Multiple active components synergistically driven heteroatom-doped porous carbon as high-performance counter electrode in dye-sensitized solar cells

A facile template-free in situ self-activation approach for the multiple active components synergistically driven porous carbon was presented via a feasible annealing process.The biomass-derived carbon without additional activation reagents was fabricated using K-rich pomelo peel(PP)as the carbon source,which possesses a high electric conductivity where abundant functional hetero-metal atoms are doped into the carbon framework that playing the role of catalytic graphitization.The K^+that exists within the biomass can induce self-activation during pyrolysis apart from the activating gases during the pyrolysis process.The resulting electrocatalyst of PP-850(PP was pyrolyzed at 850°C in an N_2atmosphere)with abundant heteroatoms possesses a higher power conversion efficiency(PCE)of 7.81%as the counter electrode(CE)of dye-sensitized solar cells(DSCs)compared with the CEs calcinated at other temperatures and a similar PCE with Pt counterpart(8.24%)based on the liquid I_3^-/I^-electrolyte.The better electrocatalytic performance is attributed to the synergistic effect between self-activation and the co-doping of nitrogen,sulfur and phosphorus all together in a carbon matrix.Due to the feasibility of large-scale production,rich heteroatom doping,the PP-derived carbon,which simplifies the procedure and decreases the cost,has a potential application for an alternative electrocatalyst for high-performance photovoltaic devices.

A new D–D–π–A dye for efficient dye-sensitized solar cells

New metal-free organic dye sensitizers containing mono-triphenylamine or bis-triphenylamine as the electron donor, a thiophene as the π-conjugated system, and a cyanoacrylic acid moiety as the electron acceptor were synthesized. The optical and electrochemical properties of the dyes were investigated,and their performance as sensitizers in solar cells was evaluated. Dye-sensitized solar cells based on dye containing bis-triphenylamine as the electron donor produced a photon-to-current conversion efficiency of 6.06%（Jsc = 14.21 m A/cm;, Voc = 0.62 V, ff = 0.69） under 100 m W/cm;simulated AM 1.5 G solar irradiation（100 m W/cm;）.

Molten salt as ultrastrong polar solvent enables the most straightforward pyrolysis towards highly efficient and stable single-atom electrocatalyst

Currently,pyrolysis as the most widely used method still has some key issues not well resolved for synthesis of carbon-supported single-atom catalysts(C-SACs),e.g.,the sintering of metal atoms at high temperature as well as the high cost and complicated preparations of precursors.In this report,molten salts are demonstrated to be marvellous medium for preparation of C-SACs by pyrolysis of small molecular precursors(ionic liquid).The ultrastrong polarity on one hand establishes robust interaction with precursor and enables better carbonization,resulting in largely enhanced yield.On the other hand,the aggregation of metal atoms is effectively refrained while no nanoparticle or cluster is formed.By this strategy,a C-SAC with atomically dispersed Fe-N_(4) sites and a high specific area over 2000 m^(2) g^(-1) is obtained,which illustrates high ORR activity in both acid and alkaline media.Moreover,this SAC exhibits superior methanol tolerance and stability after acid soaking at 85℃ for 48 h.It is believed that the molten-salts-assisted pyrolysis can be developed into a routine strategy as it not only can largely simply the synthesis of C-SACs,but also can be extended to prepare other types of SACs.

Theoretical design and experimental synthesis of counter electrode for dye-sensitized solar cells: Amino-functionalized graphene

For some specific catalytic reaction, how to construct active sites on two dimensional materials is of great scientific significance. Dye-sensitized solar cells（DSCs） can be viewed as one representative photovoltaics because in which liquid electrolyte with triiodide/iodide（I;/I;） as redox couples are involved. In this study, amino-functionalized graphene（AFG） has been designed according to theoretically analyzing iodine reduction reaction（IRR） processes and rationally screening the volcanic plot. Then, such AFG has been successfully synthesized by a simple hydrothermal method and shows high electrocatalytic activity towards IRR when serving as counter electrode in DSCs. Finally, a high conversion efficiency of 7.39% by AFG-based DSCs was obtained, which is close to that using Pt as counter electrode.

Insight into the CO2 photoreduction mechanism over 9-hydroxyphenal-1-one(HPHN) carbon quantum dots

Converting CO2 to carbon-containing fuels is an effective approach to relieving energy shortages.Carbon quantum dots(CQDs) have shown distinct properties and attracted tremendous interest in CO2 reduction.Herein,we report a joint experimental-computational mechanistic study of photoreduction CO2 to CO on the model catalyst 9-hydroxyphenal-1-one(HPHN) CQDs with known structure.Our theoretical calculations reveal that the rate-determining step is COOH·formation,which is closely related to the proton and electron transfer induced by hydrogen bonding in the excited state.According to the calculated volcano plot,the solution we proposed is addition Zn^(2+) ions.The active center changed from the hydroxyl oxygen atom to the Zn atom and the barrier of the COOH·formation step is noticeably decreased when Zn^(2+) ions are added.It is further confirmed by the experimental data that the activity of CO2 reduction increases 2.9 times when Zn^(2+) ions are added.

