Single-step conversion of lignin monomers to phenol: Bridging the gap between lignin and high-value chemicals

Transformation of lignin into high-value chemicals is hampered by the complexity of monomers obtained from lignin depolymerization. Here we report a strategy, composed of hy-dro-demethoxylation and de-alkylation reactions, that is able to chemically converge various lig-nin-derived phenolic monomers into phenol in a single-step. Using 2-methoxy-4-propylphenol as a model compound, Pt/C exhibited the best performance in hydro-demethoxylation reaction afford-ing 80% 4-propylphenol from 2-methoxy-4-propylphenol, while H-ZSM-5 was identified as the most suitable catalyst for de-alkylation, achieving 83% yield of phenol from 4-propylphenol. Since the two catalysts operate under compatible conditions, combining the two catalysts to simultane-ously promote both hydro-demethoxylation and de-alkylation reactions was achieved. Configura-tion of how to organize the catalysts is a critical parameter, where the physical mixture of the two was most effective, providing over 60% phenol from 2-methoxy-4-propylphenol in a single-step.

Interfacial engineering through lead binding using crown ethers in perovskite solar cells

In the domain of perovskite solar cells(PSCs),the imperative to reconcile impressive photovoltaic performance with lead-related issue and environmental stability has driven innovative solutions.This study pioneers an approach that not only rectifies lead leakage but also places paramount importance on the attainment of rigorous interfacial passivation.Crown ethers,notably benzo-18-crown-6-ether(B18C6),were strategically integrated at the perovskite-hole transport material interface.Crown ethers exhibit a dual role:efficiently sequestering and immobilizing Pb^(2+)ions through host-guest complexation and simultaneously establishing a robust interfacial passivation layer.Selected crown ether candidates,guided by density functional theory(DFT)calculations,demonstrated proficiency in binding Pb2+ions and optimizing interfacial energetics.Photovoltaic devices incorporating these materials achieved exceptional power conversion efficiency(PCE),notably 21.7%for B18C6,underscoring their efficacy in lead binding and interfacial passivation.Analytical techniques,including time-of-flight secondary ion mass spectrometry(ToF-SIMS),ultraviolet photoelectron spectroscopy(UPS),time-resolved photoluminescence(TRPL),and transient absorption spectroscopy(TAS),unequivocally affirmed Pb^(2+)ion capture and suppression of non-radiative recombination.Notably,these PSCs maintained efficiency even after enduring 300 h of exposure to 85%relative humidity.This research underscores the transformative potential of crown ethers,simultaneously addressing lead binding and stringent interfacial passivation for sustainable PSCs poised to commercialize and advance renewable energy applications.

Thermodynamics of Solvent Extraction of Rare and Scattered Metal-Indium with Diethylhexylmonothiophosphoric Acid

The thermodynamics of extracting In（ Ⅲ） with diethylhexylmonothiophosphoric acid as an extractant in a H2SO4 system is reported. The equilibrium molalities of In^3＋ ions were measured at a high acidity and ionic strengths varying from 0. 1 to 2.0 mol/kg in an aqueous phase containing Na2SO4 as the supporting electrolyte. The values of the standard extraction constant K^0 at various temperatures were obtained by the methods of extrapolation and polynomial approximation. The equation lgK^0 = - 51.95 - 5.93 × 10^3/T ＋ 6. 15 × 10^-2 T was also obtained and the thermodynamic quantities for the extraction process were calculated.

Study of borohydride ionic liquids as hydrogen storage materials

Stability of borohydrides is determined by the localization of the negative charge on the boron atom.Ionic liquids(ILs) allow to modify the stability of the borohydrides and promote new dehydrogenation pathways with a lower activation energy. The combination of borohydride and IL is very easy to realize and no expensive rare earth metals are required. The composite of the ILs with complex hydrides decreases the enthalpy and activation energy for the hydrogen desorption. The Coulomb interaction between borohydride and IL leads to a destabilization of the materials with a significantly lower enthalpy for hydrogen desorption. Here, we report a simple ion exchange reaction using various ILs, such as vinylbenzyltrimethylammonium chloride([VBTMA][Cl]), 1-butyl-3-methylimidazolium chloride([bmim][Cl]), and 1-ethyl-1-methylpyrrolidinium bromide([EMPY][Br]) with NaBH4 to decrease the hydrogen desorption temperature. Dehydrogenation of 1-butyl-3-methylimidazolium borohydride([bmim][BH4]) starts below 100℃. The quantity of desorbed hydrogen ranges between 2.4 wt% and 2.9 wt%, which is close to the theoretical content of hydrogen. The improvement in dehydrogenation is due to the strong amine cation that destabilizes borohydride by charge transfer.

