A new acceptor-donor-acceptor-structured nonfullerene acceptor ITCC (3,9-bis(4-(1,1-dicyanomethylene)-3-methylene-2-oxo-cyclopenta[b]thiophen)-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d':2,3-d']-s-indaceno[1,2-b:5,6-b']-dithiophene) is designed and synthesized via simple end-group modification. ITCC shows improved electron-transport properties and a high-lying lowest unoccupied molecular orbital level. A power conversion efficiency of 11.4% with an impressive V of over 1 V is recorded in photovoltaic devices, suggesting that ITCC has great potential for applications in tandem organic solar cells.
The authors report an ammonia‐assisted in situ cation‐exchange method for the synthesis of dodecagon N‐doped PdCoNi carbon‐based nanosheets (Pd‐e‐NiCo‐PBA‐C) and explore the catalytic performance. Pd‐e‐NiCo‐PBA‐C exerts extremely low overpotential and Tafel slope for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) both in acidic and alkaline media, only 47 mV, 55 mV dec−1 (pH = 0, HER) and 147 mV, 67 mV dec−1 (pH = 14, HER), and 309 mV, 67 mV dec−1 (pH = 14, OER), outperforming commercial IrO2‐based and Pt‐based catalysts. In addition, after 5000 cycles, the linear sweep voltammetry curve shows a negligible shift, indicating excellent stability performance. To test its overall water‐splitting performance, Pd‐e‐NiCo‐PBA‐C is applied as both cathode and anode materials. A high current density of 33 mA cm−2 at a battery voltage of 1.6 V is obtained, with the catalytic activity maintained at 97.3% after over 50 h. To get a further insight into the superior OER and HER performance, theoretical calculations are carried out, the better performance originates from the affinity difference of Pd and Ni atoms for gas atoms, and the replacement of inert atoms can decrease the binding energy and enhance the electrocatalytic activity.
Developing low‐cost oxygen evolution reaction (OER) catalysts with high efficiency and understanding the underlying reaction mechanism are critical for electrochemical conversion technologies. Here, an anodized Prussian blue analogue (PBA) containing Ni and Co is reported as a promising OER electrocatalyst in alkaline media. Detailed post‐mortem characterizations indicate the transformation from PBA to Ni(OH)2 during the anodic process, with the amorphous shell of the PBA facilitating the transformation by promoting greater structural flexibility. Further study with operando Raman and X‐ray photoelectron spectroscopy reveal the increase of anodic potential improves the degree of deprotonation of the transformed core‐shell PBA, leading to an increase of Ni valence. Density functional theory calculations suggest that the increase of Ni valence results in a continuous increase in the adsorption strength of oxygen‐containing species, exhibiting a volcano relationship against the OER activity. Based on the experiments and calculated results, an OER mechanism for the transformed product is proposed. The fully activated catalyst also works as the cathode and the anode for a water‐splitting electrolysis cell with a high output current density of 13.7 mA cm−2 when a cell voltage of 1.6 V applied. No obvious performance attenuation is observed after 40 h of catalysis.
The design of narrow band gap (NBG) donors or acceptors and their application in organic solar cells (OSCs) are of great importance in the conversion of solar photons to electrons. Limited by the inevitable energy loss from the optical band gap of the photovoltaic material to the open‐circuit voltage of the OSC device, the improvement of the power conversion efficiency (PCE) of NBG‐based OSCs faces great challenges. A novel acceptor–donor–acceptor structured non‐fullerene acceptor is reported with an ultra‐narrow band gap of 1.24 eV, which was achieved by an enhanced intramolecular charge transfer (ICT) effect. In the OSC device, despite a low energy loss of 0.509 eV, an impressive short‐circuit current density of 25.3 mA cm−2 is still recorded, which is the highest value for all OSC devices. The high 10.9 % PCE of the NBG‐based OSC demonstrates that the design and application of ultra‐narrow materials have the potential to further improve the PCE of OSC devices.
