Designing simple non-fused terthiophene-based electron acceptors for efficient organic solar cells

Low-cost photovoltaic materials are essential for realizing large-scale commercial applications of organic solar cells(OSCs).However,highly efficient OSCs based on low-cost photovoltaic materials are scarce due to a deficiency in understanding the structure-property relationship.Herein,we investigated two low-cost terthiophene-based electron acceptors,namely,3TC8 and 3TEH,with 3,4-bis(octan-3-yloxy)thiophene,differing only in the alkylated thiophene-bridges.Both acceptors exhibit low optical gaps(∼1.43 eV)and possess deep highest occupied molecular orbital(HOMO)levels(∼−5.8 eV).Notably,the single-crystal structure of 3TEH demonstrates highly planar conjugated backbone and strongπ-πstacking between intermolecular terminal groups,attributed to the presence of the bulky alkylated noncovalently conformational locks.Upon utilizing both acceptors to fabricate OSCs,the 3TC8-based device exhibited a power conversion efficiency(PCE)of 11.1%,while the 3TEH-based OSC demonstrated an excellent PCE of 14.4%.This PCE is the highest among OSCs based on terthiophene-containing electron acceptors.These results offer a new strategy for designing low-cost electron acceptors for highly efficient OSCs.

Pomelo biochar as an electron acceptor to modify graphitic carbon nitride for boosting visible-light-driven photocatalytic degradation of tetracycline

In this study,biochar(BC)derived from pomelo was prepared via a high-temperature calcination method to modify the graphitic carbon nitride(g-C_(3)N_(4))to synthesize the BC/g-C_(3)N_(4)composite for the degradation of the tetracycline(TC)antibiotic under visible light irradiation.The experimental results exhibit that the optimal feeding weight ratio of biochar/urea is 0.03:1 in BC/g-C_(3)N_(4)composite could show the best photocatalytic activity with the degradation rate of tetracycline is 83%in 100 min irradiation.The improvement of photocatalytic activity is mainly attributed to the following two points:(i)the strong bonding with π-π stacking between BC and g-C_(3)N_(4)make the photogenerated electrons of light-excited g-C_(3)N_(4)transfer to BC,quickly and improve the separation efficiency of carriers;(ii)the introduction of BC reduces the distance for photogenerated electrons to migrate to the surface and increases the specific surface area for providing more active sites.This study provides a sustainable,economical and promising method for the synthesis of photocatalytic materials their application to wastewater treatment.

Effect of electron acceptors H_2O_2 and O_2 on the generated reactive oxygen species ~1O_2 and OH~· in TiO_2-catalyzed photocatalytic oxidation of glycerol

The effect of the electron acceptors H2O2 and O2 on the type of generated reactive oxygen species（ROS）,and glycerol conversion and product distribution in the TiO2-catalyzed photocatalytic oxidation of glycerol was studied at ambient conditions.In the absence of an electron acceptor,only HO^·radicals were generated by irradiated UV light and TiO2.However,in the presence of the two electron acceptors,both HO^· radical and ^1O2 were produced by irradiated UV light and TiO2 in different concentrations that depended on the concentration of the electron acceptor.The use of H2O2 as an electron acceptor enhanced glycerol conversion more than O2.The type of generated value-added compounds depended on the concentration of the generated ROS.

Non-fullerene small molecule electron acceptors for high-performance organic solar cells

Fullerenes and their derivatives are important types of electron acceptor materials and play a vital role in organic solar cell devices. However, the fullerene acceptor material has some difficulties to overcome the intrinsic shortcomings, such as weak absorption in the visible range, difficulty in modification and high cost, which limit the performance of the device and the large-scale application of this type of acceptors. In recent years, non-fullerene electron acceptor material has attracted the attention of scientists due to the advantages of adjustable energy level, wide absorption, simple synthesis, low processing cost and good solubility. Researchers can use the rich chemical means to design and synthesize organic small molecules and their oligomers with specific aggregation morphology and excellent optoelectronic prop- erties. Great advances in the field of synthesis, device engineering, and device physics of non-fullerene acceptors have been achieved in the last few years. At present, non-fullerene small molecules based photovoltaic devices achieve the highest efficiency more than 13% and the efficiency gap between fullerenetype and non-fullerene-type photovoltaic devices is gradually narrowing. In this review, we explore recent progress of non-fullerene small molecule electron acceptors that have been developed and led to highefficiency photovoltaic devices and put forward the prospect of development in the future.