Unraveling and optimizing the metal-metal oxide synergistic effect in a highly active Co_(x)(CoO)_(1–x) catalyst for CO_(2) hydrogenation

The relation between catalytic reactivities and metal/metal oxide ratios, as well as the functions of the metal and the metal oxides were investigated in the CO_2 hydrogenation reaction over highly active Co_x(CoO)_(1–x)catalysts in operando. The catalytic reactivity of the samples in the CO_2 methanation improves with the increased Co O concentration. Strikingly, the sample with the highest concentration of CoO, i.e., Co_(0.2)(CoO)_(0.8), shows activity at temperatures lower than 200 °C where the other samples with less CoO are inactive. The origins of this improvement are the increased amount and moderate binding of adsorbed CO_2 on CoO sites. The derivative adsorption species are found to be intermediates of the CH4 formation. The metallic Co functions as the electronically catalytic site which provides electrons for the hydrogenation steps. As a result, an abundant amount of CoO combined with Co is the optimal composition of the catalyst for achieving the highest reactivity for CO_2 hydrogenation.

Mesoporous poly(ionic liquid)s with dual active sites for highly efficient CO_(2)conversion

Atmospheric CO_(2)concentrations are soaring due to the continued use of fossil fuels in energy production,an anthropogenic activity that is playing a leading role in global warming.Thus,research aimed at the capture and conversion of CO_(2)into value-added products,such as cyclic carbonates,is booming.While CO_(2)is an abundant,cheap,non-toxic,and readily accessible Cl feedstock,its thermodynamic stability necessitates the development of highly efficient catalysts that are able to promote chemical reactions under mild conditions.In this work,a novel mesoporous poly(ionic liquid)with dual active sites was synthesized through a facile method that involves co-polymerization,post-synthetic metalation,and supercritical CO_(2)drying.Due to a high density of nucleophilic and electrophilic sites,the as-prepared poly(ionic liquid),denoted as P2D-4BrBQA-Zn,offers excellent performance in a CO_(2)cycloaddition reaction using epichlorohydrin as the substrate(98.9%conversion and 96.9%selectivity).Moreover the reaction is carried out under mild,solvent-free,and additive-free conditions.Notably,P2D-4BrBQA-Zn also efficiently promotes the conversion of various other epoxide substrates into cyclic carbonates.Overall,the catalyst is found to have excellent substrate compatibility,stability,and recyclability.

In vivo polydopamine coating of Rhodobacter sphaeroides for enhanced electron transfer

Recent advances in coupling light-harvesting microorganisms with electronic components have led to a new generation of biohybrid devices based on microbial photocatalysts.These devices are limited by the poorly conductive interface between phototrophs and synthetic materials that inhibit charge transfer.This study focuses on overcoming this bottleneck through the metabolically-driven encapsulation of photosynthetic cells with a bio-inspired conductive polymer.Cells of the purple non sulfur bacterium Rhodobacter sphaeroides were coated with a polydopamine(PDA)nanoparticle layer via the self-polymerization of dopamine under anaerobic conditions.The treated cells show preserved light absorption of the photosynthetic pigments in the presence of dopamine concentrations ranging between 0.05–3.5 mM.The thickness and nanoparticle formation of the membrane-associated PDA matrix were further shown to vary with the dopamine concentrations in this range.Compared to uncoated cells,the encapsulated cells show up to a 20-fold enhancement in transient photocurrent measurements under mediatorless conditions.The biologically synthesized PDA can thus act as a matrix for electronically coupling the light-harvesting metabolisms of cells with conductive surfaces.

