Electrocatalytic overall water splitting(OWS),a pivotal approach in addressing the global energy crisis,aims to produce hydrogen and oxygen.However,most of the catalysts in powder form are adhesively bounding to the e...Electrocatalytic overall water splitting(OWS),a pivotal approach in addressing the global energy crisis,aims to produce hydrogen and oxygen.However,most of the catalysts in powder form are adhesively bounding to the electrodes,resulting in catalyst detachment by bubble generation and other uncertain interference,and eventually reducing the OWS performance.To surmount this challenge,we synthesized a hybrid material of Co_(3)S_(4)-pyrolysis lotus fiber(labeled as Co_(3)S_(4)-p LF)textile by hydrothermal and hightemperature pyrolysis processes for electrocatalytic OWS.Owing to the natural LF textile exposing the uniformly distributed functional groups(AOH,ANH_(2),etc.)to anchor Co_(3)S_(4)nanoparticles with hierarchical porous structure and outstanding hydrophily,the hybrid Co_(3)S_(4)-p LF catalyst shows low overpotentials at 10 m A cm^(-2)(η_(10,HER)=100 m Vη_(10,OER)=240 mV)alongside prolonged operational stability during electrocatalytic reactions.Theoretical calculations reveal that the electron transfer from p LF to Co_(3)S_(4)in the hybrid Co_(3)S_(4)-p LF is beneficial to the electrocatalytic process.This work will shed light on the development of nature-inspired carbon-based materials in hybrid electrocatalysts for OWS.展开更多
Conjugated polymers are commonly used as effective hole transport materials(HTMs) for preparation of high-performance perovskite solar cells. However, the hydrophobic nature of these materials renders it difficult to ...Conjugated polymers are commonly used as effective hole transport materials(HTMs) for preparation of high-performance perovskite solar cells. However, the hydrophobic nature of these materials renders it difficult to deposit photovoltaic perovskite layers on top via solution processing. In this article, we report a generic surface modification strategy that enables the deposition of uniform and dense perovskite films on top of non-wetting interfaces. In contrast to the previous proposed chemical modifications which might alter the optoelectronic properties of the interfacial layers, we realized a nondestructive surface modification enabled by introducing a layer of insulating mesoporous aluminum oxide(Al2O3). The surface energies of the typical non-wetting hole-transport layers(PTAA, P3 HT, and Poly-TPD) were significantly reduced by the Al2O3 modification. Benefiting from the intact optoelectronic properties of the HTMs, perovskite solar cells deposited on these interface materials show full open-circuit voltages( V OC) with high fill factors(FF) up to 80%. Our method provides an effective avenue for exploiting the full potential of the existing as well as newly developed non-wetting interface materials for the fabrication of high-performance inverted perovskite solar cells.展开更多
Metal–phthalocyanines are a class of catalytically active materials promising in energy conversion and storage fields(e.g.,electrocatalysis).However,understanding and controlling the electrochemical properties in met...Metal–phthalocyanines are a class of catalytically active materials promising in energy conversion and storage fields(e.g.,electrocatalysis).However,understanding and controlling the electrochemical properties in metal-phthalocyanine systems is challenging.Herein,we elucidate the electrocatalytic origins of a series of cobalt-phthalocyanine molecular catalysts and finetune their electronic properties at the atomic level,both experimentally and computationally.The interactions between the cobalt center and the local coordination environment are regulated by introducing either electron-donating or electron-withdrawing groups on the phthalocyanine ligand,and the spin-orbit splitting of cobalt is increased by~0.15 eV compared with the nonsubstituted ligand.Specifically,the aminated cobalt phthalocyanine-based electrocatalysts exhibit low free energies in the ratedetermining steps of the oxygen reduction(-1.68 eV)and oxygen evolution reactions(0.37 eV).This contributes to the high electrocatalytic activity(e.g.,a halfwave potential of 0.84 V and an overpotential of 0.30 V at 10 mAcm^(-2)),featuring a high selectivity of a four-electron pathway(i.e.,a negligible by-product of hydrogen peroxide).These catalysts also exhibit exceptional kinetic current density(Tafel slope of 100 mV dec^(-1))in oxygen reduction reactions,in addition to a superior power density(158 mWcm^(-2))and a high cycling stability(>1,300 cycles)in Zn-air batteries,outperforming the commercial Pt/C and/or RuO2counterparts.展开更多
基金supported by the Scientific Research Foundation of Hunan Provincial Education Department,China(22B0893)the Scientific Research Foundation of Hunan Provincial Education Department,China(20A060)。
文摘Electrocatalytic overall water splitting(OWS),a pivotal approach in addressing the global energy crisis,aims to produce hydrogen and oxygen.However,most of the catalysts in powder form are adhesively bounding to the electrodes,resulting in catalyst detachment by bubble generation and other uncertain interference,and eventually reducing the OWS performance.To surmount this challenge,we synthesized a hybrid material of Co_(3)S_(4)-pyrolysis lotus fiber(labeled as Co_(3)S_(4)-p LF)textile by hydrothermal and hightemperature pyrolysis processes for electrocatalytic OWS.Owing to the natural LF textile exposing the uniformly distributed functional groups(AOH,ANH_(2),etc.)to anchor Co_(3)S_(4)nanoparticles with hierarchical porous structure and outstanding hydrophily,the hybrid Co_(3)S_(4)-p LF catalyst shows low overpotentials at 10 m A cm^(-2)(η_(10,HER)=100 m Vη_(10,OER)=240 mV)alongside prolonged operational stability during electrocatalytic reactions.Theoretical calculations reveal that the electron transfer from p LF to Co_(3)S_(4)in the hybrid Co_(3)S_(4)-p LF is beneficial to the electrocatalytic process.This work will shed light on the development of nature-inspired carbon-based materials in hybrid electrocatalysts for OWS.
