High carrier mobility along the [111] orientation in Cu2O photoelectrodes.

Solar fuels offer a promising approach to provide sustainable fuels by harnessing sunlight1,2. Following a decade of advancement, Cu2O photocathodes are capable of delivering a performance comparable to that of photoelectrodes with established photovoltaic materials3-5. However, considerable bulk charge carrier recombination that is poorly understood still limits further advances in performance6. Here we demonstrate performance of Cu2O photocathodes beyond the state-of-the-art by exploiting a new conceptual understanding of carrier recombination and transport in single-crystal Cu2O thin films. Using ambient liquid-phase epitaxy, we present a new method to grow single-crystal Cu2O samples with three crystal orientations. Broadband femtosecond transient reflection spectroscopy measurements were used to quantify anisotropic optoelectronic properties, through which the carrier mobility along the [111] direction was found to be an order of magnitude higher than those along other orientations. Driven by these findings, we developed a polycrystalline Cu2O photocathode with an extraordinarily pure (111) orientation and (111) terminating facets using a simple and low-cost method, which delivers 7 mA cm-2 current density (more than 70% improvement compared to that of state-of-the-art electrodeposited devices) at 0.5 V versus a reversible hydrogen electrode under air mass 1.5 G illumination, and stable operation over at least 120 h.

Low-Cost Antimony Selenosulfide with Tunable Bandgap for Highly Efficient Solar Cells.

About 10% efficient antimony selenosulfide (Sb2 (S,Se)3 ) solar cell is realized by using selenourea as a hydrothermal raw material to prepare absorber layers. However, tailoring the bandgap of hydrothermal-based Sb2 (S,Se)3 film to the ideal bandgap (1.3-1.4 eV) using the selenourea for optimal efficiency is still a challenge. Moreover, the expensive selenourea dramatically increases the fabricating cost. Here, a straightforward one-step hydrothermal method is developed to prepare high-quality Sb2 (S,Se)3 films using a novel precursor sodium selenosulfate as the selenium source. By tuning the Se/(Se+S) ratio in the hydrothermal precursor solution, a series of high-quality Sb2 (S,Se)3 films with reduced density of deep defect states and tunable bandgap from 1.31 to 1.71 eV is successfully prepared. Consequently, the best efficiency of 10.05% with a high current density of 26.01 mA cm-2 is achieved in 1.35 eV Sb2 (S,Se)3 solar cells. Compared with the traditional method using selenourea, the production cost for the Sb2 (S,Se)3  devices is reduced by over 80%. In addition, the device exhibits outstanding stability, maintaining more than 93% of the initial power conversion efficiency after 30 days of exposure in the atmosphere without encapsulation. The present work definitely paves a facile and effective way to develop low-cost and high-efficiency chalcogenide-based photovoltaic devices.

Precise Control of Crystallization and Phase-Transition with Green Anti-Solvent in Wide-Bandgap Perovskite Solar Cells with Open-Circuit Voltage Exceeding 1.25 V.

Wide-bandgap perovskite solar cells (PSCs) have attracted a lot of attention due to their application in tandem solar cells. However, the open-circuit voltage (VOC ) of wide-bandgap PSCs is dramatically limited by high defect density existing at the interface and bulk of the perovskite film. Here, an anti-solvent optimized adduct to control perovskite crystallization strategy that reduces nonradiative recombination and minimizes VOC deficit is proposed. Specifically, an organic solvent with similar dipole moment, isopropanol (IPA) is added into ethyl acetate (EA) anti-solvent, which is beneficial to form PbI2 adducts with better crystalline orientation and direct formation of α-phase perovskite. As a result, EA-IPA (7-1) based 1.67 eV PSCs deliver a power conversion efficiency of 20.06% and a VOC of 1.255 V, which is one of the remarkable values for wide-bandgap around 1.67 eV. The findings provide an effective strategy for controlling crystallization to reduce defect density in PSCs.

Efficient Electrochemical Nitrate Reduction to Ammonia with Copper-Supported Rhodium Cluster and Single-Atom Catalysts.