Molecular design towards two-dimensional electron acceptors for efficient non-fullerene solar cells

Non-fullerene polymer solar cells(NF-PSCs) have gained wide attention recently. Molecular design of non-fullerene electron acceptors effectively promotes the photovoltaic performance of NF-PSCs. However,molecular electron acceptors with 2-dimensional(2 D) configuration and conjugation are seldom reported.Herein, we designed and synthesized a series of novel 2 D electron acceptors for efficient NF-PSCs. With rational optimization on the conjugated moieties in both vertical and horizontal direction, these 2 D electron acceptors showed appealing properties, such as good planarity, full-spectrum absorption, high absorption extinction coefficient, and proper blend morphology with donor polymer. A high PCE of 9.76%was achieved for photovoltaic devices with PBDB-T as the donor and these 2 D electron acceptors. It was also found the charge transfer between the conjugated moieties in two directions of these 2 D molecules contributes to the utilization of absorbed photos, resulting in an exceptional EQE of 87% at 730 nm. This work presents rational design guidelines of 2 D electron acceptors, which showed great promise to achieve high-performance non-fullerene polymer solar cells.

Characterization of phosphorus removal bacteria in （AO）^2 SBR system by using different electron acceptors

Characteristics of phosphorus removal bacteria were investigated by using three different types of electron acceptors, as well as the positive role of nitrite in phosphorus removal process. An （AO）^2 SBR （anaerobic-aerobic-anoxic-aerobic sequencing batch reactor） was thereby employed to enrich denitrifying phosphorus removal bacteria for simultaneously removing phosphorus and nitrogen via auoxic phosphorus uptake, Ammonium oxidation was controlled at the first phase of the nitrification process. Nitrite-inhibition batch tests illustrated that nitrite was not an inhibitor to phosphorus uptake process, but served as an alternative electron acceptor to nitrate and oxygen if the concentration was under the inhibition level of 40mg NO2 - N·L^- 1. It implied that in addition to the two well-accepted groups of phosphorus removal bacterium （ one can only utilize oxygen as electron acceptor, P1, while the other can use both oxygen and nitrate as electron acceptor, P2 ）, a new group of phosphorus removal bacterium P3, which could use oxygen, nitrate and nitrite as electron acceptor to take up phosphorus were identified in the test system. To understand （AO）^2 SBR sludge better, the relative population of the different bacteria in this system, plus another A/O SBR sludge （ seed sludge） were respectively estimated by the phosphorus uptake batch tests with either oxygen or nitrate or nitrite as electron acceptor. The results demonstrated that phosphorus removal capability of （AO）^2 SBR sludge had a little degradation after A/O sludge was cultivated in the （AO）^2 mode over a long period of time. However, deuitrifying phosphorus removal bacteria （ P2 and P3 ） was significantly enriched showed by the relative population of the three types of bacteria, which implied that energy for aeration and COD consumption could be reduced in theory.

PHOTOINDUCED CHARGE TRANSFER POLYMERIZATION OF STYRENE INITIATED BY ELECTRON ACCEPTOR

Photoinduced charge transfer polymerization of styrene(St) with electron acceptor as initiator was investigated. In case of fumaronitrile (FN) or maleic anhydride (MA) as initiator the polymerization takes place regularly, whereas the tetrachloro-1,4-benzenequinone (TCQ), 2,3-dichloro-5, 6-dicyano-1, 4-benzenequinone (DDQ). or tetracyano ethylene (TCNE) as initiator the polymerization proceeds reluctantly only after the photoaddition reaction. A mechanism was proposed that free radicals would be formed following the charge and proton transfer in the exciplex formed between St and electron accepters.

Fused thienobenzene-thienothiophene electron acceptors for organic solar cells

Small molecule ladder-type heteroarenes IHBT-2F is designed and synthesized with strong electrondonating and molecular packing properties, where the central unit, fused thienobenzene-thienothiphene (IHBT), is attached with the strong electron-deficient 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (2FIC) as the end group. The counterpart IDBT-2F with indancenodibenzothiophene (IDBT) mainchain is sythesized for comparison, in which thieno[3,2-b]thiophene (TT) core of IHBT is replaced by benzene core. Relative to benzene-core IDBT-2F, TT-core IHBT-2F shows a much higher highest occupied molecular orbital energy level (IHBT-2F:-5.46 eV;IDBT-2F:-5.72 eV) and significantly redshifted absorption, due to the π-donor capability of the sulfur atom, the larger π-conjugation and stronger intermolecular π-π stacking. The as-cast organic solar cells (OSCs) based on blends of PTB7-Th donor and IHBT-2F acceptor without additional treatments exhibit power conversion efficiencies (PCEs) as high as 8.74%, which is much higher than that of PTB7-Th:IDBT-2F (6.73%).

