Atomically dispersed asymmetric cobalt electrocatalyst for efficient hydrogen peroxide production in neutral media.

Electrochemical hydrogen peroxide (H2O2) production (EHPP) via a two-electron oxygen reduction reaction (2e- ORR) provides a promising alternative to replace the energy-intensive anthraquinone process. M-N-C electrocatalysts, which consist of atomically dispersed transition metals and nitrogen-doped carbon, have demonstrated considerable EHPP efficiency. However, their full potential, particularly regarding the correlation between structural configurations and performances in neutral media, remains underexplored. Herein, a series of ultralow metal-loading M-N-C electrocatalysts are synthesized and investigated for the EHPP process in the neutral electrolyte. CoNCB material with the asymmetric Co-C/N/O configuration exhibits the highest EHPP activity and selectivity among various as-prepared M-N-C electrocatalyst, with an outstanding mass activity (6.1 × 105 A gCo-1 at 0.5 V vs. RHE), and a high practical H2O2 production rate (4.72 mol gcatalyst-1 h-1 cm-2). Compared with the popularly recognized square-planar symmetric Co-N4 configuration, the superiority of asymmetric Co-C/N/O configurations is elucidated by X-ray absorption fine structure spectroscopy analysis and computational studies.

Spectroscopic Identification of Active Sites of Oxygen-Doped Carbon for Selective Oxygen Reduction to Hydrogen Peroxide.

The electrochemical synthesis of hydrogen peroxide (H2 O2 ) via a two-electron (2 e- ) oxygen reduction reaction (ORR) process provides a promising alternative to replace the energy-intensive anthraquinone process. Herein, we develop a facile template-protected strategy to synthesize a highly active quinone-rich porous carbon catalyst for H2 O2 electrochemical production. The optimized PCC900 material exhibits remarkable activity and selectivity, of which the onset potential reaches 0.83 V vs. reversible hydrogen electrode in 0.1 M KOH and the H2 O2 selectivity is over 95 % in a wide potential range. Comprehensive synchrotron-based near-edge X-ray absorption fine structure (NEXAFS) spectroscopy combined with electrocatalytic characterizations reveals the positive correlation between quinone content and 2 e- ORR performance. The effectiveness of chair-form quinone groups as the most efficient active sites is highlighted by the molecule-mimic strategy and theoretical analysis.

Cathode-Electrolyte Interface Modification by Binder Engineering for High-Performance Aqueous Zinc-Ion Batteries.

A stable cathode-electrolyte interface (CEI) is crucial for aqueous zinc-ion batteries (AZIBs), but it is less investigated. Commercial binder poly(vinylidene fluoride) (PVDF) is widely used without scrutinizing its suitability and cathode-electrolyte interface (CEI) in AZIBs. A water-soluble binder is developed that facilitated the in situ formation of a CEI protecting layer tuning the interfacial morphology. By combining a polysaccharide sodium alginate (SA) with a hydrophobic polytetrafluoroethylene (PTFE), the surface morphology, and charge storage kinetics can be confined from diffusion-dominated to capacitance-controlled processes. The underpinning mechanism investigates experimentally in both kinetic and thermodynamic perspectives demonstrate that the COO- from SA acts as an anionic polyelectrolyte facilitating the adsorption of Zn2+ ; meanwhile fluoride atoms on PTFE backbone provide hydrophobicity to break desolvation penalty. The hybrid binder is beneficial in providing a higher areal flux of Zn2+ at the CEI, where the Zn-Birnessite MnO2 battery with the hybrid binder exhibits an average specific capacity 45.6% higher than that with conventional PVDF binders; moreover, a reduced interface activation energy attained fosters a superior rate capability and a capacity retention of 99.1% in 1000 cycles. The hybrid binder also reduces the cost compared to the PVDF/NMP, which is a universal strategy to modify interface morphology.

Investigation of a Biomass Hydrogel Electrolyte Naturally Stabilizing Cathodes for Zinc-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) have the potential to be utilized in a grid-scale energy storage system owing to their high energy density and cost-effective properties. However, the dissolution of cathode materials and the irreversible extraction of preintercalated metal ions in the electrode materials restrict the stability of AZIBs. Herein, a cathode-stabilized ZIB strategy is reported based on a natural biomass polymer sodium alginate as the electrolyte coupling with a Na+ preintercalated δ-Na0.65Mn2O4·1.31H2O cathode. The dissociated Na+ in alginate after gelation directly stabilizes the cathodes by preventing the collapse of layered structures during charge processes. The as-fabricated ZIBs deliver a high capacity of 305 mA h g-1 at 0.1 A g-1, 10% higher than the ZIBs with an aqueous electrolyte. Further, the hybrid polymer electrolyte possessed an excellent Coulombic efficiency above 99% and a capacity retention of 96% within 1000 cycles at 2 A g-1. A detailed investigation combining ex situ experiments uncovers the charge storage mechanism and the stability of assembled batteries, confirming the reversible diffusions of both Zn2+ and preintercalated Na+. A flexible device of ZIBs fabricated based on vacuum-assisted resin transfer molding possesses an outstanding performance of 160 mA h g-1 at 1 A g-1, which illustrates their potential for wearable electronics in mass production.