基金supported by the National Natural Science Foundation of China (Grant no. 61705090)
文摘Conjugated polymers are commonly used as effective hole transport materials(HTMs) for preparation of high-performance perovskite solar cells. However, the hydrophobic nature of these materials renders it difficult to deposit photovoltaic perovskite layers on top via solution processing. In this article, we report a generic surface modification strategy that enables the deposition of uniform and dense perovskite films on top of non-wetting interfaces. In contrast to the previous proposed chemical modifications which might alter the optoelectronic properties of the interfacial layers, we realized a nondestructive surface modification enabled by introducing a layer of insulating mesoporous aluminum oxide(Al2O3). The surface energies of the typical non-wetting hole-transport layers(PTAA, P3 HT, and Poly-TPD) were significantly reduced by the Al2O3 modification. Benefiting from the intact optoelectronic properties of the HTMs, perovskite solar cells deposited on these interface materials show full open-circuit voltages( V OC) with high fill factors(FF) up to 80%. Our method provides an effective avenue for exploiting the full potential of the existing as well as newly developed non-wetting interface materials for the fabrication of high-performance inverted perovskite solar cells.
基金supported by the National Natural Science Foundation of China(S.P.,Project Nos.22378105 and 51703056X.X.,Project No.52172087)+5 种基金China Hunan Provincial Science and Technology Department(S.P.,Project No.2018JJ3028)China Fundamental Research Funds for the Central Universities(S.P.,Project Nos.021400541109030031)China Changsha Science and Technology Bureau(S.P.,Project No.kq2208015)China Petroleum&Chemical Corporation(W.X.,Project Nos.219012-3 and 420071-3)the National Supercomputing Center in Changsha(S.P.,Grant No.G2023016)the X-ray absorption spectroscopy and the small/wide angle X-ray scattering beamlines at the Australian Synchrotron,part of ANSTO(S.P.,Grant Nos.18766 and 20570)。
文摘Metal–phthalocyanines are a class of catalytically active materials promising in energy conversion and storage fields(e.g.,electrocatalysis).However,understanding and controlling the electrochemical properties in metal-phthalocyanine systems is challenging.Herein,we elucidate the electrocatalytic origins of a series of cobalt-phthalocyanine molecular catalysts and finetune their electronic properties at the atomic level,both experimentally and computationally.The interactions between the cobalt center and the local coordination environment are regulated by introducing either electron-donating or electron-withdrawing groups on the phthalocyanine ligand,and the spin-orbit splitting of cobalt is increased by~0.15 eV compared with the nonsubstituted ligand.Specifically,the aminated cobalt phthalocyanine-based electrocatalysts exhibit low free energies in the ratedetermining steps of the oxygen reduction(-1.68 eV)and oxygen evolution reactions(0.37 eV).This contributes to the high electrocatalytic activity(e.g.,a halfwave potential of 0.84 V and an overpotential of 0.30 V at 10 mAcm^(-2)),featuring a high selectivity of a four-electron pathway(i.e.,a negligible by-product of hydrogen peroxide).These catalysts also exhibit exceptional kinetic current density(Tafel slope of 100 mV dec^(-1))in oxygen reduction reactions,in addition to a superior power density(158 mWcm^(-2))and a high cycling stability(>1,300 cycles)in Zn-air batteries,outperforming the commercial Pt/C and/or RuO2counterparts.