The electrochemical nitrate reduction reaction (NITRR) provides a promising solution for restoring the imbalance in the global nitrogen cycle while enabling a sustainable and decentralized route to source ammonia. Here, we demonstrate a novel electrocatalyst for NITRR consisting of Rh clusters and single-atoms dispersed onto Cu nanowires (NWs), which delivers a partial current density of 162 mA cm-2 for NH3 production and a Faradaic efficiency (FE) of 93 % at -0.2 V vs. RHE. The highest ammonia yield rate reached a record value of 1.27 mmol h-1 cm-2 . Detailed investigations by electron paramagnetic resonance, in situ infrared spectroscopy, differential electrochemical mass spectrometry and density functional theory modeling suggest that the high activity originates from the synergistic catalytic cooperation between Rh and Cu sites, whereby adsorbed hydrogen on Rh site transfers to vicinal *NO intermediate species adsorbed on Cu promoting the hydrogenation and ammonia formation.

Selective C-C Coupling in Carbon Dioxide Electroreduction via Efficient Spillover of Intermediates As Supported by Operando Raman Spectroscopy.

Developing efficient systems for the conversion of carbon dioxide to valuable chemicals using solar power is critical for mitigating climate change and ascertaining the world's future supply of clean fuels. Here, we introduce a mesoscopic cathode consisting of Cu nanowires decorated with Ag islands, by the reduction of Ag-covered Cu2O nanowires prepared via galvanic replacement reaction. This catalyst enables CO2 reduction to ethylene and other C2+ products with a faradaic efficiency of 76%. Operando Raman spectroscopy reveals intermediate formation of CO at Ag sites which undergo subsequent spillover and hydrogenation on the Cu nanowires. Our Cu-Ag bimetallic design enables a ∼95% efficient spillover of intermediates from Ag to Cu, delivering an improved activity toward the formation of ethylene and other C2+ products. We also demonstrate a solar to ethylene conversion efficiency of 4.2% for the photoelectrochemical CO2 reduction using water as electron and proton donor, and solar power together with perovskite photovoltaics to drive the uphill reaction.

Atomic Layer Deposition of ZnO on CuO Enables Selective and Efficient Electroreduction of Carbon Dioxide to Liquid Fuels.

Electrochemical reduction of carbon dioxide, if powered by renewable electricity, could serve as a sustainable technology for carbon recycling and energy storage. Among all the products, ethanol is an attractive liquid fuel. However, the maximum faradaic efficiency of ethanol is only ≈10 % on polycrystalline Cu. Here, CuZn bimetallic catalysts were synthesized by in situ electrochemical reduction of ZnO-shell/CuO-core bi-metal-oxide. Dynamic evolution of catalyst was revealed by STEM-EDS mapping, showing the migration of Zn atom and blending between Cu and Zn. CuZn bimetallic catalysts showed preference towards ethanol formation, with the ratio of ethanol/ethylene increasing over five times regardless of applied potential. We achieved 41 % faradaic efficiency for C2+ liquids with this catalyst. Transitioning from H-cell to an electrochemical flow cell, we achieved 48.6 % faradaic efficiency and -97 mA cm-2 partial current density for C2+ liquids at only -0.68 V versus reversible hydrogen electrode in 1 m KOH. Operando Raman spectroscopy showed that CO binding on Cu sites was modified by Zn. Free CO and adsorbed *CH3 are believed to combine and form *COCH3 intermediate, which is exclusively reduced to ethanol.

Hyperbranched TiO2-CdS nano-heterostructures for highly efficient photoelectrochemical photoanodes.

Quasi-1D-hyperbranched TiO2 nanostructures are grown via pulsed laser deposition and sensitized with thin layers of CdS to act as a highly efficient photoelectrochemical photoanode. The device properties are systematically investigated by optimizing the height of TiO2 scaffold structure and thickness of the CdS sensitizing layer, achieving photocurrent values up to 6.6 mA cm-2 and reaching saturation with applied biases as low as 0.35 VRHE. The high internal conversion efficiency of these devices is to be found in the efficient charge generation and injection of the thin CdS photoactive film and in the enhanced charge transport properties of the hyperbranched TiO2 scaffold. Hence, the proposed device represents a promising architecture for heterostructures capable of achieving high solar-to-hydrogen efficiency.

