A g-C3N4/rGO/Cs3Bi2Br9 mediated Z-scheme heterojunction for enhanced photocatalytic CO2 reduction.

Photocatalytic CO2 reduction plays a crucial role in advancing solar fuels, and enhancing the efficiency of the chosen photocatalysts is essential for sustainable energy production. This study demonstrates advancements in the performance of g-C3N4 as a photocatalyst achieved through surface modifications such as exfoliation to increase surface area and surface oxidation for improved charge separation. We also introduce reduced graphene oxide (rGO) in various ratios to both bulk and exfoliated g-C3N4, which effectively mitigates charge recombination and establishes an optimal ratio for enhanced efficiency. g-C3N4/rGO serves to fabricate a hybrid organic/inorganic heterojunction with Cs3Bi2Br9, resulting in a g-C3N4/rGO/Cs3Bi2Br9 composite. This leads to a remarkable increase in photocatalytic conversion of CO2 and H2O to CO, H2 and CH4 at rates of 54.3 (±2.0) µmole- g-1 h-1, surpassing that of pure Cs3Bi2Br9 (11.2 ± 0.4 µmole- g-1 h-1) and bulk g-C3N4 (5.5 ± 0.5 µmole- g-1 h-1). The experimentally determined energy diagram indicates that rGO acts as a solid redox mediator between g-C3N4 and Cs3Bi2Br9 in a Z-scheme heterojunction configuration, ensuring that the semiconductor (Cs3Bi2Br9) with the shallowest conduction band drives the reduction and the one with the deepest valence band (g-C3N4) drives the oxidation. The successful formation of this high-performance heterojunction underscores the potential of the developed composite as a photocatalyst for CO2 reduction, offering promising prospects for advancing the field of solar fuels and achieving sustainable energy goals.

Enhancing the Efficiency and Stability of Tin-Lead Perovskite Solar Cells via Sodium Hydroxide Dedoping of PEDOT:PSS.

Tin-lead (Sn-Pb) perovskite solar cells (PSCs) have gained interest as candidates for the bottom cell of all-perovskite tandem solar cells due to their broad absorption of the solar spectrum. A notable challenge arises from the prevalent use of the hole transport layer, PEDOT:PSS, known for its inherently high doping level. This high doping level can lead to interfacial recombination, imposing a significant limitation on efficiency. Herein, NaOH is used to dedope PEDOT:PSS, with the aim of enhancing the efficiency of Sn-Pb PSCs. Secondary ion mass spectrometer profiles indicate that sodium ions diffuse into the perovskite layer, improving its crystallinity and enlarging its grains. Comprehensive evaluations, including photoluminescence and nanosecond transient absorption spectroscopy, confirm that dedoping significantly reduces interfacial recombination, resulting in an open-circuit voltage as high as 0.90 V. Additionally, dedoping PEDOT:PSS leads to increased shunt resistance and high fill factor up to 0.81. As a result of these improvements, the power conversion efficiency is enhanced from 19.7% to 22.6%. Utilizing NaOH to dedope PEDOT:PSS also transitions its nature from acidic to basic, enhancing stability and exhibiting less than a 7% power conversion efficiency loss after 1176 h of storage in N2 atmosphere.

Ultrastable halide perovskite CsPbBr3 photoanodes achieved with electrocatalytic glassy-carbon and boron-doped diamond sheets.

Halide perovskites exhibit exceptional optoelectronic properties for photoelectrochemical production of solar fuels and chemicals but their instability in aqueous electrolytes hampers their application. Here we present ultrastable perovskite CsPbBr3-based photoanodes achieved with both multifunctional glassy carbon and boron-doped diamond sheets coated with Ni nanopyramids and NiFeOOH. These perovskite photoanodes achieve record operational stability in aqueous electrolytes, preserving 95% of their initial photocurrent density for 168 h of continuous operation with the glassy carbon sheets and 97% for 210 h with the boron-doped diamond sheets, due to the excellent mechanical and chemical stability of glassy carbon, boron-doped diamond, and nickel metal. Moreover, these photoanodes reach a low water-oxidation onset potential close to +0.4 VRHE and photocurrent densities close to 8 mA cm-2 at 1.23 VRHE, owing to the high conductivity of glassy carbon and boron-doped diamond and the catalytic activity of NiFeOOH. The applied catalytic, protective sheets employ only earth-abundant elements and straightforward fabrication methods, engineering a solution for the success of halide perovskites in stable photoelectrochemical cells.