Orientation controlled photogenerated carriers on selfsupporting CdS/Ni_(3)S_(2) paper toward photocatalytic hydrogen evolution and biomass upgrading

The appropriate regulation of band structure is an effective strategy in constructing efficient photocatalytic systems.Present photocatalytic system mainly employs powder photocatalysts,which makes their recovery reliant on expensive separation processes and severely limits their industrial application.Herein,we constructed a novel CdS/Ni_(3)S_(2)heterostructure using free-standing and flexible nickel fiber paper as the matrix.The regulated energy band structure achieves effective electron–hole separation.The as-synthesized flexible photocatalyst exhibits considerable photocatalytic activity toward the H_(2)evolution reaction under visible-light irradiation,with an H_(2)production rate of5.63μmol·cm^(-2)·h^(-1)(14.1 mmol·g^(-1)cat·h^(-1)according to the catalyst loading content).Additionally,the otherwisewasted excited holes simultaneously drive organic transformations to yield value-added organic products,thus markedly improving the photocatalytic H_(2)evolution rate.Such a photocatalytic system is scaled up further,where a self-supported 20 cm×25 cm sample achieves a champion H_(2)production rate of 60-80μmol·h^(-1)under practical sun irradiation.This newly developed self-supported photocatalyst produces opportunities for practical solar H2production with biomass upgrading.

An Analytical Model for the Electrolyser Performance Derived from Materials Parameters

Hydrogen is seen as a key element for the transition from a fossil fuel based economy to a renewable, sustainable economy. Hydrogen can be used either directly as an energy carrier or as a feedstock for the reduction of CO2 to synthetic hydrocarbons. Hydrogen can be produced by electrolysis, decomposing water in oxygen and hydrogen. This paper presents an overview of the three major electrolysis technologies: acidic (PEM), alkaline (AEL) and solid oxide electrolysis (SOEC). An updated list of existing electrolysers and commercial providers is provided. Most interestingly, the specific prices of commercial devices are also given when available. Despite tremendous development of the PEM technology in the past decades, the largest and most efficient electrolysers are still alkaline. Thus, this technology is expected to play a key role in the transition to the hydrogen society. A detailed description of the components in an alkaline electrolyser and an analytical model of the process are provided. The analytical model allows investigating the influence of the different operating parameters on the efficiency. Specifically, the effect of temperature on the electrolyte conductivity—and thus on the efficiency—is analyzed. It is found that in the typical range of operating temperatures for alkaline electrolysers of 65°C - 220°C, the efficiency varies by up to 3.5 percentage points, increasing from 80% to 83.5% at 65°C and 220°C, respectively.

Assembling a Photoactive 2D Puzzle: From Bulk Powder to LargeArea Films of Semiconducting Transition-Metal Dichalcogenide Nanosheets

Two-dimensional(2D)semiconducting materials are poised to revolutionize ultrathin,high-performance optoelectronic devices.In particular,transition-metal dichalcogenides(TMDs)are well-suited for applications requiring robust and stable materials such as electrocatalytic,photocatalytic,and photo-electrochemical devices.One of the most compelling assets of these materials is the ability to produce and process 2D TMDs in the nanosheet form using solution-based(SB)exfoliation methods.Compared to other methods,SB techniques are typically inexpensive,efficient,and more suitable for scale-up and industrial implementation.In acknowledgment of the importance of this area,much work has been done to develop various SB methods starting from the exfoliation of bulk crystalline TMD materials to the chemical modification of final devices consisting of thin films of semiconducting 2D TMD nanosheets.However,not all SB methods are equally compatible or interchangeable,and they result in very diverse material and device properties.Therefore,the aim of this Account is to provide an overview of the developed SB techniques that can serve as a guide for assembling high-performance thin films of 2D TMDs.We start by introducing the most popular methods for producing 2D TMDs using liquid-phase exfoliation(LPE),discussing their working mechanisms as well as their advantages and disadvantages.Notably we highlight a recently developed LPE technique using electro-intercalation that draws on the advantages of previously presented methods.Next,we discuss processing the as-produced 2D TMD nanosheets via SB separating techniques designed for size and morphology selection while also presenting the ongoing challenges in this area.We then examine SB methods for processing the selected 2D nanomaterial dispersions into semiconducting thin films.Various methods are compared and contrasted,and special attention is paid to a recently developed method that carefully deposits 2D TMD nanoflakes with preferential alignment and has been shown scalable to the meter-squared size range.Finally,we explore strategies for increasing the optoelectronic performance of the TMD films via device engineering and defect management.We scrutinize these posttreatments based on the final device application,which are explicitly discussed.In all of the discussed processes we present the most promising SB techniques giving critical analysis and insight from experience.While we provide our own“best practices”,we stress the use of adaptability and critical thinking when designing specifically tailored procedures.By providing examples of different uses and measured improvements in one comprehensive guide,we hope to simplify process-development and aid researchers in making their own unique photoactive 2D“puzzles”.

