catalyst demonstrates a large power density of 172 mW cm⁻². Furthermore, it shows a small charge-discharge potential gap of 0.51 V at 5 mA cm⁻² and outstanding discharge-charge cycling durability. This study provides a feasible design concept to achieve multifunctional catalysts and promotes the development of rechargeable ZABs.     

Ni1−xCoxSe2?C/ZnIn2S4 Hybrid Nanocages with Strong 2D/2D Hetero-Interface Interaction Enable Efficient H2-Releasing Photocatalysis

Designing a semiconductor-based heterostructure photocatalyst for achieving the efficient separation of photogenerated electron-hole pairs is highly important for enhancing H₂ releasing photocatalysis. Here, a new class of Ni_1−xCo_xSe₂–C/ZnIn₂S₄ hierarchical nanocages with abundant and compact ZnIn₂S₄ nanosheets/Ni_1−xCo_xSe₂^ C nanosheets 2D/2D hetero–interfaces, is designed and synthesized. The constructed heterostructure photocatalyst exposes rich hetero-junctions, supplying the broad and short transfer paths for charge carriers. The close contacts of these two kinds of nanosheets induce a strong interaction between ZnIn₂S₄ and Ni_1−xCo_xSe₂ C, improving the separation and transfer of photo-generated electron-hole pairs. As a consequence, the distinctive Ni_1−xCo_xSe₂ C/ZnIn₂S₄ hierarchical nanocages without using additional noble-metal cocatalysts, display remarkable H₂-relaesing photocatalytic activity with a rate of 5.10 mmol g⁻¹ h⁻¹ under visible light irradiation, which is 6.2 and 30 times higher than those of fresh ZnIn₂S₄ nanosheets and bare Ni_1−xCo_xSe₂ C nanocages, respectively. Spectroscopic characterizations and theory calculations reveal that the strong interaction between ZnIn₂S₄ and Ni_1−xCo_xSe₂ C 2D/2D hetero-interfaces can powerfully promote the separation of photo-generated charge carriers and the electrons transfer from ZnIn₂S₄ to Ni_1−xCo_xSe₂ C.