Conjugated Acetylenic Polymers Grafted Cuprous Oxide as an Efficient Z-Scheme Heterojunction for Photoelectrochemical Water Reduction

As attractive materials for photoeletrochemical hydrogen evolution reaction (PEC HER), conjugated polymers (e.g., conjugated acetylenic polymers [CAPs]) still show poor PEC HER performance due to the associated serious recombination of photogenerated electrons and holes. Herein, taking advantage of the in situ conversion of nanocopper into Cu₂O on copper cellulose paper during catalyzing of the Glaser coupling reaction, a general strategy for the construction of a CAPs/Cu₂O Z-scheme heterojunction for PEC water reduction is demonstrated. The as-fabricated poly(2,5-diethynylthieno[3,2-b]thiophene) (pDET)/Cu₂O Z-scheme heterojunction exhibits a carrier separation efficiency of 16.1% at 0.3 V versus reversible hydrogen electrode (RHE), which is 6.7 and 1.4-times higher respectively than those for pDET and Cu₂O under AM 1.5G irradiation (100 mW cm⁻²) in the 0.1 m Na₂SO₄ aqueous solution. Consequently, the photocurrent of the pDET/Cu₂O Z-scheme heterojunction reaches ≈ 520 µ A cm⁻² at 0.3 V versus RHE, which is much higher than pDET ( ≈ 80 µ A cm⁻²), Cu₂O ( ≈ 100 µ A cm⁻²), and the state-of-the-art cocatalyst-free organic or organic-semiconductor-based heterojunctions/homojunctions photocathodes (1–370 µ A cm⁻²). This work advances the design of polymer-based Z-scheme heterojunctions and high-performance organic photoelectrodes.     

Highly Efficient Hydrogen Evolution from a Mesoporous Hybrid of Nickel Phosphide Nanoparticles Anchored on Cobalt Phosphosulfide/Phosphide Nanosheet Arrays

Facile design of low‐cost and high‐efficiency catalysts with earth‐abundant and cheap materials is desirable to replace platinum (Pt) for the hydrogen evolution reaction (HER) in water splitting, but the development of such HER catalysts with Pt‐like activity using simple strategies remains challenging. A mesoporous hybrid catalyst of nickel phosphides nanoparticles and cobalt phosphosulfide/phosphide (CoS|Ni|P) nanosheet arrays for HER is reported here, which is developed by a facile three‐step approach consisting of electrodeposition, thermal sulfurization, and phosphorization. This hybrid catalyst is highly robust and stable in acid for HER, and is distinguished by very low overpotentials of 41, 88, and 150 mV to achieve 10, 100, and 1000 mA cm^?2, respectively, as well as a small Tafel slope (45.2 mV dec^?1), and a large exchange current density (964 µA cm^?2). It is among the most efficient earth‐abundant catalysts reported thus far for HER. More importantly, this electrocatalyst has electrochemical durability over 20 h under a wide range of current densities (up to 1 A cm^?2) in acidic conditions, as well as very high turnover frequencies of 0.40 and 1.26 H₂ s^?1 at overpotentials of 75 and 100 mV, respectively, showing that it has great potential for practical applications in large‐scale water electrolysis.     

Hydrogen Terminated Germanene for a Robust Self‐Powered Flexible Photoelectrochemical Photodetector

As a rising star in the family of graphene analogues, germanene shows great potential for electronic and optical device applications due to its unique structure and electronic properties. It is revealed that the hydrogen terminated germanene not only maintains a high carrier mobility similar to that of germanene, but also exhibits strong light–matter interaction with a direct band gap, exhibiting great potential for photoelectronics. In this work, few‐layer germanane (GeH) nanosheets with controllable thickness are successfully synthesized by a solution‐based exfoliation–centrifugation route. Instead of complicated microfabrication techniques, a robust photoelectrochemical (PEC)‐type photodetector, which can be extended to flexible device, is developed by simply using the GeH nanosheet film as an active electrode. The device exhibits an outstanding photocurrent density of 2.9 µA cm^?2 with zero bias potential, excellent responsivity at around 22 µA W^?1 under illumination with intensity ranging from 60 to 140 mW cm^?2, as well as short response time (with rise and decay times, t_r = 0.24 s and t_d = 0.74 s). This efficient strategy for a constructing GeH‐based PEC‐type photodetector suggests a path to promising high‐performance, self‐powered, flexible photodetectors, and it also paves the way to a practical application of germanene.     

