Dopamine Semiquinone Radical Doped PEDOT:PSS: Enhanced Conductivity,Work Function and Performance in Organic Solar Cells

Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been is applied as hole transport material in organic electronic devices for more than 20 years. However, the redundant sulfonic acid group of PEDOT:PSS has often been overlooked. Herein, PEDOT:PSS‐DA is prepared via a facile doping of PEDOT:PSS with dopamine hydrochloride (DA·HCl) which reacts with the redundant sulfonic acid of PSS. The PEDOT:PSS‐DA film exhibits enhanced work function and conductivity compared to those of PEDOT:PSS. PEDOT:PSS‐DA‐based devices show a power conversion efficiency of 16.55% which is the highest in organic solar cells (OSCs) with (poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)‐4‐fluorothiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithio‐phene))‐co‐(1,3‐di(5‐thiophene‐2‐yl)‐5,7‐bis(2‐ethylhexyl)‐benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione))] (PM6):(2,2′‐((2Z,2′Z)‐((12,13‐bis(2‐ethylhexyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2′′,3′:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2‐g]thieno[2′,3′:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile) (Y6) as the active layer. Furthermore, PEDOT:PSS‐DA also exhibits enhanced performance in three other donor/acceptor systems, exhibiting high compatibility in OSCs. This work demonstrates that doping PEDOT:PSS with various amino derivatives is a potentially efficient strategy to enhance the performance of PEDOT:PSS in organic electronic devices.     

Stable Li Metal Anode Enabled by Space Confinement and Uniform Curvature through Lithiophilic Nanotube Arrays

The application of lithium (Li) metal anodes in rechargeable batteries is primarily restricted by Li dendrite growth on the metal's surface, which leads to shortened cycle life and safety concerns. Herein, well‐spaced nanotubes with ultrauniform surface curvature are introduced as a Li metal anode structure. The ultrauniform nanotubular surface generates uniform local electric fields that evenly attract Li‐ions to the surface, thereby inducing even current density distribution. Moreover, the well‐defined nanotube spacing offers Li diffusion pathways to the electroactive areas as well as the confined spaces to host deposited Li. These structural attributes create a unique electrodeposition manner; i.e., Li metal homogenously deposits on the nanotubular wall, causing each Li nanotube to grow in circumference without obvious sign of dendritic formation. Thus, the full‐cell battery with the spaced Li nanotubes exhibits a high specific capacity of 132 mA h g^?1 at 1 C and an excellent coulombic efficiency of ≈99.85% over 400 cycles.     

Hollow CuS Nanoboxes as Li‐Free Cathode for High‐Rate and Long‐Life Lithium Metal Batteries

Transition metal sulfides hold promising potentials as Li‐free conversion‐type cathode materials for high energy density lithium metal batteries. However, the practical deployment of these materials is hampered by their poor rate capability and short cycling life. In this work, the authors take the advantage of hollow structure of CuS nanoboxes to accommodate the volume expansion and facilitate the ion diffusion during discharge–charge processes. As a result, the hollow CuS nanoboxes achieve excellent rate performance (≈371 mAh g^?1 at 20 C) and ultra‐long cycle life (>1000 cycles). The structure and valence evolution of the CuS nanobox cathode are identified by scanning electron microscopy, transmission electron microscopy, and X‐ray photoelectron spectroscopy. Furthermore, the lithium storage mechanism is revealed by galvanostatic intermittent titration technique and operando Raman spectroscopy for the initial charge–discharge process and the following reversible processes. These results suggest that the hollow CuS nanobox material is a promising candidate as a low‐cost Li‐free cathode material for high‐rate and long‐life lithium metal batteries.     