Polydopamine-coated photoautotrophic bacteria for improving extracellular electron transfer in living photovoltaics

Living photovoltaics are microbial electrochemical devices that use whole cell–electrode interactions to convert solar energy to electricity.The bottleneck in these technologies is the limited electron transfer between the microbe and the electrode surface.This study focuses on enhancing this transfer by engineering a polydopamine(PDA)coating on the outer membrane of the photosynthetic microbe Synechocystis sp.PCC6803.This coating provides a conductive nanoparticle shell to increase electrode adhesion and improve microbial charge extraction.A combination of scanning electron microscopy(SEM),transmission electron microscopy(TEM),UV–Vis absorption,and Raman spectroscopy measurements were used to characterize the nanoparticle shell under various synthesis conditions.The cell viability and activity were further assessed through oxygen evolution,growth curve,and confocal fluorescence microscopy measurements.The results show sustained cell growth and detectable PDA surface coverage under slightly alkaline conditions(pH 7.5)and at low initial dopamine(DA)concentrations(1 mM).The exoelectrogenicity of the cells prepared under these conditions was also characterized through cyclic voltammetry(CV)and chronoamperometry(CA).The measurements show a three-fold enhancement in the photocurrent at an applied bias of 0.3 V(vs.Ag/AgCl[3 M KCl])compared to non-coated cells.This study thus lays the framework for engineering the next generation of living photovoltaics with improved performances using biosynthetic electrodes.

Lanthanide NIR luminescence for telecommunications, bioanalyses and solar energy conversion

Present-day advanced technologies heavily rely on the exciting magnetic and spectroscopic properties of lanthanide ions. In particular, their ability to generate well-characterized and intense near-infrared (NIR) luminescence is exploited in any modern fiber-optic telecommunication network. In this feature article, we first summarize the whereabouts underlying the design of highly luminescent NIR molecular edifices and materials. We then focus on describing the main trends in three applications related to this spectral range: telecommunications, biosciences, and solar energy conversion. In telecommunications, efforts concentrate presently on getting easily processable polymer-based waveguide amplifiers. Upconversion nanophosphors emitting in the visible after NIR excitation are now ubiquitous in many bioanalyses while their application to bio-imaging is still in its early stages; however, highly sensitive NIR-NIR systems start to be at hand for both in vitro and in vivo imaging, as well as dual probes combining magnetic resonance and optical imaging. Finally, both silicon-based and dye-sensitized solar cells benefit from the downconversion and upconversion capabilities of lanthanide ions to harvest UV and NIR solar light and to boost the overall quantum efficiency of these next-generation devices.

Enhancing bioelectricity generation in microbial fuel cells and biophotovoltaics using nanomaterials

Microbial fuel cells and biophotovoltaics represent promising technologies for green bioelectricity generation.However,these devices suffer from low durability and efficiency that stem from their reliance on living organisms to act as catalysts.Such limitations can be overcome with augmented capabilities enabled by nanotechnology.This review presents an overview of the different nanomaterials used to enhance bioelectricity generation through improved light harvesting,extracellular electron transfer,and anode performance.The implementation of nanomaterials in whole-cell energy devices holds promise in developing bioelectrical devices that are suitable for industry.