Cu2O Nanowire Photocathodes for Efficient and Durable Solar Water Splitting.

Due to its abundance, scalability, and nontoxicity, Cu2O has attracted extensive attention toward solar energy conversion, and it is the best performing metal oxide material. Until now, the high efficiency devices are all planar in structure, and their photocurrent densities still fall well below the theoretical value of 14.5 mA cm(-2) due to the incompatible light absorption and charge carrier diffusion lengths. Nanowire structures have been considered as a rational and promising approach to solve this issue, but due to various challenges, performance improvements through the use of nanowires have rarely been achieved. In this work, we develop a new synthetic method to grow Cu2O nanowire arrays on conductive fluorine-doped tin oxide substrates with well-controlled phase and excellent electronic and photonic properties. Also, we introduce an innovative blocking layer strategy to enable high performance. Further, through material engineering by combining a conformal nanoscale p-n junction, durable protective overlayer, and uniform catalyst decoration, we have successfully fabricated Cu2O nanowire array photocathodes for hydrogen generation from solar water splitting delivering unprecedentedly high photocurrent densities of 10 mA cm(-2) and stable operation beyond 50 h, establishing a new benchmark for metal oxide based photoelectrodes.

Covalent Immobilization of a Molecular Catalyst on Cu2O Photocathodes for CO2 Reduction.

Sunlight-driven CO2 reduction is a promising way to close the anthropogenic carbon cycle. Integrating light harvester and electrocatalyst functions into a single photoelectrode, which converts solar energy and CO2 directly into reduced carbon species, is under extensive investigation. The immobilization of rhenium-containing CO2 reduction catalysts on the surface of a protected Cu2O-based photocathode allows for the design of a photofunctional unit combining the advantages of molecular catalysts with inorganic photoabsorbers. To achieve large current densities, a nanostructured TiO2 scaffold, processed at low temperature, was deposited on the surface of protected Cu2O photocathodes. This led to a 40-fold enhancement of the catalytic photocurrent as compared to planar devices, resulting in the sunlight-driven evolution of CO at large current densities and with high selectivity. Potentiodynamic and spectroelectrochemical measurements point toward a similar mechanism for the catalyst in the bound and unbound form, whereas no significant production of CO was observed from the scaffold in the absence of a molecular catalyst.

Solution transformation of Cu2O into CuInS2 for solar water splitting.

Though Cu2O has demonstrated high performance as a photocathode for solar water splitting, its band gap is too large for efficient use as the bottom cell in tandem configurations. Accordingly, copper chalcopyrites have recently attracted much attention for solar water splitting due to their smaller and tunable band gaps. However, their fabrication is mainly based on vacuum evaporation, which is an expensive and energy consuming process. Here, we have developed a novel and low-cost solution fabrication method, and CuInS2 was chosen as a model material due to its smaller band gap compared to Cu2O and relatively simple composition. The nanostructured CuInS2 electrodes were synthesized at low temperature in crystalline form by solvothermal treatment of electrochemically deposited Cu2O films. Following the coating of overlayers and decoration with Pt catalyst, the as-fabricated CuInS2 electrode demonstrated water splitting photocurrents of 3.5 mA cm(-2) under simulated solar illumination. To the best of our knowledge, this is the highest performance yet reported for a solution-processed copper chalcopyrite electrode for solar water splitting. Furthermore, the electrode showed good stability and had a broad incident photon-to-current efficiency (IPCE) response to wavelengths beyond 800 nm, consistent with the smaller bandgap of this material.

Nanowire perovskite solar cell.

