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.

A novel metal-free porous covalent organic polymer for efficient room-temperature photocatalytic CO_(2) reduction via dry-reforming of methane

At room temperature,the conversion of greenhouse gases into valuable chemicals using metal-free catalysts for dry reforming of methane(DRM) is quite promising and challenging.Herein,we developed a novel covalent organic porous polymer (TPE-COP) with rapid charge separation of the electron–hole pairs for DRM driven by visible light at room temperature,which can efficiently generate syngas (CO and H_(2)).Both electron donor (tris(4-aminophenyl)amine,TAPA) and acceptor (4,4',4'',4'''-((1 E,1'E,1''E,1'''E)-(ethene-1,1,2,2-tetrayltetrakis (benzene-4,1-diyl))tetrakis (ethene-2,1-diyl))tetrakis (1-(4-formylbenzyl)quinolin-1-ium),TPE-CHO) were existed in TPE-COP,in which the push–pull effect between them promoted the separation of photogenerated electron–hole,thus greatly improving the photocatalytic activity.Density functional theory (DFT) simulation results show that TPE-COP can form charge-separating species under light irradiation,leading to electrons accumulation in TPE-CHO unit and holes in TAPA,and thus efficiently initiating DRM.After 20 h illumination,the photocatalytic results show that the yields reach 1123.6 and 30.8μmol g^(-1)for CO and H_(2),respectively,which are significantly higher than those of TPE-CHO small molecules.This excellent result is mainly due to the increase of specific surface area,the enhancement of light absorption capacity,and the improvement of photoelectron-generating efficiency after the formation of COP.Overall,this work contributes to understanding the advantages of COP materials for photocatalysis and fundamentally pushes metal-free catalysts into the door of DRM field.

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.

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.

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.

Photophysics, morphology and device performances correlation on non-fullerene acceptor based binary and ternary solar cells

Non-fullerene acceptor(NFA) based organic solar cells(OSCs) are of high efficiency and low energy loss and low recombination features, which is owing to the advantage of non-fullerene acceptors. The photophysics investigation of non-fullerene solar cells, in comparing to fullerene based analogue as well as mixed acceptor ternary blends could help to understand the working mechanism of NFA functioning mechanism. We choose PBDB-T donor, the fullerene derivative PC71 BM acceptor, and the non-fullerene acceptor ITIC as the model system, to construct binary and ternary solar cells, which then subject to ultrafast spectroscopy investigation. The charge transfer pathway in binary and ternary blends is revealed.And it is seen that ITIC leads to a faster exciton separation and exciton diffusion. ITIC in blends suppresses the geminate recombination and shows smaller amount of charge transfer states, which is beneficial for the device performance. And the addition of ITIC enhances the crystallinity for both donor and acceptor leads to a morphology change of forming bicontinuous crystalline networks and phase separation. In a consequence, fill factor and JSC, increase dramatically for the related OSC.

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.

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.

Biological nitrogen removal with enhanced phosphate uptake in (AO)2SBR using single sludge system

Simultaneous biological phosphorus and nitrogen removal with enhanced anoxic phosphate uptake via nitrite was investigated in an anaerobic-aerobic-anoxic-aerobic sequencing batch reactor((AO)2 SBR). The system showed stable phosphorus and nitrogen removal performance, and average removals for COD, TN and TP were 90%, 91% and 96%, respectively. The conditions of pH 7.5—8.0 and temperature 32℃ were found detrimental to nitrite oxidation bacteria but favorable to ammonia oxidizers, and the corresponding specific oxygen uptake rates(SOUR) for phase 1 and 2 of nitrification process were 0.7 and 15 mgO 2/(gVSS·h) in respect, which led to the nitrite accumulation in aerobic phase of(AO)2 SBR. Respiratory tests showed that 40 mgNO 2-N/L did not deteriorate the sludge activity drastically, and it implied that exposure of sludge to nitrite periodically enabled the biomass to have more tolerance capacity to resist the restraining effects from nitrite. In addition, batch tests were carried out and verified that denitrifying phosphorus accumulation organisms(DPAOs) could be enriched in a single sludge system coexisting with nitrifiers by introducing an anoxic phase in an anaerobic-aerobic SBR, and the ratio of the anoxic phosphate uptake capacity to aerobic phosphate uptake capacity was 45%. It was also found that nitrite(up to 20 mgNO 2-N/L) was not inhibitory to anoxic phosphate uptake and could serve as an electron acceptor like nitrate, but presented poorer efficiency compared with nitrate.