BiVO4 Photoanodes Enhanced with Metal Phosphide Co-Catalysts: Relevant Properties to Boost Photoanode Performance.

Achieving highly performant photoanodes for oxygen evolution is key to developing photoelectrochemical devices for solar water splitting. In this work, BiVO4 photoanodes are enhanced with a series of core-shell structured bimetallic nickel-cobalt phosphides (MPs), and key insights into the role of co-catalysts are provided. The best BiVO4 /Ni1.5 Co0.5 P and BiVO4 /Ni0.5 Co1.5 P photoanodes achieve a 3.5-fold increase in photocurrent compared with bare BiVO4 . It is discovered that this enhanced performance arises from a synergy between work function, catalytic activity, and capacitive ability of the MPs. Distribution of relaxation times analysis reveals that the contact between the MPs, BiVO4 , and the electrolyte gives rise to three routes for hole injection into the electrolyte, all of which are significantly improved by the presence of a second metal cation in the co-catalyst. Kinetic studies demonstrate that the significantly improved interfacial charge injection is due to a lower charge-transfer resistance, enhanced oxygen-evolution reaction kinetics, and larger surface hole concentrations, providing deeper insights into the carrier dynamics in these photoanode/co-catalyst systems for their rational design.

Shape-Controlled Synthesis of Cu3TeO6 Nanoparticles with Photocatalytic Features.

Cu3TeO6 (CTO) has been synthesized by hydrothermal synthesis applying different pH values without any template or a calcination step to control the crystalline phase and the morphology of nanoparticles. The physicochemical properties characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, N2 adsorption, X-ray photoelectron spectroscopy, and diffuse reflectance ultraviolet-visible (DRUV-vis) spectroscopy techniques revealed that the pH values significantly influence the crystal growth. In acidic media (pH = 2), crystal growth has not been achieved. At pH = 4, the yield is low (10%), and the CTO presents irregular morphology. At pH = 6, the yield increases (up to 71%) obtaining an agglomeration of nanoparticles into spherical morphology. At basic conditions (pH = 8), the yield increases up to 90% and the morphology is the same as the sample obtained at pH = 6. At high basic conditions (pH = 10), the yield is similar (92%), although the morphology changes totally to dispersed nanoparticles. Importantly, the as-prepared CTO semiconductor presents photocatalytic activity for H2 production using triethanolamine as a sacrificial agent under visible light illumination. The results also revealed that the nanoparticles agglomerated in a spherical morphology with larger surface area presented almost double activities in H2 production compared to heterogeneously sized particles. These results highlight the suitable optoelectronic properties, including optical band gap, energy levels, and photoconductivity of CTO semiconductors for their use in photocatalytic H2 production.

Cs3Bi2Br9/g-C3N4 Direct Z-Scheme Heterojunction for Enhanced Photocatalytic Reduction of CO2 to CO.

Lead-free halide perovskite derivative Cs3Bi2Br9 has recently been found to possess optoelectronic properties suitable for photocatalytic CO2 reduction reactions to CO. However, further work needs to be performed to boost charge separation for improving the overall efficiency of the photocatalyst. This report demonstrates the synthesis of a hybrid inorganic/organic heterojunction between Cs3Bi2Br9 and g-C3N4 at different ratios, achieved by growing Cs3Bi2Br9 crystals on the surface of g-C3N4 using a straightforward antisolvent crystallization method. The synthesized powders showed enhanced gas-phase photocatalytic CO2 reduction in the absence of hole scavengers of 14.22 (±1.24) µmol CO g-1 h-1 with 40 wt % Cs3Bi2Br9 compared with 1.89 (±0.72) and 5.58 (±0.14) µmol CO g-1 h-1 for pure g-C3N4 and Cs3Bi2Br9, respectively. Photoelectrochemical measurements also showed enhanced photocurrent in the 40 wt % Cs3Bi2Br9 composite, demonstrating enhanced charge separation. In addition, stability tests demonstrated structural stability upon the formation of a heterojunction, even after 15 h of illumination. Band structure alignment and selective metal deposition studies indicated the formation of a direct Z-scheme heterojunction between the two semiconductors, which boosted charge separation. These findings support the potential of hybrid organic/inorganic g-C3N4/Cs3Bi2Br9 Z-scheme photocatalyst for enhanced CO2 photocatalytic activity and improved stability.