High-Efficiency Perovskite Light-Emitting Diodes with Improved Interfacial Contact.

Unbalanced charge injection is one of the major issues that hampers the efficiency of perovskite light-emitting diodes (PeLEDs). Through engineering the device structure with multiple hole transport layers (HTLs), i.e., poly(9,9-dioctyl-fluorene-co-N-(4-butylphenyl)diphenylamine) (TFB)/poly(9-vinylcarbazole) (PVK) and nickel oxide (NiOx)/TFB/PVK, efficient PeLED devices have been successfully demonstrated. However, in a typical solution-processed PeLED with multiple HTLs, the underlying conjugated HTL could be easily redissolved by the ink of the following one, which not only dramatically deteriorates the electrical property of HTLs but also influences the quality of the top perovskite films. In this work, through inserting a thin atomic layer-deposited aluminum oxide (Al2O3) layer between HTLs and the perovskite layer, an improved interfacial contact can be achieved, which enables us to obtain perovskite films with enhanced characteristics and balanced charge injection in the resultant PeLEDs. In addition, because of the proper refractive index (r), the presence of the Al2O3 layer also favors the light out-coupling of PeLEDs. As a result, we fabricate green PeLEDs with good repeatability and external quantum efficiency of 17.0%, which is approximately 60% higher than that of the control device without Al2O3. Our work provides a promising avenue to enhance interfacial contact between the charge transport layer and perovskite for efficient perovskite-based optoelectronic devices.

Prominent Heat Dissipation in Perovskite Light-Emitting Diodes with Reduced Efficiency Droop for Silicon-Based Display.

Solution-processed perovskite light-emitting diodes (LEDs) possess outstanding optoelectronic properties for potential solid-state display applications. However, poor device stability results in significant efficiency droop partly being ascribed to Joule heating when LEDs are operated at high current densities. Herein, we used monocrystal silicon (c-Si) as the substrate and a charge injection layer to alleviate the thermal affection in perovskite LED (PeLED). By incorporating silicon oxide (SiOx) and poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-(4,4'-(N-(4-butylphenyl) (TFB) layers to tune the charge injection balance in a c-Si-based device, a PeLED achieves an external quantum efficiency of 2.12% with a current efficiency of 6.06 cd A-1. Benefiting from excellent heat dissipation of c-Si, the PeLEDs display reduced efficiency droop and extended operational lifetime. Furthermore, both electroluminescent (EL) dynamic information and static pattern displays of a c-Si-based PeLED have been successfully demonstrated. These results reveal the feasibility of potential practical c-Si-based PeLEDs with reduced efficiency droop for EL display applications.

Constant Electricity Generation in Nanostructured Silicon by Evaporation-Driven Water Flow.

Recently, hydrovoltaic technology emerged as a novel renewable energy harvesting method, which dramatically extends the capability to harvest water energy. However, the urgent issue restricting its device performance is poor carrier transport properties of the solid surface if large charged interface is considered simultaneously. Herein, a hydrovoltaic device based on silicon nanowire arrays (SiNWs), which provide large charged surface/volume ratio and excellent carrier transport properties, yields sustained electricity by a carrier concentration gradient induced by evaporation-induced water flow inside nanochannels. The device can yield direct current with a short-circuit current density of over 55 µA cm-2 , which is three orders larger than a previously reported analogous device (approximately 40 nA cm-2 ). Moreover, it exhibits a constant output power density of over 6 µW cm-2 and an open-circuit voltage of up to 400 mV. Our finding may pave a way for developing energy-harvesting devices from ubiquitous evaporation-driven internal water flow in nature with semiconductor material of silicon.

Fabricating CsPbX3-Based Type I and Type II Heterostructures by Tuning the Halide Composition of Janus CsPbX3/ZrO2 Nanocrystals.

Fabricating CsPbX3-based heterostructures has proven to be a feasible way to tune their photophysical properties. Here, we report the successful fabrication of Janus CsPbX3/ZrO2 heterostructure nanocrystals (NCs), in which each CsPbX3 NC is partially covered by ZrO2. According to the band alignment, CsPbBr3/ZrO2 and CsPbI3/ZrO2 can be indexed as type I and type II composites, respectively. The type I composites display great enhancement in photoluminescence quantum yield (from 63 to 90%) and photoluminescence lifetime (from 12.9 to 66.1 ns) because of the charge carrier confinement and passivation effect provided by ZrO2. In contrast, the type II composites can be used in photocatalytic reduction of CO2 because electrons and holes are effectively separated and accumulated in ZrO2 and CsPbI3, respectively, under irradiation. Janus CsPbBr3/ZrO2 NCs showed a stability much higher than that of pristine CsPbBr3 against polar solvent treatment. A stable and highly efficient light-emitting device with luminous efficiency up to 55 lm W-1 is fabricated by using CsPbBr3/ZrO2 NCs as the green light source. This work may not only enrich the family of surface-passivated perovskite materials but also provide a good example for the rational design of specific composites in the metal halide perovskite field.