Thiophene‐Bridged Donor–Acceptor sp2‐Carbon‐Linked 2D Conjugated Polymers as Photocathodes for Water Reduction

Photoelectrochemical (PEC) water reduction, converting solar energy into environmentally friendly hydrogen fuel, requires delicate design and synthesis of semiconductors with appropriate bandgaps, suitable energy levels of the frontier orbitals, and high intrinsic charge mobility. In this work, the synthesis of a novel bithiophene‐bridged donor–acceptor‐based 2D sp²‐carbon‐linked conjugated polymer (2D CCP) is demonstrated. The Knoevenagel polymerization between the electron‐accepting building block 2,3,8,9,14,15‐hexa(4‐formylphenyl) diquinoxalino[2,3‐a:2′,3′‐c]phenazine (HATN‐6CHO) and the first electron‐donating linker 2,2′‐([2,2′‐bithiophene]‐5,5′‐diyl)diacetonitrile (ThDAN) provides the 2D CCP‐HATNThDAN (2D CCP‐Th). Compared with the corresponding biphenyl‐bridged 2D CCP‐HATN‐BDAN (2D CCP‐BD), the bithiophene‐based 2D CCP‐Th exhibits a wide light‐harvesting range (up to 674 nm), a optical energy gap (2.04 eV), and highest energy occupied molecular orbital–lowest unoccupied molecular orbital distributions for facilitated charge transfer, which make 2D CCP‐Th a promising candidate for PEC water reduction. As a result, 2D CCP‐Th presents a superb H₂‐evolution photocurrent density up to ≈7.9 µA cm^?2 at 0 V versus reversible hydrogen electrode, which is superior to the reported 2D covalent organic frameworks and most carbon nitride materials (0.09–6.0 µA cm^?2). Density functional theory calculations identify the thiophene units and cyano substituents at the vinylene linkage as active sites for the evolution of H₂.     

Modulation of Inverse Spinel Fe3O4 by Phosphorus Doping as an Industrially Promising Electrocatalyst for Hydrogen Evolution

Fe‐based oxides have been seldom reported as electrocatalysts for the hydrogen evolution reaction (HER), limited by their weak intrinsic activity and conductivity. Herein, phosphorus doping modulation is used to construct inverse spinel P‐Fe₃O₄ with dual active sites supported on iron foam (P‐Fe₃O₄/IF) for alkaline HER with an extremely low overpotential of 138 mV at 100 mA cm^?2. The obtained inverse spinel Fe–O–P derived from controllable phosphorization can provide an octahedral Fe site and O atom, which bring about the unusual dissociation mechanisms of two water molecules to greatly accelerate the proton supply in alkaline media. Meanwhile, the ΔG_H of the P atom in Fe–O–P as an active site is theoretically calculated to be 0.01 eV. Notably, the NiFe LDH/IF⁽⁺⁾||P‐Fe₃O₄/IF^(?) couple achieves an onset potential of 1.47 V (vs RHE) for overall water splitting, with excellent stability for more than 1000 h at a current density of 1000 mA cm^?2, and even for 25 000 s at 10 000 mA cm^?2 in 6.0 m KOH at 60 °C. The excellent catalyst stability and low‐cost merits of P‐Fe₃O₄/IF may hold promise for industrial hydrogen production. This work may reveal a new design strategy of earth‐abundant materials for large‐scale water splitting.     

