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| Open AccessThe carbonyl-lock mechanism underlying non-aromatic fluorescence in biological matter
Recent experimental evidence shows a new type of intrinsic fluorescence in biomolecules void of aromatic chemical compounds whose origin is unclear. Here, the authors use non-adiabatic AIMD simulations to show a potential carbonyl-lock mechanism originating this phenomenon.
- Gonzalo Díaz Mirón
- , Jonathan A. Semelak
- & Uriel N. Morzan
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Article
| Open AccessAnaerobic photoinduced Cu(0/I)-mediated Glaser coupling in a radical pathway
The reaction mechanism of the historic copper-catalyzed Glaser coupling has been debated to be based on redox cycles of Cu ions in specific oxidation states or on a radical mechanism based on Cu(0)/Cu(I). Here, the authors demonstrate two coexisting Glaser coupling pathways which can be differentiated by anaerobic/irradiation or aerobic reaction conditions
- Siqi Zhang
- & Liang Zhao
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Article
| Open AccessNanomechanical action opens endo-lysosomal compartments
Endo-lysosomal escape is a highly inefficient process. Here the authors present a lipid-based nanoscale molecular machine that achieves efficient cytosolic transport of biologics by destabilizing endo-lysosomal compartments through nanomechanical action upon light irradiation.
- Yu Zhao
- , Zhongfeng Ye
- & Qiaobing Xu
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Article
| Open AccessMulti-scale molecular dynamics simulations of enhanced energy transfer in organic molecules under strong coupling
Placing an organic material in an optical cavity can enhance exciton transport, but the mechanism is poorly understood. Here, using molecular dynamics simulations, the authors obtained atomistic insights into that mechanism.
- Ilia Sokolovskii
- , Ruth H. Tichauer
- & Gerrit Groenhof
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Article
| Open AccessKinetics of the xanthophyll cycle and its role in photoprotective memory and response
This study explores how the photosynthetic alga Nannochloropsis oceanica, rapidly adapts to changing light conditions, using a short-term “memory" system involving the xanthophyll cycle, which is widespread in photosynthetic organisms.
- Audrey Short
- , Thomas P. Fay
- & Graham R. Fleming
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Article
| Open AccessPhotoelectrochemical oxidative C(sp3)−H borylation of unactivated hydrocarbons
Organoboron compounds are of high interest in organic synthesis due to the versatility of boryl substituents that allows access to further modifications. Here, the authors report on the development of an oxidative C(sp3)−H borylation reaction under metal- and oxidant-free conditions, enabled by photoelectrochemical strategy
- Ping-Fu Zhong
- , Jia-Lin Tu
- & Wujiong Xia
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Article
| Open AccessVisible light-triggered selective C(sp2)-H/C(sp3)-H coupling of benzenes with aliphatic hydrocarbons
The direct and selective coupling between unactivated C(sp2)-H and C(sp3)-H bonds is widely recognized as one of the most challenging tasks in organic synthesis. Here, the authors present an iron halidepromoted photochemical aerobic oxidation strategy for achieving such transformations.
- Qian-Yu Li
- , Shiyan Cheng
- & Lei Gong
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Article
| Open AccessMetal-free photoinduced C(sp3)–H/C(sp3)–H cross-coupling to access α‑tertiary amino acid derivatives
The cross-dehydrogenative coupling (CDC) reaction is the most efficient method for constructing α-tertiary amino acids (ATAAs). Here, the authors present a mild, metal-free CDC reaction for the construction of ATAAs with good regioselectivity.
- Yujun Li
- , Shaopeng Guo
- & Ke Zheng
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Article
| Open AccessA metal-free photoactive nitrogen-doped carbon nanosolenoid with broad absorption in visible region for efficient photocatalysis
Carbon nanosolenoid materials with Riemann surfaces have unique structures and novel physical properties. Here, the authors report a nitrogen-doped carbon nanosolenoid heterojunction material with distinctive photocatalytic properties for light driven hydrogen production and organic transformations.
- Yu Zhou
- , Xinyu Zhang
- & Pingwu Du
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Article
| Open AccessDecarboxylation of β-boryl NHPI esters enables radical 1,2-boron shift for the assembly of versatile organoborons
The 1,2 migration reaction on tetracoordinate boron species have been well investigated but less work looked on 1,2-boryl radical shift for the construction of organoborons. Here, the authors demonstrate a visible-light-induced photoredox neutral decarboxylative radical cross-coupling reaction, which undergoes a radical 1,2-boron shift to give a translocated C-radical for further capture of versatile radical acceptors
- Yu Guo
- , Xiaosha Wang
- & Qiuling Song
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Article
| Open AccessLaser-induced nitrogen fixation
Emerged sustainable techniques for nitrogen fixation still lack ammonia yield rate to be practically relevant. Here, the authors demonstrate a laser–induced method to deliver a yield rate of 30.9 µmol s-1 cm−2 at ambient conditions, which is two orders of magnitude higher than other methods.