Corrosion of Q235 steel affected by Pseudodesulfovibrio cashew differed with electron acceptors

Sulfate and nitrate reducing bacteria are important culprits for microbiologically influenced corrosion(MIC)using sulfate and nitrate as electron acceptors,respectively.Sulfate and nitrate hold different standard electrode potentials,which may lead to differences in corrosion,but their effects on corrosion by the same bacteria have not been reported.The corrosion of Q235 steel affected by Pseudodesulfovibrio cashew(P.cashew)in the sulfate and nitrate media under carbon starvation was studied.It was found that sulfate and nitrate did not lead to differences in corrosion under abiotic conditions.However,P.cashew promoted corrosion in both cases,and the consumption of H_(2)was the main mechanism for MIC.In addition,corrosion was more severe in the sulfate media.The higher corrosivity of P.cashew with sulfate as the electron acceptor is closely related to the higher number of sessile cells in the biofilm,higher bacterial motility,more hydrogen production pathways,and the increased gene expression of enzymes related to energy synthesis.

Designing high-performance nonfused ring electron acceptors via side-chain engineering

The side-chain has a significant influence on the optical properties and aggregation behaviors of the organic small molecule acceptors,which becomes an important strategy to optimize the photovoltaic performance of organic solar cells.In this work,we designed and synthesized three brand-new nonfused ring electron acceptors(NFREAs)OC4-4Cl-Ph,OC4-4Cl-Th,and OC4-4Cl-C8 with hexylbenzene,hexylthiophene,and octyl side chains on theπ-bridge units.Compared with OC4-4Cl-Ph and OC4-4Cl-Th,OC4-4Cl-C8 with linear alkyl side chain has more red-shift absorption,which is conducive to obtaining higher short-circuit current density.Additionally,the OC4-4Cl-C8 film exhibits a longer exciton diffusion distance,and the D18:OC4-4Cl-C8 blend film displays faster hole transfer,weaker bimolecular recombination,and more efficient exciton transport.Furthermore,The D18:OC4-4Cl-C8 blend films may effectively form interpenetrating networks that resemble nanofibrils,which can facilitate exciton dissociation and charge transport.Finally,OC4-4Cl-C8-based devices can be created a marvellously power conversion efficiency(PCE)of 16.56%,which is much higher than OC4-4Cl-Ph(12.29%)-and OC4-4Cl-Th-based(11.00%)ones,being the highest PCE among the NFREA based binary devices.All in all,we have validated that side-chain engineering is an efficient way to achieve high-performance NFREAs.

Near-infrared non-fused electron acceptors for efficient organic photovoltaics

Developing narrow-bandgap organic semiconductors is important to facilitate the advancement of organic photovoltaics(OPVs). Herein, two near-infrared non-fused ring acceptors(NIR NFRAs), PTBFTT-F and PTBFTT-Cl have been developed with A-π_A-π_D-D-π_D-π_A-A non-fused structures. It is revealed that the introduction of electron deficient π-bridge(π_A) and multiple intramolecular noncovalent interactions effectively retained the structural planarity and intramolecular charge transfer of NFRAs, extending strong NIR photon absorption up to 950 nm. Further, the chlorinated acceptor, with the enlarged π-surface compared to the fluorinated counterpart, promoted not only molecular stacking in solid, but also the desirable photochemical stability in ambient, which are helpful to thereby improve the exciton and charge dynamics for the corresponding OPVs. Overall, this work provides valuable insights into the design of NIR organic semiconductors.

Enhancing Photovoltaic Performance of Nonfused-Ring Electron Acceptors via Asymmetric End-Group Engineering and Noncovalently Conformational Locks

By employing the asymmetric end-group engineering,an asymmetric nonfused-ring electron acceptor(NFREA)was designed and synthesized.Compared with the symmetric analogs(NoCA-17 and NoCA-18),NoCA-19 possesses broader light absorption range,more coplanarπ-conjugated backbone,and appropriate crystallinity according to the experimental and theoretical results.The organic solar cells based on J52:NoCA-19 exhibited a power conversion efficiency as high as 12.26%,which is much higher than those of J52:NoCA-17(9.50%)and J52:NoCA-18(11.77%),mainly due to more efficient exciton dissociation,better and balanced charge mobility,suppressed recombination loss,shorter charge extraction time,longer charge carrier lifetimes,and more favorable blend film morphology.These findings demonstrate the great potential of asymmetric end-group engineering in exploring low-cost and high-performance NFREAs.