Spinel Structural Disorder Influences Solar‐Water‐Splitting Performance of ZnFe2O4 Nanorod Photoanodes

Zinc spinel ferrite, ZnFe₂O₄ (ZFO), is an emerging photoanode material for photoelectrochemical (PEC) solar fuel production. However, a lack of fundamental insight into the factors limiting the photocurrent has prevented substantial advance in its performance. Herein, it is found that ZFO nanorod array photoelectrodes with varying crystallinity exhibit vastly different PEC properties. Using a sacrificial hole scavenger (H₂O₂), spatially defined carrier generation, and electrochemical impedance spectroscopy, it is shown that ZFO with a relatively poor crystallinity but a higher spinel inversion degree (due to cation disorder) exhibits superior photogenerated charge separation efficiency and improved majority charge carrier transport compared to ZFO with higher crystallinity and a lower inversion degree. Conversely, the latter condition leads to better charge injection efficiency. Optimization of these factors, and the addition of a nickel–iron oxide cocatalyst overlayer, leads to a new benchmark solar photocurrent for ZFO of 1.0 mA cm^?2 at 1.23 V versus reversible hydrogen electrode (RHE) and 1.7 mA cm^?2 at 1.6 V versus RHE. Importantly, the observed correlation between the cation disorder and the PEC performance represents a new insight into the factors important to the PEC performance of the spinel ferrites and suggests a path to further improvement.     

GaP/GaNP Heterojunctions for Efficient Solar‐Driven Water Oxidation

The growth and characterization of an n‐GaP/i‐GaNP/p⁺‐GaP thin film heterojunction synthesized using a gas‐source molecular beam epitaxy (MBE) method, and its application for efficient solar‐driven water oxidation is reported. The TiO₂/Ni passivated n‐GaP/i‐GaNP/p⁺‐GaP thin film heterojunction provides much higher photoanodic performance in 1 m KOH solution than the TiO₂/Ni‐coated n‐GaP substrate, leading to much lower onset potential and much higher photocurrent. There is a significant photoanodic potential shift of 764 mV at a photocurrent of 0.34 mA cm^?2, leading to an onset potential of ≈0.4 V versus reversible hydrogen electrode (RHE) at 0.34 mA cm^?2 for the heterojunction. The photocurrent at the water oxidation potential (1.23 V vs RHE) is 1.46 and 7.26 mA cm^?2 for the coated n‐GaP and n‐GaP/i‐GaNP/p⁺‐GaP photoanodes, respectively. The passivated heterojunction offers a maximum applied bias photon‐to‐current efficiency (ABPE) of 1.9% while the ABPE of the coated n‐GaP sample is almost zero. Furthermore, the coated n‐GaP/i‐GaNP/p⁺‐GaP heterojunction photoanode provides a broad absorption spectrum up to ≈620 nm with incident photon‐to‐current efficiencies (IPCEs) of over 40% from ≈400 to ≈560 nm. The high low‐bias performance and broad absorption of the wide‐bandgap GaP/GaNP heterojunctions render them as a promising photoanode material for tandem photoelectrochemical (PEC) cells to carry out overall solar water splitting.     

Polymer Doping Enables a Two‐Dimensional Electron Gas for High‐Performance Homojunction Oxide Thin‐Film Transistors

High‐performance solution‐processed metal oxide (MO) thin‐film transistors (TFTs) are realized by fabricating a homojunction of indium oxide (In₂O₃) and polyethylenimine (PEI)‐doped In₂O₃ (In₂O₃:x% PEI, x = 0.5–4.0 wt%) as the channel layer. A two‐dimensional electron gas (2DEG) is thereby achieved by creating a band offset between the In₂O₃ and PEI‐In₂O₃ via work function tuning of the In₂O₃:x% PEI, from 4.00 to 3.62 eV as the PEI content is increased from 0.0 (pristine In₂O₃) to 4.0 wt%, respectively. The resulting devices achieve electron mobilities greater than 10 cm² V^?1 s^?1 on a 300 nm SiO₂ gate dielectric. Importantly, these metrics exceed those of the devices composed of the pristine In₂O₃ materials, which achieve a maximum mobility of ≈4 cm² V^?1 s^?1. Furthermore, a mobility as high as 30 cm² V^?1 s^?1 is achieved on a high‐k ZrO₂ dielectric in the homojunction devices. This is the first demonstration of 2DEG‐based homojunction oxide TFTs via band offset achieved by simple polymer doping of the same MO material.     