New insight into the ultra-long lifetime of excitons in organic-inorganic perovskite： Reverse intersystem crossing

Recently, an effective exciton diffusion length L exceeding 100μm has been reported for organic- inorganic halide perovskites owing to both the high mobility and ultra-long lifetime of the excitons; however, the origin of ultra-long L is still unclear in nature. In some photoelectric materials, reverse intersystem crossing （RISC） from the triplet to the singlet state can enhance the quantum yield of pho- toluminescence greatly. In this study, our theoretical investigation indicated that the energy difference △E_st between the singlet state and the triplet state of CH_3NH_3Pbl_3 was less than 0.1 eV, which represents one crucial prerequisite for the occurrence of RISC. Meanwhile, the experimental results showed that the photoluminescence lifetime increased with the increasing temperature, a typical feature of RISC. Based on this study, we put forward the hypothesis that the ultra-long lifetime of excitons in organic-inorganic halide perovskite might be caused by the RISC process. This may provide a new insight into the important photophysical properties of such novel photovoltaic materials.

A positive correlation between local photocurrent and grain size in a perovskite solar cell

Developing an interplay between the local morphological character and its local photovoltaic(PV)parameters in a perovskite thin film is essential for guiding the construction of highly-efficient perovskite solar cells(PSCs). To achieve a higher PSC performance, great efforts have been devoted to the growth of larger perovskite grains;however, how the gain size can influence the PSC performance in a working device remains unclear. Herein, using laser-scanned confocal microscopy coupled with a photocurrent detection module, we realize local photocurrent, photoluminescence(PL) intensity and PL lifetime mappings directly in a working PSC. For perovskite grains of various sizes(from ~500 nm to a few micrometers), their local photocurrent exhibit a statically positive correlation with the grain size, but anti-correlated with the grain’s local PL intensity. This result suggests that a larger perovskite grain likely has fewer defects and more importantly better interfacial contact with the charge collection layers and thus leads to higher charge collection efficiency, and the optimum grain size is found to be ≥2 μm.Our result provides important guidance to the growth and control of perovskite microstructures toward the further improvement of PSC performance.

Asymmetrically ligated single atomic nickel sites for efficient hydrogen peroxide electrosynthesis

Atomic transition-metal-nitrogen-carbon electrocatalysts hold great promise as alternatives to benchmark Pt in the oxygen reduction reaction.The pristine metal centers with quasi square-planar D_(4h) configuration,however,still suffer from unfavorable energetics and thereby strong activity/selectivity trade-off during the catalytic process.Here we present a ligand-field engineering of single-atom Ni-N-C catalysts to boost the sluggish kinetics via rationally constructing prototypical asymmetrically ligated Ni-N_(3)O_(1) sites.The as-obtained Ni-supported multi-walled carbon nanotubes with molten salt-treated(defined as Ni/CNS)catalyst delivered an excellent H_(2)O_(2) selectivity(>90%)within a wide potential window(0.2–0.7 V vs.reversible hydrogen electrode(RHE))and robust stability(for 10 h)in alkaline medium.Combined electron paramagnetic resonance and theoretical analysis rationalize this finding and demonstrate that the broken symmetry facilitates the electron transfer of a σ* to O–O orbital as compared to the Ni-N_(4) counterpart,playing an indispensable role in efficient O_(2) activation.

Tuned single atom coordination structures mediated by polarization force and sulfur anions for photovoltaics

Impeding high temperature sintering is challengeable for synthesis of carbon-supported single-atom catalysts (C-SACs), which requires high-cost precursor and strictly-controlled procedures. Herein, by virtue of the ultrastrong polarity of salt melts, sintering of metal atoms is effectively suppressed. Meanwhile, doping with inorganic sulfur anions not only produces sufficient anchoring sites to achieve high loading of atomically dispersed Co up to 13.85 wt.%, but also enables their electronic and geometric structures to be well tuned. When served as a cathode catalyst in dye-sensitized solar cells, the C-SAC with Co-N4-S2 moieties exhibits high activity towards the iodide reduction reaction (IRR), achieving a higher power conversion efficiency than that of conventional Pt counterpart. Density function theory (DFT) calculations revealed that the superior IRR activity was ascribed to the unique structure of Co-N4-S2 moieties with lower reaction barriers and moderate binding energy of iodine on the Co center, which was beneficial to I2 dissociation.