Perovskite Solar Cells Yielding Reproducible Photovoltage of 1.20 V

High photovoltages and power conversion efciencies of perovskite solar cells(PSCs)can be realized by controlling the undesired nonradiative charge carrier recombination.Here,we introduce a judicious amount of guanidinium iodide into mixed-cation and mixed-halide perovskite flms to suppress the parasitic charge carrier recombination,which enabled the fabrication of>20%efcient and operationally stable PSCs yielding reproducible photovoltageas high as 1.20 V.By introducing guanidinium iodide into the perovskite precursor solution,the bandgap of the resulting absorber material changed minimally;however,the nonradiative recombination diminished considerably as revealed by time-resolved photoluminescence and electroluminescence studies.Furthermore,using capacitance-frequency measurements,we were able to correlate the hysteresis features exhibited by the PSCs with interfacial charge accumulation.Tis study opens up a path to realize new record efciencies for PSCs based on guanidinium iodide doped perovskite flms.

Controllable CO adsorption determines ethylene and methane productions from CO_(2) electroreduction

Among all CO2 electroreduction products,methane(CH4)and ethylene(C_(2)H_(4))are two typical and valuable hydrocarbon products which are formed in two different pathways:hydrogenation and dimerization reactions of the same CO intermediate.Theoretical studies show that the adsorption configurations of CO intermediate determine the reaction pathways towards CH4/C_(2)H_(4).However,it is challenging to experimentally control the CO adsorption configurations at the catalyst surface,and thus the hydrocarbon selectivity is still limited.Herein,we seek to synthesize two well-defined copper nanocatalysts with controllable surface structures.The two model catalysts exhibit a high hydrocarbon selectivity toward either CH4(83%)or C_(2)H_(4)(93%)under identical reduction conditions.Scanning transmission electron microscopy and X-ray absorption spectroscopy characterizations reveal the low-coordination Cu^(0)sites and local Cu^(0)/Cu^(+)sites of the two catalysts,respectively.CO-temperature programed desorption,in-situ attenuated total reflection Fourier transform infrared spectroscopy and density functional theory studies unveil that the bridge-adsorbed CO(CO_(B))on the low-coordination Cu^(0)sites is apt to be hydrogenated to CH4,whereas the bridge-adsorbed CO plus linear-adsorbed CO(CO_(B)+CO_(L))on the local Cu^(0)/Cu^(+)sites are apt to be coupled to C_(2)H_(4).Our findings pave a new way to design catalysts with controllable CO adsorption configurations for high hydrocarbon product selectivity.

Preface to the Special Issue of Rare Earth Luminescent Materials

Lanthanide photonics,and more particularly lanthanide luminescence,is at the heart of applications as diverse as lighting devices,displays,lasers,optical fibers and associated telecommunication networks,security markings,solar energy conversion and photocatalysis,or bioanalysis and bioimaging.

Roles of Anions in Pyridinecarboxamide-copper（Ⅱ） Supramolecular Networks

Three complexes Cu（ppca）2（H2O）2（NO3）2 （1）, Cu2（μ-OH）2（ppca）2（H2O）4）·（ClO4）2 （2） and Cu2（μ-CH3COO）4（ppca）2（3） have been synthesized by the reaction of copper（Ⅱ） salts with N-phenyl-4-pyridinecarboxamide （ppca） and characterized. For anions, in complex 1, NO3^- coordinated with copper（Ⅱ）, in complex 2 perchlorate anion did not take part in coordination, the copper（Ⅱ） cations were connected by μ-OH to form a dinuclear unit, and complex 3 had a dimeric copper（Ⅱ） carboxylate paddle-wheel core. Noncovalent interactions linked these complexes to form supramolecular networks. Different coordinating modes of anions controlled modes of intennolecular interactions, which resulted in different final structures.

A Triethyleneglycol C60 Mono-adduct Derivative for Efficient Electron Transport in Inverted Perovskite Solar Cells