Organolead iodide perovskite, CH3NH3PbI3, was prepared in the form of nanowire by means of a small quantity of aprotic solvent in two-step spin-coating procedure. One-dimensional nanowire perovskite with the mean diameter of 100 nm showed faster carrier separation in the presence of hole transporting layer and higher lateral conductivity than the three-dimensional nanocuboid crystal. Reduction in dimensionality resulted in the hypsochromic shift of both absorption and fluorescence spectra, indicative of more localized exciton states in nanowires. The best performing device employing nanowire CH3NH3PbI3 delivered photocurrent density of 19.12 mA/cm(2), voltage of 1.052 V, and fill factor of 0.721, leading to a power conversion efficiency (PCE) of 14.71% at standard AM 1.5G solar illumination. A small I-V hysteresis was observed, where a PCE at forward scan was measured to be 85% of the PCE at reverse scan.

3D carbon/cobalt-nickel mixed-oxide hybrid nanostructured arrays for asymmetric supercapacitors.

The electrochemical performance of supercapacitors relies not only on the exploitation of high-capacity active materials, but also on the rational design of superior electrode architectures. Herein, a novel supercapacitor electrode comprising 3D hierarchical mixed-oxide nanostructured arrays (NAs) of C/CoNi3 O4 is reported. The network-like C/CoNi3 O4 NAs exhibit a relatively high specific surface area; it is fabricated from ultra-robust Co-Ni hydroxide carbonate precursors through glucose-coating and calcination processes. Thanks to their interconnected three-dimensionally arrayed architecture and mesoporous nature, the C/CoNi3 O4 NA electrode exhibits a large specific capacitance of 1299 F/g and a superior rate performance, demonstrating 78% capacity retention even when the discharge current jumps by 100 times. An optimized asymmetric supercapacitor with the C/CoNi3 O4 NAs as the positive electrode is fabricated. This asymmetric supercapacitor can reversibly cycle at a high potential of 1.8 V, showing excellent cycling durability and also enabling a remarkable power density of ∼13 kW/kg with a high energy density of ∼19.2 W·h/kg. Two such supercapacitors linked in series can simultaneously power four distinct light-emitting diode indicators; they can also drive the motor of remote-controlled model planes. This work not only presents the potential of C/CoNi3 O4 NAs in thin-film supercapacitor applications, but it also demonstrates the superiority of electrodes with such a 3D hierarchical architecture.

Synthesis of free-standing metal sulfide nanoarrays via anion exchange reaction and their electrochemical energy storage application.

Metal sulfides are an emerging class of high-performance electrode materials for solar cells and electrochemical energy storage devices. Here, a facile and powerful method based on anion exchange reactions is reported to achieve metal sulfide nanoarrays through a topotactical transformation from their metal oxide and hydroxide preforms. Demonstrations are made to CoS and NiS nanowires, nanowalls, and core-branch nanotrees on carbon cloth and nickel foam substrates. The sulfide nanoarrays exhibit superior redox reactivity for electrochemical energy storage. The self-supported CoS nanowire arrays are tested as the pseudo-capacitor cathode, which demonstrate enhanced high-rate specific capacities and better cycle life as compared to the powder counterparts. The outstanding electrochemical properties of the sulfide nanoarrays are a consequence of the preservation of the nanoarray architecture and rigid connection with the current collector after the anion exchange reactions.

Three-dimensional graphene foam supported Fe3O4 lithium battery anodes with long cycle life and high rate capability.

Fe3O4 has long been regarded as a promising anode material for lithium ion battery due to its high theoretical capacity, earth abundance, low cost, and nontoxic properties. However, up to now no effective and scalable method has been realized to overcome the bottleneck of poor cyclability and low rate capability. In this article, we report a bottom-up strategy assisted by atomic layer deposition to graft bicontinuous mesoporous nanostructure Fe3O4 onto three-dimensional graphene foams and directly use the composite as the lithium ion battery anode. This electrode exhibits high reversible capacity and fast charging and discharging capability. A high capacity of 785 mAh/g is achieved at 1C rate and is maintained without decay up to 500 cycles. Moreover, the rate of up to 60C is also demonstrated, rendering a fast discharge potential. To our knowledge, this is the best reported rate performance for Fe3O4 in lithium ion battery to date.