Lead-Free Halide Perovskite Cs2AgBiBr6/Bismuthene Composites for Improved CH4 Production in Photocatalytic CO2 Reduction.

CO2 photocatalytic conversion into value-added fuels through solar energy is a promising way of storing renewable energy while simultaneously reducing the concentration of CO2 in the atmosphere. Lead-based halide perovskites have recently shown great potential in various applications such as solar cells, optoelectronics, and photocatalysis. Even though they show high performance, the high toxicity of Pb2+ along with poor stability under ambient conditions restrains the application of these materials in photocatalysis. In this respect, we developed an in situ assembly strategy to fabricate the lead-free double perovskite Cs2AgBiBr6 on a 2D bismuthene nanosheet prepared by a ligand-assisted reprecipitation method for a liquid-phase CO2 photocatalytic reduction reaction. The composite improved the production and selectivity of the eight-electron CH4 pathway compared with the two-electron CO pathway, storing more of the light energy harvested by the photocatalyst. The Cs2AgBiBr6/bismuthene composite shows a photocatalytic activity of 1.49(±0.16) µmol g-1 h-1 CH4, 0.67(±0.14) µmol g-1 h-1 CO, and 0.75(±0.20) µmol g-1 h-1 H2, with a CH4 selectivity of 81(±1)% on an electron basis with 1 sun. The improved performance is attributed to the enhanced charge separation and suppressed electron-hole recombination due to good interfacial contact between the perovskite and bismuthene promoted by the synthesis method.

Scalable All-Inorganic Halide Perovskite Photoanodes with >100 h Operational Stability Containing Earth-Abundant Materials.

The application of halide perovskites in the photoelectrochemical generation of solar fuels and feedstocks is hindered by the instability of perovskites in aqueous electrolytes and the use of expensive electrode and catalyst materials, particularly in photoanodes driving kinetically slow water oxidation. Here, solely earth-abundant materials are incorporated to fabricate a CsPbBr3 -based photoanode that reaches a low onset potential of +0.4 VRHE and 8 mA cm-2 photocurrent density at +1.23 VRHE for water oxidation, close to the radiative efficiency limit of CsPbBr3 . This photoanode retains 100% of its stabilized photocurrent density for more than 100 h of operation by replacing once the inexpensive graphite sheet upon signs of deterioration. The improved performance is due to an efficiently electrodeposited NiFeOOH catalyst on a protective self-adhesive graphite sheet, and enhanced charge transfer achieved by phase engineering of CsPbBr3 . Devices with >1 cm2 area, and low-temperature processing demonstrate the potential for low capital cost, stable, and scalable perovskite photoanodes.

Understanding Effects of Alkyl Side-Chain Density on Polaron Formation Via Electrochemical Doping in Thiophene Polymers.

Polarons exist when charges are injected into organic semiconductors due to their strong coupling with the lattice phonons, significantly affecting electronic charge-transport properties. Understanding the formation and (de)localization of polarons is therefore critical for further developing organic semiconductors as a future electronics platform. However, there are very few studies reported in this area. In particular, there is no direct in situ monitoring of polaron formation and identification of its dependence on molecular structure and impact on electrical properties, limiting further advancement in organic electronics. Herein, how a minor modification of side-chain density in thiophene-based conjugated polymers affects the polaron formation via electrochemical doping, changing the polymers' electrical response to the surrounding dielectric environment for gas sensing, is demonstrated. It is found that the reduction in side-chain density results in a multistep polaron formation, leading to an initial formation of localized polarons in thiophene units without side chains. Reduced side-chain density also allows the formation of a high density of polarons with fewer polymer structural changes. More numerous but more localized polarons generate a stronger analyte response but without the selectivity between polar and non-polar solvents, which is different from the more delocalized polarons that show clear selectivity. The results provide important molecular understanding and design rules for the polaron formation and its impact on electrical properties.