Here, a sol-gel method is used to prepare a Prussian blue analogue (NiFe-PBA) precursor with a 2D network, which is further annealed to an Fe 3 O 4 /NiC x composite (NiFe-PBA-gel-cal), inheriting the ultrahigh specific surface area of the parent structure. When the composite is used as both anode and cathode catalyst for overall water splitting, it requires low voltages of 1.57 and 1.66 V to provide a current density of 100 mA cm −2 in alkaline freshwater and simulated seawater, respectively, exhibiting no obvious attenuation over a 50 h test. Operando Raman spectroscopy and X-ray photoelectron spectroscopy indicate that NiOOH 2-x active species containing high-valence Ni 3+ /Ni 4+ are in situ generated from NiC x during the water oxidation. Density functional theory calculations combined with ligand field theory reveal that the role of high valence states of Ni is to trigger the production of localized O 2p electron holes, acting as electrophilic centers for the activation of redox reactions for oxygen evolution reaction. After hydrogen evolution reaction, a series of ex situ and in situ investigations indicate the reduction from Fe 3+ to Fe 2+ and the evolution of Ni(OH) 2 are the origin of the high activity.
Herein, a facile and efficient synthesis of microstructured Co3O4 for both supercapacitor and water‐splitting applications is reported. Metal cations (Fe3+, Cu2+) serve as structure‐directing agents regulating the structure of Co compounds, which are subsequently annealed to yield Co3O4. Detailed characterizations and density functional theory (DFT) calculations reveal that the in situ Cl‐doping introduces oxygen defects and provides abundant electroactive sites, and narrows the bandgap, which enhances the electron excitation of the as‐formed Co3O4. The as‐prepared Cl‐doped Co3O4 hierarchical nanospheres (Cl‐Co3O4‐h) display a high specific capacitance of 1629 F g−1 at 1 A g−1 as an electrode for supercapacitors, with excellent rate capability and cyclability. The Cl‐Co3O4‐h//activated carbon (AC) asymmetric supercapacitor (ASC) electrode achieves a specific capacitance of 237 F g−1 at 1 A g−1, with an energy density of 74 Wh kg−1 at a power density of 807 W kg−1 and even maintains 47 Wh kg−1 at the higher‐power density of 24.2 kW kg−1. An integrated electrolyzer for water‐splitting with Cl‐Co3O4‐h as both cathode and anode can be driven by Cl‐Co3O4‐h//AC ASC. The electrolyzer provides a high current density of 35 mA cm–2 at a cell voltage of 1.6 V, with good current density retention over 50 h.
The rational construction of efficient and low-cost electrocatalysts
for the hydrogen evolution reaction (HER) is critical to seawater
electrolysis. Herein, trimetallic heterostructured core–shell
nanoboxes based on Prussian blue analogues (Ni–Co@Fe–Co
PBA) were synthesized using an iterative coprecipitation strategy.
The same coprecipitation procedure was used for the preparation of
the PBA core and shell, with the synthesis of the shell involving
chemical etching during the introduction of ferrous ions. Due to its
unique structure and composition, the optimized trimetallic Ni–Co@Fe–Co
PBA possesses more active interfacial sites and a high specific surface
area. As a result, the developed Ni–Co@Fe–Co PBA electrocatalyst
exhibits remarkable electrocatalytic HER performance with small overpotentials
of 43 and 183 mV to drive a current density of 10 mA cm–2 in alkaline freshwater and simulated seawater, respectively. Operando
Raman spectroscopy demonstrates the evolution of Co2+ from
Co3+ in the catalyst during HER. Density functional theory
simulations reveal that the H*–N adsorption sites lower the
barrier energy of the rate-limiting step, and the introduced Fe species
improve the electron mobility of Ni–Co@Fe–Co PBA. The
charge transfer at the core–shell interface leads to the generation
of H* intermediates, thereby enhancing the HER activity. By pairing
this HER catalyst (Ni–Co@Fe–Co PBA) with another core–shell
PBA OER catalyst (NiCo@A-NiCo-PBA-AA) reported by our group, the fabricated
two-electrode electrolyzer was found to achieve high output current
densities of 44 and 30 mA cm–2 at a low voltage
of 1.6 V in alkaline freshwater and simulated seawater, respectively,
exhibiting remarkable durability over a 100 h test.
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