Hierarchical CdS Nanorod@SnO2 Nanobowl Arrays for Efficient and Stable Photoelectrochemical Hydrogen Generation

An efficient photoanode based on CdS nanorod@SnO₂ nanobowl (CdS NR@SnO₂ NB) arrays is designed and fabricated by the preparation of SnO₂ nanobowl arrays via nanosphere lithography followed by hydrothermal growth of CdS nanorods on the inner surface of the SnO₂ nanobowls. A photoelectrochemical (PEC) device constructed by using this hierarchical CdS NR@SnO₂ NB photoanode presents significantly enhanced performance with a photocurrent density of 3.8 mA cm^?2 at 1.23 V versus a reversible hydrogen electrode (RHE) under AM1.5G solar light irradiation, which is about 2.5 times higher than that of CdS nanorod arrays. After coating with a thin layer of SiO₂, the photostability of the CdS NR@SnO₂ NB arrays is greatly enhanced, resulting in a stable photoanode with a photocurrent density of 3.0 mA cm^?2 retained at 1.23 V versus the RHE. The much improved performance of the CdS NR@SnO₂ NB arrays toward PEC hydrogen generation can be ascribed to enlarged surface area arising from the hierarchical nanostructures, improved light harvesting owing to the NR@NB architecture containing multiple scattering centers, and enhanced charge separation/collection efficiency due to the favorable CdS–SnO₂ heterojunction.     

Phosphorus‐Rich Colloidal Cobalt Diphosphide (CoP2) Nanocrystals for Electrochemical and Photoelectrochemical Hydrogen Evolution

Developing earth‐abundant and efficient electrocatalysts for photoelectrochemical water splitting is critical to realizing a high‐performance solar‐to‐hydrogen energy conversion process. Herein, phosphorus‐rich colloidal cobalt diphosphide nanocrystals (CoP₂ NCs) are synthesized via hot injection. The CoP₂ NCs show a Pt‐like hydrogen evolution reaction (HER) electrocatalytic activity in acidic solution with a small overpotential of 39 mV to achieve ?10 mA cm^?2 and a very low Tafel slope of 32 mV dec^?1. Density functional theory (DFT) calculations reveal that the high P content both physically separates Co atoms to prevent H from over binding to multiple Co atoms, while simultaneously stabilizing H adsorbed to single Co atoms. The catalytic performance of the CoP₂ NCs is further demonstrated in a metal–insulator–semiconductor photoelectrochemical device consisting of bottom p‐Si light absorber, atomic layer deposition Al–ZnO passivation layers, and the CoP₂ cocatalyst. The p‐Si/AZO/TiO₂/CoP₂ photocathode shows a photocurrent density of ?16.7 mA cm^?2 at 0 V versus reversible hydrogen electrode (RHE) and an output photovoltage of 0.54 V. The high performance and stability are attributed to the junction between p‐Si and AZO, the corrosion‐resistance of the pinhole‐free TiO₂ protective layer, and the fast HER kinetics of the CoP₂ NCs.     

Facile,Room Temperature,Electroless Deposited (Fe1−x,Mnx)OOH Nanosheets as Advanced Catalysts: The Role of Mn Incorporation