Solution-processable polymers of intrinsic microporosity for gas-phase carbon dioxide photoreduction.

Four solution-processable, linear conjugated polymers of intrinsic porosity are synthesised and tested for gas phase carbon dioxide photoreduction. The polymers' photoreduction efficiency is investigated as a function of their porosity, optical properties, energy levels and photoluminescence. All polymers successfully form carbon monoxide as the main product, without the addition of metal co-catalysts. The best performing single component polymer yields a rate of 66 µmol h-1 m-2, which we attribute to the polymer exhibiting macroporosity and the longest exciton lifetimes. The addition of copper iodide, as a source of a copper co-catalyst in the polymers shows an increase in rate, with the best performing polymer achieving a rate of 175 µmol h-1 m-2. The polymers are active for over 100 h under operating conditions. This work shows the potential of processable polymers of intrinsic porosity for use in the gas phase photoreduction of carbon dioxide towards solar fuels.

A Review on Halide Perovskite-Based Photocatalysts: Key Factors and Challenges.

A growing number of research articles have been published on the use of halide perovskite materials for photocatalytic reactions. These articles extend these materials' great success from solar cells to photocatalytic technologies such as hydrogen production, CO2 reduction, dye degradation, and organic synthesis. In the present review article, we first describe the background theory of photocatalysis, followed by a description on the properties of halide perovskites and their development for photocatalysis. We highlight key intrinsic factors influencing their photocatalytic performance, such as stability, electronic band structure, and sorption properties. We also discuss and shed light on key considerations and challenges for their development in photocatalysis, such as those related to reaction conditions, reactor design, presence of degradable organic species, and characterization, especially for CO2 photocatalytic reduction. This review on halide perovskite photocatalysts will provide a better understanding for their rational design and development and contribute to their scientific and technological adoption in the wide field of photocatalytic solar devices.

Structural evolution of iron forming iron oxide in a deep eutectic-solvothermal reaction.

Deep eutectic solvents (DES) and their hydrated mixtures are used for solvothermal routes towards greener functional nanomaterials. Here we present the first static structural and in situ studies of the formation of iron oxide (hematite) nanoparticles in a DES of choline chloride : urea where xurea = 0.67 (aka. reline) as an exemplar solvothermal reaction, and observe the effects of water on the reaction. The initial speciation of Fe3+ in DES solutions was measured using extended X-ray absorption fine structure (EXAFS), while the atomistic structure of the mixture was resolved from neutron and X-ray diffraction and empirical potential structure refinement (EPSR) modelling. The reaction was monitored using in situ small-angle neutron scattering (SANS), to determine mesoscale changes, and EXAFS, to determine local rearrangements of order around iron ions. It is shown that iron salts form an octahedral [Fe(L)3(Cl)3] complex where (L) represents various O-containing ligands. Solubilised Fe3+ induced subtle structural rearrangements in the DES due to abstraction of chloride into complexes and distortion of H-bonding around complexes. EXAFS suggests the complex forms [-O-Fe-O-] oligomers by reaction with the products of thermal hydrolysis of urea, and is thus pseudo-zero-order in iron. In the hydrated DES, the reaction, nucleation and growth proceeds rapidly, whereas in the pure DES, the reaction initially proceeds quickly, but suddenly slows after 5000 s. In situ SANS and static small-angle X-ray scattering (SAXS) experiments reveal that nanoparticles spontaneously nucleate after 5000 s of reaction time in the pure DES before slow growth. Contrast effects observed in SANS measurements suggest that hydrated DES preferentially form 1D particle morphologies because of choline selectively capping surface crystal facets to direct growth along certain axes, whereas capping is restricted by the solvent structure in the pure DES.

Hypercrosslinked Polymers as a Photocatalytic Platform for Visible-Light-Driven CO2 Photoreduction Using H2 O.