Ultrafine Co3Se4 Nanoparticles in Nitrogen‐Doped 3D Carbon Matrix for High‐Stable and Long‐Cycle‐Life Lithium Sulfur Batteries

Lithium–sulfur batteries are a promising high energy output solution for substitution of traditional lithium ion batteries. In recent times research in this field has stepped into the exploration of practical applications. However, their applications are impeded by cycling stability and short life‐span mainly due to the notorious polysulfide shuttle effect. In this work, a multifunctional sulfur host fabricated by grafting highly conductive Co₃Se₄ nanoparticles onto the surface of an N‐doped 3D carbon matrix to inhibit the polysulfide shuttle and improve the sulfur utilization is proposed. By regulating the carbon matrix and the Co₃Se₄ distribution, N‐CN‐750@Co₃Se₄‐0.1 m with abundant polar sites is experimentally and theoretically shown to be a good LiPSs absorbent and a sulfur conversion accelerator. The S/N‐CN‐750@Co₃Se₄‐0.1 m cathode shows excellent sulfur utilization, rate performance, and cyclic durability. A prolonged cycling test of the as‐fabricated S/N‐CN‐750@Co₃Se₄‐0.1 m cathode is carried out at 0.2 C for more than 5 months which delivers a high initial capacity of 1150.3 mAh g^?1 and retains 531.0 mAh g^?1 after 800 cycles with an ultralow capacity reduction of 0.067% per cycle, maintaining Coulombic efficiency of more than 99.3%. The reaction details are characterized and analyzed by ex situ measurements. This work highly emphasizes the potential capabilities of transition‐metal selenides in lithium–sulfur batteries.     

Suppressing Voltage Fading of Li‐Rich Oxide Cathode via Building a Well‐Protected and Partially‐Protonated Surface by Polyacrylic Acid Binder for Cycle‐Stable Li‐Ion Batteries

Li‐rich manganese based oxides (LRMOs) are considered an attractive high‐capacity cathode for advanced Li‐ion batteries; however, their poor cyclability and gradual voltage fading have hindered their practical applications. Herein, an efficient and facile strategy is proposed to stabilize the lattice structure of LRMOs by surface modification of polyacrylic acid (PAA). The PAA‐coated LRMO electrode exhibits only 104 mV of the voltage fading after 100 cycles and 88% capacity retention over 500 cycles. The structural stability is attributed to the carboxyl groups in PAA chains reacting with oxygen species on the surface of LRMO to form a uniform and tightly coated film, which significantly suppresses the dissolution of transition metal elements from the cathode materials into the electrolyte. Importantly, a H⁺/Li⁺ exchange reaction takes place between the LRMO and PAA, generating a proton‐doped surface layer. Density functional theory calculations and experimental evidence demonstrates that the H⁺ ions in the surface lattice efficiently inhibit the migration of transition metal ions, leading to a stabilized lattice structure. This surface modification approach may provide a new route to building a stable Li‐rich oxide cathode with high capacity retention and low voltage fading for practical Li‐ion battery applications.     

Rational Design of Nanocatalysts with Nonmetal Species Modification for Electrochemical CO2 Reduction

Converting CO₂ to valuable carbonaceous fuels and chemicals via electrochemical CO₂ reduction by using renewable energy sources is considered to be a scalable strategy with substantial environmental and economic benefits. One of the challenges in this field is to develop nanocatalysts with superior electrocatalytic activity and selectivity for targeted products. Nonmetal species modification of nanocatalysts is of great significance for the construction of distinctive active sites to overcome the kinetic limitations of CO₂ reduction. These types of modification enable the efficient control of the selectivity and significantly decrease the reaction overpotential. Herein, a comprehensive review of the recent progress of nonmetal species modification of nanocatalysts for electrochemical CO₂ reduction is presented. After discussing some fundamental parameters and the basic principles of CO₂ reduction, including possible reaction pathways in light of theoretical modeling and experiments, the identification of active sites and elucidation of reaction mechanisms are emphasized for unraveling the role of nonmetal species modification, such as heteroatom incorporation, organic molecule decoration, electrolyte engineering, and single‐atom engineering. In the final section, future challenges and constructive perspectives are provided, facilitating the accelerated advancement of mechanism research and practical applications of green carbon cycling.     