Interfacial Crosslinking for Efficient and Stable Planar TiO2 Perovskite Solar Cells.

The buried interface between the electron transport layer (ETL) and the perovskite layer plays a crucial role in enhancing the power conversion efficiency (PCE) and stability of n-i-p type perovskite solar cells (PSCs). In this study, the interface between the chemical bath deposited (CBD) titanium oxide (TiO2) ETL and the perovskite layer using multi-functional potassium trifluoromethyl sulfonate (SK) is modified. Structural and elemental analyses reveal that the trifluoromethyl sulfonate serves as a crosslinker between the TiO2 and the perovskite layer, thus improving the adhesion of the perovskite to the TiO2 ETL through strong bonding of the ─CF3 and ─SO3 - terminal groups. Furthermore, the multi-functional modifiers reduced interface defects and suppressed carrier recombination in the PSCs. Consequently, devices with a champion PCE of 25.22% and a fill factor (FF) close to 85% is achieved, marking the highest PCE and FF observed for PSCs based on CBD TiO2. The unencapsulated device maintained 81.3% of its initial PCE after operating for 1000 h.

Improving the photovoltage of Cu2O photocathodes with dual buffer layers.

Cuprous oxide (Cu2O) is a promising oxide material for photoelectrochemical water splitting (PEC), and increasing its photovoltage is the key to creating efficient overall PEC water-splitting devices. Previous reports are mostly focused on optimizing the energy band alignment between Cu2O and the n-type buffer layer to improve the photovoltage of Cu2O photocathodes. However, the band alignment between the n-type buffer layer and the protective layer is often ignored. In this work, Cu2O photocathodes with a single buffer layer (Ga2O3) and dual buffer layers (Ga2O3/ZnGeOx) are fabricated, and their PEC performances are compared. Results show that after inserting the second buffer layer (ZnGeOx), the onset potential of the Cu2O photocathode increases by 0.16 V. Operando electrochemical impedance spectroscopy measurements and analysis of the energy-level diagrams of each layer show that an energy level gradient between Ga2O3 and TiO2 is created when ZnGeOx is introduced, which eliminates the potential barrier at the interface of Ga2O3/TiO2 and improves the photovoltage of the Cu2O photocathode. Our work provides an effective approach to improve the photovoltage of photoelectrodes for solar water splitting by introducing dual buffer layers.

Electrochemical transformation of limestone into calcium hydroxide and valuable carbonaceous products for decarbonizing cement production.

The cement industry is one of the largest contributors to global CO2 emissions, which has been paid more attention to the research on converting the CO2 released by the cement production process. It is extremely challenging to decarbonize the cement industry, as most CO2 emissions result from the calcination of limestone (CaCO3) into CaO and CO2. In this work, we demonstrate an in situ electrochemical process that transforms CaCO3 into portlandite (Ca(OH)2, a key Portland cement precursor) and valuable carbonaceous products, which integrates electrochemical water splitting and CO2 reduction reaction with the chemical decomposition of CaCO3. With different metal catalyst electrodes (like Au, Ag, In, Cu, and Cu nanowires electrodes), we have achieved various valuable carbonaceous products, such as CO, formate, methane, ethylene, and ethane during the electrochemical CO2 process. Our work demonstrates a proof of concept for green and sustainable cement production.

A systematic discrepancy between the short circuit current and the integrated quantum efficiency in perovskite solar cells.

Halide perovskites solar cells are now approaching commercialisation. In this transition from academic research towards industrialisation, standardized testing protocols and reliable dissemination of performance metrics are crucial. In this study, we analyze data from over 16,000 publications in the Perovskite Database to investigate the assumed equality between the integrated external quantum efficiency and the short circuit current from JV measurements. We find a systematic discrepancy with the JV-values being on average 4% larger. This discrepancy persists across time, perovskite composition, and device architecture, indicating the need to explore new perovskite physics and update reporting protocols and assumptions in the field.