- Huize Wang
- , Ranga Rohit Seemakurthi
- & Markus Antonietti
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Article
| Open AccessTailored photoenzymatic systems for selective reduction of aliphatic and aromatic nitro compounds fueled by light
The selective enzymatic reduction of nitroaliphatic and nitroaromatic compounds is challenging. Here, the authors report selective (sun)light-driven photoenzymatic reduction of a wide variety of nitro compounds to aliphatic amines and amino-, azoxy- and azo-aromatics using flavin-dependent nitroreductases and chlorophyll as photocatalyst
- Alejandro Prats Luján
- , Mohammad Faizan Bhat
- & Gerrit J. Poelarends
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Article
| Open AccessOrganophotocatalysed synthesis of 2-piperidinones in one step via [1 + 2 + 3] strategy
The synthesis of 2-piperidinone derivatives remains challenging. Here, the authors develop an organophotocatalysed [1 + 2 + 3] strategy to enable the one-step access to diverse 2-piperidinones from ammonium salts, alkenes, and unsaturated carbonyl compounds.
- Yi-Dan Du
- , Shan Wang
- & Wei Shu
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Article
| Open AccessTricolor visible wavelength-selective photodegradable hydrogel biomaterials
Photodegradable gels are useful for regenerative medicine and tissue engineering, but typically respond to UV light. Here, the authors report a family of 3 photolabile linkers that cleave rapidly and with unique tricolor wavelength-selectivity to visible light.
- Teresa L. Rapp
- & Cole A. DeForest
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Article
| Open AccessTwo-photon nanoprobes based on bioorganic nanoarchitectonics with a photo-oxidation enhanced emission mechanism
Two-photon absorption (TPA) affords unparalleled spatiotemporal resolution for bioimaging, but the photo-oxidation tends to weaken the photoluminescence in vivo, limiting the usefulness of TPA probes. Here, the authors report self-assembling near-infrared cyanine dye-based nanoprobes of enhanced TPA fluorescence imaging capacity based on a photo-oxidation enhanced emission mechanism.
- Shukun Li
- , Rui Chang
- & Xuehai Yan
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Article
| Open AccessTheory predicts UV/vis-to-IR photonic down conversion mediated by excited state vibrational polaritons
Vibrational polaritons steer chemical reactions and control quantum states for information processing. Here the authors predict their formation during electronic photo-excitation, enabling a down-conversion of visible to infrared photons.
- Connor K. Terry Weatherly
- , Justin Provazza
- & Roel Tempelaar
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Article
| Open AccessSelective CO2 reduction to CH3OH over atomic dual-metal sites embedded in a metal-organic framework with high-energy radiation
Most approaches for CH3OH production focus on thermochemical, electrolytic, and photolytic processes. Here the authors report a radiolytic route to produce CH3OH from CO2 and water by atomic Cu-Ni dual sites embedded in a metal-organic framework.
- Changjiang Hu
- , Zhiwen Jiang
- & Jun Ma
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Article
| Open AccessVisible-light-driven reversible shuttle vicinal dihalogenation using lead halide perovskite quantum dot catalysts
The dihalogenation of alkenes is a significant chemical reaction, but its reaction conditions are demanding. Here, the authors show a photocatalytically assisted shuttle strategy using perovskite quantum dot catalysts for reversible vicinal dihalogenation under visible light illumination.
- Yonglong Li
- , Yangxuan Gao
- & Wei Xie
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Article
| Open AccessUnlocking full and fast conversion in photocatalytic carbon dioxide reduction for applications in radio-carbonylation
While the reduction of CO2 to CO is a very active research topic, use of the reduced CO in organic synthesis is not yet mature. Herein, the authors report a photocatalytic process that unlocks full CO2-to-CO conversion, opening opportunities for access to 11C- and 14C-labeled pharmaceuticals.
- Serena Monticelli
- , Alex Talbot
- & Davide Audisio
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Article
| Open AccessDeconvolution volumetric additive manufacturing
Volumetric additive manufacturing generally suffers from systematic undercuring of fine features, which limits its application range. Here, authors develop a model to predict print time variation with feature size and propose a deconvolution method, enabling precise fabrication of intricate structures.