Construction of efficient active sites through cyano‐modified graphitic carbon nitride for photocatalytic CO_(2) reduction

The active site amount of photocatalysts,being the key factors in photocatalytic reactions,directly affects the photocatalytic performance of the photocatalyst.Pristine graphitic carbon nitride(g‐C_(3)N_(4))exhibits moderate photocatalytic activity due to insufficient active sites.In this study,cyano‐modified porous g‐C_(3)N_(4)nanosheets(MCN‐0.5)were synthesized through molecular self‐assembly and alkali‐assisted strategies.The cyano group acted as the active site of the photocatalytic reaction,because the good electron‐withdrawing property of the cyano group promoted carrier separation.Benefiting from the effect of the active sites,MCN‐0.5 exhibited significantly enhanced photocatalytic activity for CO2 reduction under visible light irradiation.Notably,the photocatalytic activity of MCN‐0.5 was significantly reduced when the cyano groups were removed by hydrochloric acid(HCl)treatment,further verifying the role of cyano groups as active sites.The photoreduction of Pt nanoparticles provided an intuitive indication that the introduction of cyano groups provided more active sites for the photocatalytic reaction.Furthermore,the controlled experiments showed that g‐C_(3)N_(4)grafted with cyano groups using melamine as the precursor exhibited enhanced photocatalytic activity,which proved the versatility of the strategy for enhancing the activity of g‐C_(3)N_(4)via cyano group modification.In situ diffuse reflectance infrared Fourier transform spectroscopy and theoretical calculations were used to investigate the mechanism of enhanced photocatalytic activity for CO2 reduction by cyano‐modified g‐C_(3)N_(4).This work provides a promising route for promoting efficient solar energy conversion by designing active sites in photocatalysts.

Treating leachate mixture with anaerobic ammonium oxidation technology

Large amounts of ammonium and a low content of biodegradable chemical oxygen demand（COD） are contained in leachate from aged landfills, together with the effluent containing high concentration of nitric nitrogen after biochemical treatment. Treatment effect of anaerobic ammonium oxidation （anammox） process on the mixture of the leachate and its biochemical effluent was investigated. The results show that the average removal efficiencies of ammonium, nitric nitrogen and total nitrogen are 87.51%, 74.95% and 79.59%, respectively, corresponding to the average ratio of removed nitric nitrogen to ammonium, i.e. 1.14 during the steady phase of anammox activity. The mean removal efficiency of COD is only 24.01% during the experimental period. Thc,dcmand of total phosphorous for the anammox process is unobvious. Especially, the alkalinity and pH value of the effluent are close to those of the inftuent during the steady phase of anammox activity. In addition, it is demonstrated that the status of the anammox bioreactor can be indicated by the alkalinity and pH value during the course of the experiment. The anammox bioreactor has shown potential for nitrogen removal in the leachate mixture. However, COD and total phosphorous in the leachate mixture need further treatment for removal efficiencies of COD and total phosphorous are not good in the anammox bioreactor.

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.

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.

Insight into the efficiency-stability-cost balanced organic solar cell based on a polymerized nonfused-ring electron acceptor

Organic solar cells(OSCs)have attracted extensive attention from both academia and industry in recent years due to their remarkable improvement in power conversion efficiency(PCE).However,the Golden Triangle(the balance of efficiency-stability-cost)required for large-scale industrialization of OSCs still remains a great challenge.Here,a new nonfused-ring electron acceptor(NFREA)BF and its polymerized counterpart PBF were designed and synthesized,and their photovoltaic performance,storage stability and material cost were systematically investigated.When blended with a widely-used polymer donor PBDB-T,the PBFbased all-polymer solar cell(all-PSC)displayed a record high PCE of 12.61%for polymerized NFREAs(PNFREAs)with an excellent stability(95.2%of initial PCE after 800 h storage),superior to the BF counterpart.Impressively,PBF-based allPSC possesses the highest industrial figure-of-merit(i-FOM)value of 0.309 based on an efficiency-stability-cost evaluation,in comparison to several representative OSC systems(such as PM6:Y6 and PBDB-T:PZ1).This work provides an insight into the balance of efficiency,stability,and cost,and also indicates that the PNFREAs are promising materials toward the commercial application of OSCs.