Inverted perovskite solar cells(PSCs)have attracted increasing attention in recent years owing to their low-temperature fabrication proces s.However,they suffer from a limited number of electron transport materials available with[6,6]-phenyl C61 butyric acid methyl ester(PCBM)to be the most widely studied based on its appropriate energy levels and high electron mobility.The low relative permittivity and aggregation tendency upon illumination of PCBM,however,compromises the solar cell efficiency whereas its modest hydrophobicity negatively impacts on the device stability.Alternative electron transport materials with desired properties and appropriate degree of hydrophobicity are thus desirable for further developments in inverted PSCs.Herein,we synthesize a triethyleneglycol C60 mono-adduct derivative(termed as EPF03)and test it as a novel electron transport material to replace PCBM in inverted PSCs based on a quadruple cation(RbCsMAFA)perovskite.We also compare this derivative with two novel fullerenes decorated with two(EPF01)or one dodecyl(EPF02)long side chains.The latter two fail to perform efficiently in inverted PSCs whereas the former enabled a power conversion efficiency of 18.43%,which represents a 9%improvement compared to the reference device using PCBM(17.21%).The enhanced performance mainly stems from improved electron extraction and reduced recombination enabled by the insertion of the large relative permittivity amongst other properties of EPF03.Furthermore,our results indicate that triethylene glycol side chains can also passivate perovskite trap states,suppress ion migration and enhance photostability and long-term stability of EPF03 based perovskite solar cells.

Regulated CO adsorption by the electrode with OH^(-) repulsive property for enhancing C–C coupling

Electrochemical CO_(2) reduction driven by renewable electricity is one of the promising strategies to store sus-tainable energy as fuels.However,the selectivity of value-added multi-carbon products remains poor for further application of this process.Here,we regulate CO adsorption by forming a Nafion layer on the copper(Cu)electrode that is repulsive to OH^(-),contributing to enhanced selectivity of CO_(2) reduction to C_(2) products with the suppression of C 1 products.The operando Raman spectroscopy indicates that the local OH^(-)would adsorb on part of active sites and decrease the adsorption of CO.Therefore,the electrode with repulsive to OH^(-)can adjust the concentration of OH^(-),leading to the increased adsorption of CO and enhanced C–C coupling.This work shows that electrode design could be an effective strategy for improving the selectivity of CO_(2) reduction to multi-carbon products.

Lanthanide mechanoluminescence

Mechanoluminescence （ML） is the emission of light consecutive to a mechanical force or stress imposed to a crystalline material. Many inorganic and organic compounds present this phenomenon that is known for over 400 years. Lanthanide and uranyl salts were among the first substances investigated for this property. Mechanoluminescence, also referred to as triboluminescence, is often considered as being a badly understood phenomenon. In fact it is because of two main reasons. Firstly, a variety of different mechanical stresses, from simple rubbing, to applied pressure, crushing, impact of a weight, ultrasound, laser-generated shock wave, crystallization, dissolution of crystals, or even wind can trigger it. Secondly, ML is very sensitive to the purity and morphology of the sample： in inorganic compounds, generation of traps by doping ＂impurities＂ （e.g. lanthanide ions） is responsible for light emission so that the exact composition of the sample has to be known to a very detailed level; for chelates, the crystallization conditions are crucial since they often generate extended networks of weak interactions that are instrumental in triggering ML when they are broken. In fact mechanisms of ML are relatively well known and theories and models often reproduce very well the experiments. Additionally, practical applications are at hand, for example stress, crack, and impact sensors based on SrAI204：Eu11 or Et3NH[Eu（dbm）4] are used to test structures and materials as diverse as road bridges, reinforced concrete elements, pressur- ized containers or airplane wings and to image the propagation of cracks or stress distribution. Military and security applications involve detecting the passage of vehicle or soldiers and producing counter- feiting inks while more joyful applications are luminous balls, wrapping papers and adhesive tapes. Not only bulk materials, but micro- and nanoparticles feature mechanoluminescent properties and single particle manipulation under an AFM allows one to produce light sources that could be useful to several photonic applications, including bio-applications. The review starts with a short historical background of ML, discussing definitions, and providing some theoretical bases. It then presents instrumental setups before covering all aspects of lanthanide mechanoluminescence, starting with simple salts, then doped inorganic compounds （irradiated and non- irradiated） and finally chelates. Mechanoluminescent sensors are described with various actual and potential applications. Literature is covered until April 2017. The wealth of information gathered during the past 20 years in the field and the broad understanding of the phenomenon attained show that the field is presently ready for a quantitative leap forward. Many subjects are waiting to be developed, including NIR mechanoluminescence or bio-applications based on single mechanoluminescent particle light sources; in addition, designing new types of mechanoluminescent materials with techniques par- alleling the developments in other aspects of lanthanide photonics could prove extremely rewarding.