Herein, bimetallic iron (Fe)–manganese (Mn) oxyhydroxide ((Fe_1−x,Mn_x)OOH, FeMnOOH) nanosheets on fluorine‐doped tin oxide conducting substrates and on semiconductor photoanodes are synthesized by a facile, room temperature, electroless deposition method as catalysts for both electrochemical and photo‐electrochemical (PEC) water splitting, respectively. Surprisingly, Mn‐doped FeOOH can significantly modulate the nanosheet morphology to increase the active surface area, boost more active sites, and augment the intrinsic activity by tuning the electronic structure of FeOOH. Due to the 2D nanosheet architecture, the optimized FeMnOOH exhibits superior electrochemical activity and outstanding durability for the oxygen evolution reaction with a low overpotential of 246 mV at 10 mA cm⁻² and 414 mV at 100 mA cm⁻², and long‐term stability for 40 h without decay, which is comparable to the best electrocatalysts for water oxidation reported in the literature. By integrating with semiconductor photoanodes (such as α‐Fe₂O₃ nanorod (NR) arrays), bimetallic FeMnOOH catalysts achieve solar‐driven water splitting with a significantly enhanced PEC performance (3.36 mA cm⁻² at 1.23 V vs reversible hydrogen electrode (RHE)) with outstanding long‐term stability (≈8 h) compared to that of the bare Fe₂O₃ NR (0.92 mA cm⁻² at 1.23 V vs RHE).     

Cobalt Covalent Doping in MoS2 to Induce Bifunctionality of Overall Water Splitting

The layer‐structured MoS₂ is a typical hydrogen evolution reaction (HER) electrocatalyst but it possesses poor activity for the oxygen evolution reaction (OER). In this work, a cobalt covalent doping approach capable of inducing HER and OER bifunctionality into MoS₂ for efficient overall water splitting is reported. The results demonstrate that covalently doping cobalt into MoS₂ can lead to dramatically enhanced HER activity while simultaneously inducing remarkable OER activity. The catalyst with optimal cobalt doping density can readily achieve HER and OER onset potentials of ?0.02 and 1.45 V (vs reversible hydrogen electrode (RHE)) in 1.0 m KOH. Importantly, it can deliver high current densities of 10, 100, and 200 mA cm^?2 at low HER and OER overpotentials of 48, 132, 165 mV and 260, 350, 390 mV, respectively. The reported catalyst activation approach can be adapted for bifunctionalization of other transition metal dichalcogenides.     

Scalable Design of Two‐Dimensional Oxide Nanosheets for Construction of Ultrathin Multilayer Nanocapacitor

Large size of capacitors is the main hurdle in miniaturization of current electronic devices. Herein, a scalable solution‐based layer‐by‐layer engineering of metallic and high‐κ dielectric nanosheets into multilayer nanosheet capacitors (MNCs) with overall thickness of ≈20 nm is presented. The MNCs are built through neat tiling of 2D metallic Ru_0.95O₂^0.2? and high‐κ dielectric Ca₂NaNb₄O₁₃^? nanosheets via the Langmuir–Blodgett (LB) approach at room temperature which is verified by cross‐sectional high‐resolution transmission electron microscopy (HRTEM). The resultant MNCs demonstrate a high capacitance of 40–52 µF cm^?2 and low leakage currents down to 10^?5–10^?6 A cm^?2. Such MNCs also possess complimentary in situ robust dielectric properties under high‐temperature measurements up to 250 °C. Based on capacitance normalized by the thickness, the developed MNC outperforms state‐of‐the‐art multilayer ceramic capacitors (MLCC, ≈22 µF cm^?2/5 × 10⁴ nm) present in the market. The strategy is effective due to the advantages of facile, economical, and ambient temperature solution assembly.     

Synergistic Phase and Disorder Engineering in 1T‐MoSe2 Nanosheets for Enhanced Hydrogen‐Evolution Reaction

MoSe₂ is a promising earth‐abundant electrocatalyst for the hydrogen‐evolution reaction (HER), even though it has received much less attention among the layered dichalcogenide (MX₂) materials than MoS₂ so far. Here, a novel hydrothermal‐synthesis strategy is presented to achieve simultaneous and synergistic modulation of crystal phase and disorder in partially crystallized 1T‐MoSe₂ nanosheets to dramatically enhance their HER catalytic activity. Careful structural characterization and defect characterization using positron annihilation lifetime spectroscopy correlated with electrochemical measurements show that the formation of the 1T phase under a large excess of the NaBH₄ reductant during synthesis can effectively improve the intrinsic activity and conductivity, and the disordered structure from a lower reaction temperature can provide abundant unsaturated defects as active sites. Such synergistic effects lead to superior HER catalytic activity with an overpotential of 152 mV versus reversible hydrogen electrode (RHE) for the electrocatalytic current density of j = ?10 mA cm^?2, and a Tafel slope of 52 mV dec^?1. This work paves a new pathway for improving the catalytic activity of MoSe₂ and generally MX₂‐based electrocatalysts via a synergistic modulation strategy.     