- Antony Orth
- , Daniel Webber
- & Chantal Paquet
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Article
| Open AccessDiaryl-hemiindigos as visible light, pH, and heat responsive four-state switches and application in photochromic transparent polymers
Hemiindigo derivatives can act as photoswitches, but their applicability is limited by synthetic challenges. Here, the authors report the synthesis of modified photoswitches and demonstrate four-state switching, chemical fueling, and reversible inscription into transparent polymers.
- Maximilian Sacherer
- , Frank Hampel
- & Henry Dube
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Article
| Open AccessLong-term durability of metastable β-Fe2O3 photoanodes in highly corrosive seawater
Achieving long-term stable photoelectrochemical water decomposition in highly corrosive seawater remains a challenge. Here, the authors report a strategy for enhancing metal-oxygen interaction to achieve high stability of metastable β-Fe2O3 photoelectrochemical seawater splitting.
- Changhao Liu
- , Ningsi Zhang
- & Zhigang Zou
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Article
| Open AccessAggregation-regulated room-temperature phosphorescence materials with multi-mode emission, adjustable excitation-dependence and visible-light excitation
Room temperature phosphorescent materials have potential in a range of applications, but it is challenging to achieve multiple emission and excitation modes. Here, the authors report the development of RTP materials with different emission modes by regulating the aggregation state.
- Jingxuan You
- , Xin Zhang
- & Jun Zhang
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Article
| Open AccessAccessing parity-forbidden d-d transitions for photocatalytic CO2 reduction driven by infrared light
This study demonstrates the effectiveness and generality of utilizing ultrathin Cu-based hydrotalcite-like hydroxy salts as catalysts for infrared light-driven CO2 reduction based on their d-d orbital transition mechanism.
- Xiaodong Li
- , Li Li
- & Xinliang Feng
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Article
| Open AccessSub-picosecond collapse of molecular polaritons to pure molecular transition in plasmonic photoswitch-nanoantennas
Pump-probe spectroscopy is a versatile technique to explore ultrafast dynamics on the femtosecond timescale. Here the authors report a pump-probe experiment and quantum modeling combined study revealing dynamics of collective polaritonic states that are formed between a molecular photoswitch and plasmonic nanoantennas.
- Joel Kuttruff
- , Marco Romanelli
- & Nicolò Maccaferri
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Article
| Open AccessChalcogen-bridged coordination polymer for the photocatalytic activation of aryl halides
Chalcogen-bridged naphthalene diimide coordination polymers are designed and synthesised as potent excited state reductants for the activation of inert bonds in a series of aryl halides.
- Le Zeng
- , Tiexin Zhang
- & Chunying Duan
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Article
| Open AccessPhotoredox-catalyzed diastereoselective dearomative prenylation and reverse-prenylation of electron-deficient indole derivatives
Prenylated and reverse-prenylated indoline alkaloids are widely present in nature. Here, the authors demonstrate a tandem photoredox radical dearomatization/Claisen rearrangement of electron-deficient indoles for the rapid assembly of these privileged scaffolds.
- Xuexue Chang
- , Fangqing Zhang
- & Yangbin Liu
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Article
| Open AccessIntegrated halide perovskite photoelectrochemical cells with solar-driven water-splitting efficiency of 20.8%
High-efficiency photoelectrodes, which integrate light absorption with catalysis, have been limited to costly materials. Here, the authors develop an anticorrosion barrier that enables low-cost semiconductors for integrated solar fuel devices with 20.8% solar-to-hydrogen energy conversion efficiency.
- Austin M. K. Fehr
- , Ayush Agrawal
- & Aditya D. Mohite
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Article
| Open AccessArylcarboxylation of unactivated alkenes with CO2 via visible-light photoredox catalysis
Despite the importance of polycyclic carboxylic acids and derivatives in various fields, general methods for the arylcarboxylation of alkenes with CO2 remain elusive. Here, the authors transform unactivated alkenes into high value-added polycyclic carboxylic acids and derivatives via visible-light photoredox-catalysis, using CO2 as the one-carbon feedstock.
- Wei Zhang
- , Zhen Chen
- & Da-Gang Yu
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Article
| Open AccessSolution-processable polymers of intrinsic microporosity for gas-phase carbon dioxide photoreduction
This works presents a series of solution processable, conjugated polymers of intrinsic microporosity, which are used as photocatalysts for carbon dioxide reduction to carbon monoxide in the presence of hydrogen.
