Xing Qian

Benzo[a]carbazole-Based Donor−π–Acceptor Type Organic Dyes for Highly Efficient Dye-Sensitized Solar Cells

A novel class of metal-free organic dyes based on benzo[a]carbazole have been designed, synthesized, and used in dye-sensitized solar cells for the first time. These types of dyes consisted of a cyanoacrylic acid moiety as the electron acceptor/anchoring group and different electron-rich spacers such as thiophene (JY21), furan (JY22), and oligothiophene (JY23) as the π-linkers. The photophysical, electrochemical, and photovoltaic properties, as well as theoretical calculations of these dyes were investigated. The photovoltaic performances of these dyes were found to be highly relevant to the π-conjugated linkers. In particular, dye JY23 exhibited a broad IPCE response with a photocurrent signal up to about 740 nm covering the most region of the UV-visible light. A DSSC based on JY23 showed the best photovoltaic performance with a Jsc of 14.8 mA cm(-2), a Voc of 744 mV, and a FF of 0.68, achieving a power conversion efficiency of 7.54% under standard AM 1.5 G irradiation.

Template synthesis of CoSe2/Co3Se4 nanotubes: tuning of their crystal structures for photovoltaics and hydrogen evolution in alkaline medium

Tubular-structured nanomaterials with tailorable crystal structures and shell architectures whose properties can be tuned without changing their chemical compositions are attractive in electrochemical energy conversion and storage fields. Herein, we report the fabrication of tubular-structured orthorhombic CoSe2 (o-CoSe2) and cubic CoSe2 (c-CoSe2) by calcining monoclinic Co3Se4 nanotubes (Co3Se4 NTs) prepared by a facile precursor transformation method. Benefiting from advantageous structural features, including functional shells and well-defined interior voids, the tubular-structured o-CoSe2 showed a high power conversion efficiency of 9.34% as a counter electrode catalyst for dye-sensitized solar cells (DSSCs), superior to that of a Pt counter electrode (8.15%), under AM 1.5 G irradiation. In addition, the o-CoSe2 nanotubes also demonstrated excellent electrocatalytic activity in terms of low onset overpotential (∼54 mV) and small Tafel slope (∼65.9 mV per decade) as a hydrogen evolution reaction (HER) catalyst in alkaline medium. Hence, this work provides a promising strategy to selectively design and synthesize highly active electrocatalysts for energy conversion.

Hierarchical Porous Co9S8/Nitrogen-Doped Carbon@MoS2 Polyhedrons as pH Universal Electrocatalysts for Highly Efficient Hydrogen Evolution Reaction

The development of highly active and stable earth-abundant electrocatalysts to reduce or eliminate the reliance on noble-metal based ones for hydrogen evolution reaction (HER) over a broad pH range remains a great challenge. Herein, hierarchical porous Co9S8/N-doped carbon@MoS2 (Co9S8/NC@MoS2) polyhedrons have been synthesized by a facile hydrothermal approach using highly conductive Co/NC polyhedrons composed of cobalt nanoparticles embedded in N-doped carbon matrices as both the structural support and cobalt source. The Co/NC polyhedrons were prepared by direct carbonization of Co-based zeolitic imidazolate framework (ZIF-67) in Ar atmosphere. Benefiting from the prominent synergistic effect of N-doped carbon enhancing the conductivity of the hybrid, MoS2 and Co9S8 providing abundant catalytically active sites as well as the well-defined polyhedral structure promoting mechanical stability, the as-synthesized Co9S8/NC@MoS2 shows excellent HER activity and good stability over a broad pH range, with onset overpotentials of 4, 38, and 45 mV, Tafel slopes of 60.3, 68.8, and 126.1 mV dec-1, and overpotentials of 67, 117, and 261 mV at 10 mA cm-2 in 1.0 M KOH, 0.5 M H2SO4, and 1.0 M phosphate buffer solution (PBS), respectively. This work provides a general and promising approach for the design and synthesis of inexpensive and efficient pH-universal HER electrocatalysts.