Fabry–Pérot Oscillation and Room Temperature Lasing in Perovskite Cube‐Corner Pyramid Cavities

Recently, organometal halide perovskite‐based optoelectronics, particularly lasers, have attracted intensive attentions because of its outstanding spectral coherence, low threshold, and wideband tunability. In this work, high‐quality CH₃NH₃PbBr₃ single crystals with a unique shape of cube‐corner pyramids are synthesized on mica substrates using chemical vapor deposition method. These micropyramids naturally form cube‐corner cavities, which are eminent candidates for small‐sized resonators and retroreflectors. The as‐grown perovskites show strong emission ≈530 nm in the vertical direction at room temperature. A special Fabry–Pérot (F–P) mode is employed to interpret the light confinement in the cavity. Lasing from the perovskite pyramids is observed from 80 to 200 K, with threshold ranging from ≈92 µJ cm^?2 to 2.2 mJ cm^?2, yielding a characteristic temperature of T₀ = 35 K. By coating a thin layer of Ag film, the threshold is reduced from ≈92 to 26 µJ cm^?2, which is accompanied by room temperature lasing with a threshold of ≈75 µJ cm^?2. This work advocates the prospect of shape‐engineered perovskite crystals toward developing micro‐sized optoelectronic devices and potentially investigating light–matter coupling in quantum optics.     

Network-like CuInS<Subscript>2</Subscript> photocathode and modified with noble metal co-catalyst for photoelectrochemical water splitting

It is of great significance to explore new preparation methods and control the morphology and proportion of metal ions for the photoelectrochemical (PEC) water splitting of ternary sulfide photoelectrode. In this paper, the network-like CuInS₂ film photocathodes were firstly prepared by hydrothermal growth method. The effects of different [Cu²⁺]/[In³⁺] molar ratios and concentrations of growth solution on CuInS₂ films were investigated in detail. The mechanism of the synthetic reaction was studied. The best PEC photocurrent density of the CuInS₂ film photoelectrode is ??0.81 mA/cm² at ??0.6 V versus RHE when the [Cu²⁺]/[In³⁺] molar ratio is 0.4, the growth solution concentration is 8 mmol/L CuCl₂·2H₂O, 20 mmol/L InCl₃·4H₂O and 60 mmol/L C₂H₅NS. For the purpose of further improving photoelectrochemical properties of CuInS₂ thin films, the Pt co-catalyst was loaded. The synthesized CuInS₂–Pt thin film yielded a photocurrent density for ??1.92 mA/cm² at ??0.6 V versus RHE due to the fast photogenerated electrons capture ability of Pt co-catalyst. The method of constructing photoelectrode film and the co-catalyst mechanism contributes to a sensational way for PEC water splitting of sulfide.     

3D FTO/FTO‐Nanocrystal/TiO2 Composite Inverse Opal Photoanode for Efficient Photoelectrochemical Water Splitting

A 3D fluorine‐doped SnO₂ (FTO)/FTO‐nanocrystal (NC)/TiO₂ inverse opal (IO) structure is designed and fabricated as a new “host and guest” type of composite photoanode for efficient photoelectrochemical (PEC) water splitting. In this novel photoanode design, the highly conductive and porous FTO/FTO‐NC IO acts as the “host” skeleton, which provides direct pathways for faster electron transport, while the conformally coated TiO₂ layer acts as the “guest” absorber layer. The unique composite IO structure is fabricated through self‐assembly of colloidal spheres template, a hydrothermal method and atomic layer deposition (ALD). Owing to its large surface area and efficient charge collection, the FTO/FTO‐NC/TiO₂ composite IO photoanode shows excellent photocatalytic properties for PEC water splitting. With optimized dimensions of the SnO₂ nanocrystals and the thickness of the ALD TiO₂ absorber layers, the 3D FTO/FTO‐NC/TiO₂ composite IO photoanode yields a photocurrent density of 1.0 mA cm^?2 at 1.23 V versus reversible hydrogen electrode (RHE) under AM 1.5 illumination, which is four times higher than that of the FTO/TiO₂ IO reference photoanode.     