- Floriana Moruzzi
- , Weimin Zhang
- & Iain McCulloch
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Article
| Open AccessUncovering the chiral bias of meteoritic isovaline through asymmetric photochemistry
Excess of l-amino acids in meteorites suggests an extraterrestrial origin of biomolecular homochirality, which may stem from chiral light-matter interactions. Here the authors support this hypothesis with asymmetric photolysis experiments on racemic isovaline films, showing that circularly polarized starlight can produce l-enantiomeric excesses that can be amplified during parent bodies’ alteration.
- Jana Bocková
- , Nykola C. Jones
- & Cornelia Meinert
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Article
| Open AccessNearly 100% selective and visible-light-driven methane conversion to formaldehyde via. single-atom Cu and Wδ+
Direct solar-driven methane (CH4) reforming is highly desirable but challenging. Here, the synergy of atomic Cu species and partially reduced tungsten (Wδ+), stabilized over an oxygen-vacancy-rich WO3, enables exceptional CH4 conversion to formaldehyde (HCHO) under visible light.
- Lei Luo
- , Xiaoyu Han
- & Junwang Tang
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Article
| Open AccessSingle-atomic-site platinum steers photogenerated charge carrier lifetime of hematite nanoflakes for photoelectrochemical water splitting
The achievable photocurrent of hematite, α-Fe2O3, is typically limited far below its theoretical limit. Here, the authors engineer single Pt atomic sites with surface oxygen vacancies into hematite photoanodes, which leads to enhanced photoelectrochemical water splitting.
- Rui-Ting Gao
- , Jiangwei Zhang
- & Limin Wu
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Article
| Open AccessFerricyanide photo-aquation pathway revealed by combined femtosecond Kβ main line and valence-to-core x-ray emission spectroscopy
Reliably identifying transient intermediates is crucial to elucidate chemical reaction mechanisms. Here, the authors use femtosecond Fe Kβ main line and valence-to-core x-ray emission spectroscopy to characterize a short-lived intermediate of the aqueous ferricyanide photo-aquation reaction.
- Marco Reinhard
- , Alessandro Gallo
- & Dimosthenis Sokaras
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Article
| Open AccessDesigning reliable and accurate isotope-tracer experiments for CO2 photoreduction
Current verification of CO2 photoreduction products using isotope-tracer methods is insufficient and can provide false-positive results. Here, rigorous protocols and case studies are presented to avoid pitfalls in isotope-tracer experiments.
- Shengyao Wang
- , Bo Jiang
- & Jinhua Ye
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Article
| Open AccessPhotocatalyzed regioselective hydrosilylation for the divergent synthesis of geminal and vicinal borosilanes
Geminal and vicinal borosilanes are useful building blocks in synthetic chemistry. But in contrast to the well-established transition-metal catalyzed methods, radical approaches are rarely explored. Here, the authors report the synthesis of geminal borosilanes from α-selective hydrosilylation of alkenyl boronates via photoinduced hydrogen atom transfer (HAT) catalysis
- Degong Kong
- , Muliang Zhang
- & Jie Wu
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Article
| Open AccessPhotothermal-enabled single-atom catalysts for high-efficiency hydrogen peroxide photosynthesis from natural seawater
Photoproduction of solar fuels and important chemicals is of significant interest. Here, the authors construct a cobalt single atom-based photothermal-photocatalytic heterostructure that realizes efficient hydrogen peroxide photosynthesis from earth-abundant seawater.
- Wei Wang
- , Qun Song
- & Ning Wang
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Article
| Open AccessHigh-density frustrated Lewis pairs based on Lamellar Nb2O5 for photocatalytic non-oxidative methane coupling
To achieve efficient photocatalytic non-oxidative methane coupling, a strong polarization environment with abundant activation sites for C-H scissoring is needed. This can be created through the fabrication of high-density frustrated Lewis pairs on lamellar Nb2O5 using a thermal-reduction promoted phase-transition process.
- Ziyu Chen
- , Yutao Ye
- & Jinlong Zhang
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Article
| Open AccessAn electron-hole rich dual-site nickel catalyst for efficient photocatalytic overall water splitting
Vast majority of photocatalysts for hydrogen production relies on additional sacrificial agents and noble metal cocatalysts. It is of great importance yet challenging to achieve photocatalytic overall water splitting with decent performance. Here, the authors report Ni2P based photocatalyst assisted by H2O2-craking reaction for overall water splitting with H2 and O2 production of 1507 μmol h−1 g−1 H2 and 702 μmol h−1 g−1.