Enhancing Photovoltaic Performance of Ladder-Type Heteroarene-Based Electron Acceptors by Modulating Molecular Packing

Comprehensive Summary,The development of novel building blocks with sp3-hybridized-carbon-free conjugated skeletons is important to further advance and enrich nonfullerene acceptors(NFAs),but this remains a challenge due to the lack of strategies to effectively modulate the aggregation behavior of resulting NFAs.Herein,two novel nitrogen-bridged octacyclic ladder-type heteroarenes end-capped with thiophene rings(BTPS)or selenophene rings(BTPSe)are designed and synthesized as the donor cores for constructing NFAs(MQX-2 and MQX-4).It is found that replacing the sulfur atoms(MQX-2)at the outer positions of the heteroarene core with selenium atoms(MQX-4)can effectively modulate the molecular packing mode of the NFAs.The incorporation of selenium atoms induces stronger O···Se noncovalent interaction than O···S,thus promoting the formation of mixed H/J-type aggregates in MQX-4.Benefiting from more electron hopping channels,MQX-4 exhibits higher electron transport(more than 1-fold enhancement)and photovoltaic properties compared to MQX-2,which forms only H-type aggregates.

Design and Synthesis of N-Alkylaniline-Substituted Low Band-Gap Electron Acceptors for Photovoltaic Application

A novel electron donating unit,namely N-octyl-N-phenyl-thiophene(OPT),was designed in preparing electron acceptors with non-fused ring chemical structures.By introducing different functional atoms/groups into the para-position of phenyl in the OPT units,three non-fused ring acceptors(NFREAs),C8-2F,FC8-2F and MeC8-2F,were synthesized.The absorption spectrum of the three acceptors can be extended to about 950 nm with band-gaps of 1.28—1.32 eV due to the strong electron donating ability of OPT.The frontier molecular orbital distribution of OPT based molecules obtained by quantum chemistry calculation results reveals that their energy alignment can be finely tuned to meet different requirements.Moreover,by changing the substituents on the OPT units,their Flory-Huggins interaction parameter(χ)with the donor will be greatly influenced and different phase separation behavior can be accomplished.After blended with PBDB-TF,the FC8-2F-based cell yields short circuit current density(J_(sc))of 23.21 mA·cm^(-2),fill factor(FF)of 72.11%and the highest power conversion efficiency(PCE)of 12.42%.This work provides a new pathway for molecular design of new NFREAs,and demonstrates the application potential of OPT unit in realizing low band-gap photovoltaic materials.

Realizing compact three-dimensional charge transport networks of asymmetric electron acceptors for efficient organic solar cells

Asymmetry has been demonstrated an effective approach in recent years to tune the structural and energetic orders of nonfullerene electron acceptors(NFAs)to prepare efficient organic solar cells(OSCs).In this article,five asymmetric NFAs,namely C9BTP-BO-Th Cl-2F,C9BTP-BO-Cl-2F,C9BTP-BO-2Cl-2F,C7BTP-BO-2Cl-2F and C5BTP-BO-2Cl-2F possessing varied asymmetric end-groups and alkyl chains are synthesized to tune the charge transport networks formed within these NFAs.We found that the enhanced planarity in the asymmetric NFA can facilitate closerπ-πstacking distance in either the A-to-A or A-toD type NFA dimers,whilst the larger dipole moment can promote the formation of three-dimensional(3D)charge transport networks among NFAs.Taking those advantages,C7BTP-BO-2Cl-2F exhibit a compact 3D honeycomb network with a high packing coefficient of 72.1%and molecular packing density of 0.48 g/cm^(3),contributing to a superior power conversion efficiency of 18.0%when employing PM6 as the donor,with an open-circuit voltage of 0.85 V,short-circuit current of26.7 m A cm^(-2)and fill factor of 79.3%.Our work provides guidelines in engineering the end group and side chains of asymmetric NFAs to achieve compact charge transport networks for high efficiency OSCs.