A–D–A’–D–A type nonfused ring electron acceptors for efficient organic solar cells via synergistic molecular packing and orientation control

Nonfused ring electron acceptors(NFREAs)are promising candidates for future commercialization of organic solar cells(OSCs)due to their simple synthesis.Still,the power conversion efficiencies(PCEs)of NFREA-based OSCs have large room for improvement.In this work,by merging end group halogenation and side chain engineering,we developed four A-D-A’-D-A type NFREAs,which we refer to as EH-4F,C4-4F,EH-4Cl,and C4-4Cl.Single crystal X-ray diffraction revealed that multiple intermolecular S⋅⋅⋅F interactions between cyclopentadithiophene and 5,6-difluoro-3-(dicyanomethylene)indanone could cause an unfavorable dimer formation,leading to ineffectiveπ-πstackings in EH-4F and C4-4F,whereas no such dimer was found in EH-4Cl and C4-4Cl after replacing with 5,6-dichloro-3-(dicyanomethylene)indanone.Moreover,although the shorter n-butyl side chain resulted in a closer molecular packing in C4-4Cl,EH-4Cl(2-ethylhexyl substitution)with proper crystallinity exhibited enhanced face-on orientation in thin film,which is favorable for vertical charge transport and further reducing charge recombination.As a result,a PCE of 13.0%is obtained for EH-4Cl-based OSC with a fill factor of 0.70.This work highlights the importance of molecular packing and orientation control toward future high-performance A-D-A’-D-A type NFREAs.

From Perylene Dimide Polymers to Fused-Ring Electron Acceptors:A 15-Year Exploration Journey of Nonfullerene Acceptors

Fullerene derivatives are classic electron acceptor materials for organic solar cells (Oscs) but possess some intrinsic drawbacks such as weak visiblelightabsorption,limitedoptoelectronic property tunability,dificult purification and photochemical/morphological instability.Fullereneacceptors area bottleneck restricting further development of this field. Ourgroup pioneered the exploration of novel nonfulerene acceptors in China in 2006,andinitiated the research of two representative acceptor systems, rylene dimide polymer and fused-ring electron acceptor (FREA).FREA breaks the theoreticalefficiencylimit of fullerene-based OsCs (-13%) and promotes the whole field to an unprecedented prosperity with efficiency of 20%, heraldinga nonfullerene era for OsCs.In this review, we revisit 15-year nonfullerene exploration journey,summarize the design principles,molecular engineeringstrategies, physical mechanisms and device applications of these two nonfullerene acceptor systems, and propose some possible researchtopics in the nearfuture.

A Simple Nonfused Ring Electron Acceptor with a Power Conversion Efficiency over 16%

By simplifying the r-bridge unit,a nonfused ring electron acceptor(NFREA)BM-2F was designed and synthesized with several high-yield steps.The specific molecular structure features of BM-2F are planar molecular backbone and out-of-plane side chain,which is favorable for charge transport and can suppress the over-aggregation.BM-2F based neat and blend films display obvious face-on molecular orientation.Specially,D18:BM-2F based blend film can form good bicontinuous interpenetrating network.More excitingly,a power conversion efficiency of 16.15%was achieved with D18:BM-2F based photovoltaic devices,which is the highest one based on NFREAs.Our researches manifest that NFREA is a promising direction for low-cost and high-performance organic solar cells.

Small molecular non-fullerene electron acceptors for P3HT-based bulk-heterojunction solar cells

Three small molecules with the same arms and different cores of perylene diimide(PDI)or indaceno[2,1-b:6,5-b']dithiophene(IDT)were designed and synthesized as the acceptor materials for P3HT-based bulk-heterojunction(BHJ)solar cells.The impacts of the different cores on the optical absorption,electrochemical properties,electron mobility,film morphology,photoluminescene characteristics,and solar cell performance were thoroughly studied.The three compounds possess a broad absorption covering the wavelength range of 400–700 nm and relatively low lowest unoccupied molecular orbital(LUMO)energy levels of?3.86,?3.81 and?3.99 eV.The highest power conversion efficiency of 0.82%was achieved for the BHJ solar cells based on SM3 as the acceptor material,the compound with a PDI core.