The design of robust, high-performance photocatalysts is key for the success of solar fuel production by CO2 conversion. In this study, hypercrosslinked polymer (HCP) photocatalysts have been developed for the selective reduction of CO2 to CO, combining excellent CO2 sorption capacities, good general stabilities, and low production costs. HCPs are active photocatalysts in the visible light range, significantly outperforming the benchmark material, TiO2 P25, using only sacrificial H2 O. It is hypothesized that superior H2 O adsorption capacities facilitate access to photoactive sites, improving photocatalytic conversion rates when compared to sacrificial H2 . These polymers are an intriguing set of organic photocatalysts, displaying no long-range order or extended π-conjugation. The as-synthesized networks are the sole photocatalytic component, requiring no added cocatalyst doping or photosensitizer, representing a highly versatile and exciting platform for solar-energy conversion.

Synergistic Effect of Simultaneous Doping of Ceria Nanorods with Cu and Cr on CO Oxidation and NO Reduction.

Ceria particles play a key role in catalytic applications such as automotive three-way catalytic systems in which toxic CO and NO are oxidized and reduced to safe CO2 and N2 , respectively. In this work, we explore the incorporation of Cu and Cr metals as dopants in the crystal structure of ceria nanorods prepared by a single-step hydrothermal synthesis. XRD, Raman and XPS confirm the incorporation of Cu and Cr in the ceria crystal lattices, offering ceria nanorods with a higher concentration of oxygen vacancies. XPS also confirms the presence of Cr and Cu surface species. H2 -TPR and XPS analysis show that the simultaneous Cu and Cr co-doping results in a catalyst with a higher surface Cu concentration and a much-enhanced surface reducibility, in comparison with either undoped or singly doped (Cu or Cr) ceria nanorods. While single Cu doping enhances catalytic CO oxidation and Cr doping improves catalytic NO reduction, co-doping with both Cu and Cr enhances the benefits of both dopants in a synergistic manner employing roughly a quarter of dopant weight.

Silver-Decorated TiO2 Inverse Opal Structure for Visible Light-Induced Photocatalytic Degradation of Organic Pollutants and Hydrogen Evolution.

TiO2 inverse opal (TIO) structures were prepared by the conventional wet chemical method, resulting in well-formed structures for photocatalytic activity. The obtained structures were functionalized with liquid flame spray-deposited silver nanoparticles (AgNPs). The nanocomposites of TIO and AgNPs were extensively characterized by various spectroscopies such as UV, Raman, X-ray diffraction, energy-dispersive spectroscopy, and X-ray photoelectron spectroscopy combined with microscopic methods such as scanning electron microscopy, transmission electron microscopy (TEM), and high-resolution TEM. The characterization confirmed that high-quality heterostructures had been fabricated with evenly and uniformly distributed AgNPs. Fabrication of anatase TiO2 was confirmed, and formation of AgNPs was verified with surface plasmon resonant properties. The photocatalytic activity results measured in the gas phase showed that deposition of AgNPs increases photocatalytic activity both under UVA and visible light excitation; moreover, enhanced hydrogen evolution was demonstrated under visible light.

Graphite-protected CsPbBr3 perovskite photoanodes functionalised with water oxidation catalyst for oxygen evolution in water.

Metal-halide perovskites have been widely investigated in the photovoltaic sector due to their promising optoelectronic properties and inexpensive fabrication techniques based on solution processing. Here we report the development of inorganic CsPbBr3-based photoanodes for direct photoelectrochemical oxygen evolution from aqueous electrolytes. We use a commercial thermal graphite sheet and a mesoporous carbon scaffold to encapsulate CsPbBr3 as an inexpensive and efficient protection strategy. We achieve a record stability of 30 h in aqueous electrolyte under constant simulated solar illumination, with currents above 2 mA cm-2 at 1.23 VRHE. We further demonstrate the versatility of our approach by grafting a molecular Ir-based water oxidation catalyst on the electrolyte-facing surface of the sealing graphite sheet, which cathodically shifts the onset potential of the composite photoanode due to accelerated charge transfer. These results suggest an efficient route to develop stable halide perovskite based electrodes for photoelectrochemical solar fuel generation.

A facile way to produce epoxy nanocomposites having excellent thermal conductivity with low contents of reduced graphene oxide.