Author Correction: Solution-processed perovskite light emitting diodes with efficiency exceeding 15% through additive-controlled nanostructure tailoring.

The original version of this Article contained an error in the spelling of the author Dan Credgington, which was incorrectly given as Dan Credington. This has now been corrected in both the PDF and HTML versions of the Article.

Consecutive Interfacial Transformation of Cesium Lead Halide Nanocubes to Ultrathin Nanowires with Improved Stability.

Although all-inorganic CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) have been considered as a promising material for photoelectronic devices, their applications are still limited because of their poor stability and the lack of in-depth understanding. Here, we demonstrate a post-treatment method for the preparation of ultrathin CsPbX3 nanowires (NWs) by treating CsPbBr3 nanocubes with thiourea solution. A systematic study showed a consecutive interfacial transformation process, in which CsPbBr3 nanocubes were first converted to Cs4PbBr6 NCs in the presence of thiourea, followed by a further transformation to CsPbBr3 NCs through an interfacial CsX-stripping process. To reduce the surface energy, an oriented attachment process has been realized and CsPbBr3 NCs aggregated to form ultrathin NWs. The ultrathin CsPbBr3 NWs exhibited high photoluminescence quantum yield (up to 60%) and high resistance to water treatment, which can be attributed to the surface passivation by thiourea. In addition to thiourea, cysteine and thioacetamide that contain the thiol group can also be used to trigger this transformation. This work can not only offer a facile method for the synthesis of efficient and stable ultrathin CsPbBr3 NWs but also help to reveal the in-depth mechanisms which may be very useful in the field of metal halide perovskite NCs.

Solution-processed perovskite light emitting diodes with efficiency exceeding 15% through additive-controlled nanostructure tailoring.

Organometal halide perovskites (OHP) are promising materials for low-cost, high-efficiency light-emitting diodes. In films with a distribution of two-dimensional OHP nanosheets and small three-dimensional nanocrystals, an energy funnel can be realized that concentrates the excitations in highly efficient radiative recombination centers. However, this energy funnel is likely to contain inefficient pathways as the size distribution of nanocrystals, the phase separation between the OHP and the organic phase. Here, we demonstrate that the OHP crystallite distribution and phase separation can be precisely controlled by adding a molecule that suppresses crystallization of the organic phase. We use these improved material properties to achieve OHP light-emitting diodes with an external quantum efficiency of 15.5%. Our results demonstrate that through the addition of judiciously selected molecular additives, sufficient carrier confinement with first-order recombination characteristics, and efficient suppression of non-radiative recombination can be achieved while retaining efficient charge transport characteristics.

Cs4PbX6 (X = Cl, Br, I) Nanocrystals: Preparation, Water-Triggered Transformation Behavior, and Anti-Counterfeiting Application.

As a promising material, Cs4PbX6 (X = Cl, Br, I) nanocrystals (NCs) have attracted much attention. However, their luminescent property is still under debate. In this work, we first systematically studied the colloidal preparation of Cs4PbX6 NCs. It is found that the critical parameter for the formation of Cs4PbX6 NCs is the ratio between Cs and Pb. Pure Cs4PbX6 NCs are nonluminescent. The luminescence property of previous reported Cs4PbX6 NCs may come from the impurity of luminescent CsPbX3 NCs. No coexistence of both Cs4PbX6 and CsPbX3 phase has been found in one single nanoparticle. The water-triggered transformation from nonluminescent Cs4PbX6 NCs to luminescent CsPbX3 NCs has been quantitatively studied. The potential application of Cs4PbX6 NCs in humidity sensor and anticounterfeiting have been demonstrated. This work is important because it not only confirmed the nonluminescent nature of Cs4PbX6 NCs but also demonstrated the potential application of such NCs.

Boosting Perovskite Light-Emitting Diode Performance via Tailoring Interfacial Contact.