PVP Treatment Induced Gradient Oxygen Doping in In2S3 Nanosheet to Boost Solar Water Oxidation of WO3 Nanoarray Photoanode

The photoelectrochemical performance of the WO₃ photoanode is limited by the severe charge recombination in the bulk phase and at the WO₃/electrolyte interface. Herein, In₂S₃ nanosheets are integrated onto the surface of the WO₃ nanowall array photoanode, followed by a facile polyvinylpyrrolidone (PVP) solution treatment. The PVP treatment results in sulfur vacancies and a gradient oxygen doping into In₂S₃ from surface to interior, which induces the formation of a gradient energy band distribution. The gradient band structured In₂S₃ and type II band alignment at the WO₃/In₂S₃ interface simultaneously create a channel that favors photogenerated electrons to migrate from the surface to the conductive substrate, thereby suppressing bulk carrier recombination. Meanwhile, the sulfur vacancies and oxygen doping contribute to increased charge carrier concentration, prolonged carrier lifetime, more active sites, and small interfacial transfer impedance. As a consequence, the PVP treated WO₃/In₂S₃ heterostructure photoanode exhibits a significantly enhanced photocurrent of 1.61 mA cm^?2 at 1.23 V versus reversible hydrogen electrode (RHE) and negative onset potential of 0.02 V versus RHE.     

Allotransplantation of adult spinal cord tissues after complete transected spinal cord injury: Long-term survival and functional recovery in canines

Science China Life Sciences - Spinal cord injury (SCI), especially complete transected SCI, leads to loss of cells and extracellular matrix and functional impairments. In a previous study, we...     

Elevated intracellular cyclic-di-GMP level in Shewanella oneidensis increases expression of c-type cytochromes

Electrochemically active biofilms are capable of exchanging electrons with solid electron acceptors and have many energy and environmental applications such as bioelectricity generation and environmental remediation. The performance of electrochemically active biofilms is usually dependent on c-type cytochromes, while biofilm development is controlled by a signal cascade mediated by the intracellular secondary messenger bis-(3ʹ-5ʹ) cyclic dimeric guanosine monophosphate (c-di-GMP). However, it is unclear whether there are any links between the c-di-GMP regulatory system and the expression of c-type cytochromes. In this study, we constructed a S. oneidensis MR-1 strain with a higher cytoplasmic c-di-GMP level by constitutively expressing a c-di-GMP synthase and it exhibited expected c-di-GMP-influenced traits, such as lowered motility and increased biofilm formation. Compared to MR-1 wild-type strain, the high c-di-GMP strain had a higher Fe(III) reduction rate (21.58 vs 11.88 pM of Fe(III)/h cell) and greater expression of genes that code for the proteins involved in the Mtr pathway, including CymA, MtrA, MtrB, MtrC and OmcA. Furthermore, single-cell Raman microspectroscopy (SCRM) revealed a great increase of c-type cytochromes in the high c-di-GMP strain as compared to MR-1 wild-type strain. Our results reveal for the first time that the c-di-GMP regulation system indirectly or directly positively regulates the expression of cytochromes involved in the extracellular electron transport (EET) in S. oneidensis, which would help to understand the regulatory mechanism of c-di-GMP on electricity production in bacteria.     

Alpine grassland plants grow earlier and faster but biomass remains unchanged over 35 years of climate change

Satellite data indicate significant advancement in alpine spring phenology over decades of climate warming, but corresponding field evidence is scarce. It is also unknown whether this advancement results from an earlier shift of phenological events, or enhancement of plant growth under unchanged phenological pattern. By analyzing a 35‐year dataset of seasonal biomass dynamics of a Tibetan alpine grassland, we show that climate change promoted both earlier phenology and faster growth, without changing annual biomass production. Biomass production increased in spring due to a warming‐induced earlier onset of plant growth, but decreased in autumn due mainly to increased water stress. Plants grew faster but the fast‐growing period shortened during the mid‐growing season. These findings provide the first in situ evidence of long‐term changes in growth patterns in alpine grassland plant communities, and suggest that earlier phenology and faster growth will jointly contribute to plant growth in a warming climate.