A well-dispersed phase of exfoliated graphene oxide (GO) nanosheets was initially prepared in water. This was concentrated by centrifugation and was mixed with a liquid epoxy resin. The remaining water was removed by evaporation, leaving a GO dispersion in epoxy resin. A stoichiometric amount of an anhydride curing agent was added to this epoxy-resin mixture containing the GO nanosheets, which was then cured at 90 °C for 1 h followed by 160 °C for 2 h. A second thermal treatment step of 200 °C for 30 min was then undertaken to reduce further the GO in situ in the epoxy nanocomposite. An examination of the morphology of such nanocomposites containing reduced graphene oxide (rGO) revealed that a very good dispersion of rGO was achieved throughout the epoxy polymer. Various thermal and mechanical properties of the epoxy nanocomposites were measured, and the most noteworthy finding was a remarkable increase in the thermal conductivity when relatively very low contents of rGO were present. For example, a value of 0.25 W/mK was measured at 30 °C for the nanocomposite with merely 0.06 weight percentage (wt%) of rGO present, which represents an increase of ~40% compared with that of the unmodified epoxy polymer. This value represents one of the largest increases in the thermal conductivity per wt% of added rGO yet reported. These observations have been attributed to the excellent dispersion of rGO achieved in these nanocomposites made via this facile production method. The present results show that it is now possible to tune the properties of an epoxy polymer with a simple and viable method of GO addition.

Autonomous self-healing structural composites with bio-inspired design.

Strong and tough natural composites such as bone, silk or nacre are often built from stiff blocks bound together using thin interfacial soft layers that can also provide sacrificial bonds for self-repair. Here we show that it is possible exploit this design in order to create self-healing structural composites by using thin supramolecular polymer interfaces between ceramic blocks. We have built model brick-and-mortar structures with ceramic contents above 95 vol% that exhibit strengths of the order of MPa (three orders of magnitude higher than the interfacial polymer) and fracture energies that are two orders of magnitude higher than those of the glass bricks. More importantly, these properties can be fully recovered after fracture without using external stimuli or delivering healing agents. This approach demonstrates a very promising route towards the design of strong, ideal self-healing materials able to self-repair repeatedly without degradation or external stimuli.

In situ thermally reduced graphene oxide/epoxy composites: thermal and mechanical properties.

Graphene has excellent mechanical, thermal, optical and electrical properties and this has made it a prime target for use as a filler material in the development of multifunctional polymeric composites. However, several challenges need to be overcome to take full advantage of the aforementioned properties of graphene. These include achieving good dispersion and interfacial properties between the graphene filler and the polymeric matrix. In the present work, we report the thermal and mechanical properties of reduced graphene oxide/epoxy composites prepared via a facile, scalable and commercially viable method. Electron micrographs of the composites demonstrate that the reduced graphene oxide (rGO) is well dispersed throughout the composite. Although no improvements in glass transition temperature, tensile strength and thermal stability in air of the composites were observed, good improvements in thermal conductivity (about 36 %), tensile and storage moduli (more than 13 %) were recorded with the addition of 2 wt% of rGO.

ATR-FTIR measurements of albumin and fibrinogen adsorption: Inert versus calcium phosphate ceramics.

Arthritis, bone fracture, bone tumors and other musculoskeletal diseases affect millions of people across the world. Nowadays, inert and bioactive ceramics are used as bone substitutes or for bone regeneration. Their bioactivity is very much dictated by the way proteins adsorb on their surface. In this work, we compared the adsorption of albumin and fibrinogen on inert and calcium phosphates ceramics (CaPs) using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) to follow in situ protein adsorption on these materials. To this effect, we developed a sol-gel technique to control the surface chemistry of an ATR-FTIR detector. Hydroxyapatite adsorbed more albumin and ß-tricalcium phosphate adsorbed more fibrinogen. Biphasic calcium phosphate presented the lowest adsorption among CaP for both proteins, illustrating the effect of surface heterogeneities. Inert ceramics adsorbed a lower amount of both proteins compared with bioactive ceramics. A significant change was observed in the conformation of the adsorbed protein versus the surface chemistry. Hydroxyapatite produced a larger loss of α-helix structure on albumin and biphasic calcium phosphate reduced ß-sheet percentage on fibrinogen. Inert ceramics produced large α-helix loss on albumin and presented weak interaction with fibrinogen. Zirconia did not adsorb albumin and titanium dioxide promoted huge denaturalization of fibrinogen.