Solution-processed perovskite light-emitting diodes (LEDs) have attracted wide attention in the past several years. However, the overall efficiency and stability of perovskite-based LEDs remain inferior to those of organic or quantum dot LEDs. Nonradiative charge recombination and the unbalanced charge injection are two critical factors that limit the device efficiency and operational stability of perovskite LEDs. Here, we develop a strategy to modify the interface between the hole transport layer and the perovskite emissive layer with an amphiphilic conjugated polymer of poly[(9,9-bis(3'-( N, N-dimethylamino)propyl)-2,7-fluorene)- alt-2,7-(9,9-dioctylfluorene)] (PFN). We show evidences that PFN improves the quality of the perovskite film, which effectively suppresses nonradiative recombination. By further improving the charge injection balance rate, a green perovskite LED with a champion current efficiency of 45.2 cd/A, corresponding to an external quantum efficiency of 14.4%, is achieved. In addition, the device based on the PFN layer exhibits improved operational lifetime. Our work paves a facile way for the development of efficient and stable perovskite LEDs.

Buried MoO x/Ag Electrode Enables High-Efficiency Organic/Silicon Heterojunction Solar Cells with a High Fill Factor.

Silicon (Si)/organic heterojunction solar cells based on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) and n-type Si have attracted wide interests because they promise cost-effectiveness and high-efficiency. However, the limited conductivity of PEDOT:PSS leads to an inefficient hole transport efficiency for the heterojunction device. Therefore, a high dense top-contact metal grid electrode is required to assure the efficient charge collection efficiency. Unfortunately, the large metal grid coverage ratio electrode would lead to undesirable optical loss. Here, we develop a strategy to balance PEDOT:PSS conductivity and grid optical transmittance via a buried molybdenum oxide/silver grid electrode. In addition, the grid electrode coverage ratio is optimized to reduce its light shading effect. The buried electrode dramatically reduces the device series resistance, which leads to a higher fill factor (FF). With the optimized buried electrode, a record FF of 80% is achieved for flat Si/PEDOT:PSS heterojunction devices. With further enhancement adhesion between the PEDOT:PSS film and Si substrate by a chemical cross-linkable silance, a power conversion efficiency of 16.3% for organic/textured Si heterojunction devices is achieved. Our results provide a path to overcome the inferior organic semiconductor property to enhance the organic/Si heterojunction solar cell.

Highly Luminescent and Stable Perovskite Nanocrystals with Octylphosphonic Acid as a Ligand for Efficient Light-Emitting Diodes.

All inorganic perovskite nanocrystals (NCs) of CsPbX3 (X = Cl, Br, I, or their mixture) are regarded as promising candidates for high-performance light-emitting diode (LED) owing to their high photoluminescence (PL) quantum yield (QY) and easy synthetic process. However, CsPbX3 NCs synthesized by the existing methods, where oleic acid (OA) and oleylamine (OLA) are generally used as surface-chelating ligands, suffer from poor stability due to the ligand loss, which drastically deteriorates their PL QY, as well as dispersibility in solvents. Herein, the OA/OLA ligands are replaced with octylphosphonic acid (OPA), which dramatically enhances the CsPbX3 stability. Owing to a strong interaction between OPA and lead atoms, the OPA-capped CsPbX3 (OPA-CsPbX3) NCs not only preserve their high PL QY (>90%) but also achieve a high-quality dispersion in solvents after multiple purification processes. Moreover, the organic residue in purified OPA-CsPbBr3 is only ∼4.6%, which is much lower than ∼29.7% in OA/OLA-CsPbBr3. Thereby, a uniform and compact OPA-CsPbBr3 film is obtained for LED application. A green LED with a current efficiency of 18.13 cd A-1, corresponding to an external quantum efficiency of 6.5%, is obtained. Our research provides a path to prepare high-quality perovskite NCs for high-performance optoelectronic devices.

Interfacial Synthesis of Highly Stable CsPbX3/Oxide Janus Nanoparticles.

The poor stability of CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) has severely impeded their practical applications. Although there are some successful examples on encapsulating multiple CsPbX3 NCs into an oxide or polymer matrix, it has remained a serious challenge for the surface modification/encapsulation using oxides or polymers at a single particle level. In this work, monodisperse CsPbX3/SiO2 and CsPbBr3/Ta2O5 Janus nanoparticles were successfully prepared by combining a water-triggered transformation process and a sol-gel method. The CsPbBr3/SiO2 NCs exhibited a photoluminescence quantum yield of 80% and a lifetime of 19.8 ns. The product showed dramatically improved stability against destruction by air, water, and light irradiation. Upon continuous irradiation by intense UV light for 10 h, a film of the CsPbBr3/SiO2 Janus NCs showed only a slight drop (2%) in the PL intensity, while a control sample of unmodified CsPbBr3 NCs displayed a 35% drop. We further highlighted the advantageous features of the CsPbBr3/SiO2 NCs in practical applications by using them as the green light source for the fabrication of a prototype white light emitting diode, and demonstrated a wide color gamut covering up to 138% of the National Television System Committee standard. This work not only provides a novel approach for the surface modification of individual CsPbX3 NCs but also helps to address the challenging stability issue; therefore, it has an important implication toward their practical applications.