Nickel Cobalt Sulfide Double-Shelled Hollow Nanospheres as Superior Bifunctional Electrocatalysts for Photovoltaics and Alkaline Hydrogen Evolution

Transition metal chalcogenides with hollow nanostructures have been considered as promising substitutes as precious metal electrocatalysts for energy conversion and storage. We synthesized NiCo2S4 double-shelled ball-in-ball hollow spheres (BHSs) via a simple solvothermal route and applied them in both dye-sensitized solar cells (DSSCs) and hydrogen evolution reactions (HERs) at the same time, which were clean and sustainable ways to convert energy. Benefiting from their remarkable structure features and advantageous chemical compositions, NiCo2S4 BHSs composed of tiny crystals possessed large surface area, well-defined interior voids, and high catalytic activity. The DSSC with NiCo2S4 BHSs under 100 mW cm-2 irradiation possessed a power conversion efficiency of 9.49% (Pt, 8.30%). Besides, NiCo2S4 BHSs as a HER catalyst also possessed a small onset overpotential (27.9 mV) and a low overpotential (89.7 mV at 10 mA cm-2) under alkaline conditions. Therefore, this work offers a sensible strategy to synthesize bifunctional electrocatalysts for DSSCs and HERs.

Stepwise synthesis of CoS2–C@CoS2 yolk–shell nanocages with much enhanced electrocatalytic performances both in solar cells and hydrogen evolution reactions

Yolk–shell nanocages possessing complex internal structure and excellent structural tenability are advantageous for the preparation of advanced catalysts. Due to outstanding features such as superior electrical, magnetic, optical and catalytic properties, non-noble metal materials with hollow nanostructures have been considered potential substitutes for highly active and stable abundant noble-metal electrocatalysts. In this study, the as-prepared CoS2–C@CoS2 yolk–shell nanocages were applied in both dye-sensitized solar cells (DSSCs) and hydrogen evolution reactions (HERs). Due to the remarkable structural features and advantageous chemical compositions, CoS2–C@CoS2 yolk–shell nanocages comprising tiny crystals possessed large surface area (161 m2 g−1), well-defined interior voids, excellent conductivity and high catalytic activity. The DSSC with CoS2–C@CoS2 achieved a high power conversion efficiency (PCE) of 9.32% under AM 1.5 G irradiation, and it outperformed the DSSC with Pt (8.24%). Besides, CoS2–C@CoS2 as a kind of HER catalyst also exhibited a low onset overpotential of 19.0 mV, small Tafel slope of 51.9 mV dec−1 and low overpotential of 79.1 mV at a current density of 10 mA cm−2 under acidic conditions (0.5 M H2SO4).

Strategic Design of Vacancy-Enriched Fe1–xS Nanoparticles Anchored on Fe3C-Encapsulated and N-Doped Carbon Nanotube Hybrids for High-Efficiency Triiodide Reduction in Dye-Sensitized Solar Cells

A new class of hybrids with the unique electrocatalytic nanoarchitecture of Fe1- xS anchored on Fe3C-encapsulated and N-doped carbon nanotubes (Fe1- xS/Fe3C-NCNTs) is innovatively synthesized through a facile one-step carbonization-sulfurization strategy. The efficient synthetic protocols on phase structure evolution and dynamic decomposition behavior enable the production of the Fe1- xS/Fe3C-NCNT hybrid with advanced structural and electronic properties, in which the Fe vacancy-contained Fe1- xS showed the 3d metallic state electrons and an electroactive Fe in +2/+3 valence, and the electronic structure of the CNT was effectively modulated by the incorporated Fe3C and N, with the work function decreased from 4.85 to 4.63 eV. The meticulous structural, electronic, and compositional control unveils the unusual synergetic catalytic properties for the Fe1- xS/Fe3C-NCNT hybrid when developed as counter electrodes (CEs) for dye-sensitized solar cells (DSSCs), in which the Fe3C- and N-incorporated CNTs with reduced work function and increased charge density provide a highway for electron transport and facilitate the electron migration from Fe3C-NCNTs to ultrahigh active Fe1- xS with the electron-donating effect, and the Fe vacancy-enriched Fe1- xS nanoparticles exhibit ultrahigh I3- adsorption and charge-transfer ability. As a consequence, the DSSC based on the Fe1- xS/Fe3C-NCNT CE delivers a high power conversion efficiency of 8.67% and good long-term stability with a remnant efficiency of 8.00% after 168 h of illumination, superior to those of traditional Pt. Furthermore, the possible catalytic mechanism toward I3- reduction is creatively proposed based on the structure-activity correlation. In this work, the structure engineering, electronic modulation, and composition control opens up new possibilities in constructing the novel electrocatalytic nanoarchitecture for highly efficient CEs in DSSCs.