A Simple Building Block with Noncovalently Conformational Locks towards Constructing Low-Cost and High-Performance Nonfused Ring Electron Acceptors

Nonfused ring electron acceptors(NFREAs)have attracted much attention due to their concise synthetic routes and low cost.However,developing high-performance NFREAs with simple structure remains a great challenge.In this work,a simple building block(POBT)with noncovalently conformational locks(No CLs)was designed and synthesized.Single-crystal X-ray study indicated the presence of S…O NOCLs in POBT,thus enabling it to possess a coplanar conformation comparable to that of fused-ring CPT.Two novel NFREAs based on CPT and POBT were developed,namely TT-CPT and TT-POBT,respectively.Besides,TT-POBT possessed a smaller Stokes shift and a reduced reorganization energy compared with TT-CPT,indicating the introduction of S…O No CLs can enhance the molecular rigidity even if simplifying the molecular structure.As a result,the TT-POBT-based PSC device afforded an impressive power conversion efficiency of 11.15%,much higher than that of TT-CPT counterpart(7.03%),mainly resulting from the tighterπ-πstacking,improved and balanced charge transport,and more favorable film morphology.This work demonstrates the potential of the simple building block POBT with No CLs towards constructing low-cost and highperformance NFREAs.

Polymer solar cells with an inverted device configuration using polyhedral oligomeric silsesquioxane-[60]fullerene dyad as a novel electron acceptor

A polyhedral oligomeric silsesquioxane-[60]fullerene (POSS-C60) dyad was designed and used as a novel electron acceptor for bulk heterojunction (BHJ) polymer solar cells (PSCs) with an inverted device configuration. The studies of time-resolved photoinduced absorption of the pristine thin film of poly[(4,4'-bis(2-ethylhexyl)dithieno[3,2-b:2',3'-d]silole)-2,6-diyl-alt-(4,7-bis (2-thienyl)-2,1,3-benzothiadiazole)-5,5'-diyl] (SiPCPDTBT) and the composite thin film of SiPCPDTBT:POSS-C60 indicated efficient electron transfer from SiPCPDTBT to POSS-C60 with inhibited back-transfer. BHJ PSCs made by SiPCPDTBT mixed with POSS-C60 yielded the power conversion efficiencies (PCEs) of 1.50%. Under the same operational conditions, PCEs observed from BHJ PSCs made by SiPCPDTBT mixed with [6,6]-phenyl-C61-butyric acid methyl ester were 0.92%. These results demonstrated that POSS-C60 is a potentially good electron acceptor for inverted BHJ PSCs.

Effects of different external carbon sources and electron acceptors on interactions between denitrification and phosphorus removal in biological nutrient removal processes

The effects of two different external carbon sources （acetate and ethanol） and electron acceptors （dissolved oxygen, nitrate, and nitrite） were investigated under aerobic and anoxic conditions with non-acclimated process bi- omass from a full-scale biological nutrient removal-activated sludge system. When acetate was added as an external carbon source, phosphate release was observed even in the presence of electron acceptors. The release rates were 1.7, 7.8, and 3.5 mg P/（g MLVSS.h） （MLVSS： mixed liquor volatile suspended solids）, respectively, for dissolved oxygen, nitrate, and nitrite. In the case of ethanol, no phosphate release was observed in the presence of electron acceptors. Results of the experiments with nitrite showed that approximately 25 mg NO2-N/L of nitrite inhibited anoxic phosphorus uptake regardless of the concentration of the tested external carbon sources. Furthermore, higher deni- trification rates were obtained with acetate （1.4 and 0.8 mg N/（g MLVSS.h）） compared to ethanol （1.1 and 0.7 mg N/ （g MLVSS.h）） for both anoxic electron acceptors （nitrate and nitrite）.

A homopolymer based on double B←N bridged bipyridine as electron acceptor for all-polymer solar cells

Polymer electron acceptors for all-polymer solar cells （all-PSCs） are usually conjugated copolymers, which contain alternating electron-rich units and electron-deficient units. In this manuscript, we report a conjugated homopolymer （P-BNBP） based on an electron-deficient unit of double B,--N bridged bipyridine, which can be used as electron acceptor for all-polymer solar cells. P-BNBP shows low-lying LUMO energy level of -3.59eV, high absorption coefficient of 1.6 ×10^5Lmo1^-1 cm^-1 at 626nm and moderate electron mobility of 4.37 ×10^-6cm^2V^-1s^-1. AII-PSC devices exhibit power conversion efficiencies of 2.44%-3.04%. These results demonstrate that conjugated homopolymers are promising as electron acceptor materials for alI-PSCs.