- Xiaoqing Yan
- , Mengyang Xia
- & Guidong Yang
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Article
| Open AccessStrong synergy between gold nanoparticles and cobalt porphyrin induces highly efficient photocatalytic hydrogen evolution
The reaction efficiency of reactants near plasmonic nanostructures can be enhanced under illumination. Here, the authors show that the activity of a Co porphyrin molecular catalyst bound to Au nanoparticles is enhanced by plasmonic effects, yielding a high photocatalytic hydrogen generation rate.
- Huixiang Sheng
- , Jin Wang
- & Gang Lu
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Article
| Open AccessPoly(heptazine imide) ligand exchange enables remarkable low catalyst loadings in heterogeneous metallaphotocatalysis
The development of heterogeneous metallaphotocatalysis is of great interest for sustainable organic synthesis. Herein, the authors demonstrate the incorporation of privileged homogeneous bipyridyl-based Ni-catalysts into highly ordered and crystalline potassium poly(heptazine imide) (K-PHI).
- Liuzhuang Xing
- , Qian Yang
- & Yunfei Cai
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Article
| Open AccessUltrafast motion in a third generation photomolecular motor
Controlling molecular motion at nanoscale is important for the design of nanomachines. Here the authors use ultrafast vibrational and electronic spectroscopy to characterize the mechanism of motion of a light driven molecular motor designed to support translational movement.
- Palas Roy
- , Wesley R. Browne
- & Stephen R. Meech
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Article
| Open AccessSinglet fission as a polarized spin generator for dynamic nuclear polarization
Singlet fission (SF) can create spin-polarized quintet states in organic systems, but this effect and its potential applications have not been sufficiently explored. Here, authors demonstrate that SF in supramolecular assemblies of pentacene chromophores improves the sensitivity of magnetic resonance of water molecules through dynamic nuclear polarization in a water-glycerol glass.
- Yusuke Kawashima
- , Tomoyuki Hamachi
- & Nobuhiro Yanai
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Article
| Open AccessDesigning covalent organic frameworks with Co-O4 atomic sites for efficient CO2 photoreduction
A class of inexpensive aminoanthraquinone organic dyes are shown to facilitate visible-light-driven CO2 reduction. Overall reaction efficiencies were found to be optimal when both electron donating and accepting groups were on a single dye molecule.
- Qian Zhang
- , Shuaiqi Gao
- & Jianji Wang
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Article
| Open AccessRoom-temperature photosynthesis of propane from CO2 with Cu single atoms on vacancy-rich TiO2
A photocatalyst for CO2 reduction to C3H8 is prepared by implanting Cu single atoms on vacancy rich TiO2 single layers. Key reaction intermediates, *CHOCO and *CH2OCOCO, are stabilized on the catalyst which promotes C-C bond formation.
- Yan Shen
- , Chunjin Ren
- & Yong Zhou
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Article
| Open AccessRed light-driven electron sacrificial agents-free photoreduction of inert aryl halides via triplet-triplet annihilation
The functionalization of aryl halides via photocatalysis typically involves the use of blue light. Here, the authors report the photoreduction of aryl halides enabled by red light; the method does not require a sacrificial electron donor.
- Le Zeng
- , Ling Huang
- & Gang Han
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Article
| Open AccessPhotocatalytic CO2 reduction with aminoanthraquinone organic dyes
A class of inexpensive aminoanthraquinone organic dyes are shown to facilitate visible-light-driven CO2 reduction. Overall reaction efficiencies were found to be optimal when both electron donating and accepting groups were on a single dye molecule.
- Qinqin Lei
- , Huiqing Yuan
- & Zhiji Han
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Article
| Open AccessReal-time observation of the buildup of polaron in α-FAPbI3
Polaron formation is considered to play a crucial role to enhance photoelectric performance of hybrid halide perovskites. Here, the authors report the real-time observation of polaron formation process by terahertz emission spectroscopy and reveal two different polaron modes in FAPbI3 films.
- Xingyu Yue
- , Chunwei Wang
- & Juan Du
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Article
| Open AccessOne-stone-for-two-birds strategy to attain beyond 25% perovskite solar cells
Long-term stability and stable efficiency are essential for large-area fabrication of perovskite solar cells. Here, the authors achieve in situ anion-fixation and undercoordinated-Pb passivation using amidino-based ligand, realizing maximum power conversion efficiency of 25.3% with T95 over 500 h.
- Tinghuan Yang
- , Lili Gao
- & Kui Zhao