MXene‐Derived Ferroelectric Crystals

This study demonstrates the first synthesis of MXene‐derived ferroelectric crystals. Specifically, high‐aspect‐ratio potassium niobate (KNbO₃) ferroelectric crystals is successfully synthesized using 2D Nb₂C, MXene, and potassium hydroxide (KOH) as the niobium and potassium source, respectively. Material analysis confirms that a KNbO₃ orthorhombic phase with Amm2 symmetry is obtained. Additionally, ferroelectricity in KNbO₃ is confirmed using standard ferroelectric, dielectric, and piezoresponse force microscopy measurements. The KNbO₃ crystals exhibit a saturated polarization of ≈21 µC cm^?2, a remnant polarization of ≈17 µC cm^?2, and a coercive field of ≈50 kV cm^?1. This discovery illustrates that the 2D nature of MXenes can be exploited to grow ferroelectric crystals.     

Room‐Temperature Solution‐Synthesized p‐Type Copper(I) Iodide Semiconductors for Transparent Thin‐Film Transistors and Complementary Electronics

Here, room‐temperature solution‐processed inorganic p‐type copper iodide (CuI) thin‐film transistors (TFTs) are reported for the first time. The spin‐coated 5 nm thick CuI film has average hole mobility (µ_FE) of 0.44 cm² V^?1 s^?1 and on/off current ratio of 5 × 10². Furthermore, µ_FE increases to 1.93 cm² V^?1 s^?1 and operating voltage significantly reduces from 60 to 5 V by using a high permittivity ZrO₂ dielectric layer replacing traditional SiO₂. Transparent complementary inverters composed of p‐type CuI and n‐type indium gallium zinc oxide TFTs are demonstrated with clear inverting characteristics and voltage gain over 4. These outcomes provide effective approaches for solution‐processed inorganic p‐type semiconductor inks and related electronics.     

2D Nanoporous Fe−N/C Nanosheets as Highly Efficient Non‐Platinum Electrocatalysts for Oxygen Reduction Reaction in Zn‐Air Battery

It is an ongoing challenge to fabricate nonprecious oxygen reduction reaction (ORR) catalysts that can be comparable to or exceed the efficiency of platinum. A highly active non‐platinum self‐supporting Fe?N/C catalyst has been developed through the pyrolysis of a new type of precursor of iron coordination complex, in which 1,4‐bis(1H‐1,3,7,8–tetraazacyclopenta(1)phenanthren‐2‐yl)benzene (btcpb) functions as a ligand complexing Fe(II) ions. The optimal catalyst pyrolyzed at 700 °C (Fe?N/C?700) shows the best ORR activity with a half‐wave potential (E_1/2) of 840 mV versus reversible hydrogen electrode (RHE) in 0.1 m KOH, which is more positive than that of commercial Pt/C (E_1/2: 835 mV vs RHE). Additionally, the Fe?N/C?700 catalyst also exhibits high ORR activity in 0.1 m HClO₄ with the onset potential and E_1/2 comparable to those of the Pt/C catalyst. Notably, the Fe?N/C?700 catalyst displays superior durability (9.8 mV loss in 0.1 m KOH and 23.6 mV loss in 0.1 m HClO₄ for E_1/2 after 8000 cycles) and better tolerance to methanol than Pt/C. Furthermore, the Fe?N/C?700 catalyst can be used for fabricating the air electrode in Zn–air battery with a specific capacity of 727 mA hg^?1 at 5 mA cm^?2 and a negligible voltage loss after continuous operation for 110 h.