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Understanding the catalytic mechanism of highly active two-dimensional electrocatalysts is crucial to their rational design. Herein, we reveal the element dependence of the reactivity of two-dimensional metal dichalcogenide sheets for electrocatalytic CO2reduction. We found that tin(IV) disulfide (SnS2) and molybdenum(IV) disulfide (MoS2) sheets exhibited Faradaic efficiencies of 63.3% and ∼0%, respectively, for formic acid. Scanning electrochemical cell microscopy and theoretical calculations were used to identify the catalytically active sites of SnS2as terraces and edges. Owing to the effective utilization of the entire surface area, SnS2can effectively accelerate catalytic reactions. This finding provides a direction for material research in two-dimensional electrocatalysts for energy-efficient chemical production from electrochemical CO2reduction, as well as for other energy devices.

Antibodies and their conjugates of fluorescent labels are widely applied in life sciences research and clinical pathology. Among diverse label types, compact quantum dots (QDs) provide advantages of multispectral multiplexing, bright signals in the deep red and infrared, and low steric hindrance. However, QD-antibody conjugates have random orientation of the antigen-binding domain which may interfere with labeling and are large (20–30 nm) and heterogeneous, which limits penetration into biospecimens. Here, we develop conjugates of compact QDs and Fab′ antibody fragments as primary immunolabels. Fab′ fragments are conjugated site-specifically through sulfhydryl groups distal to antigen-binding domains, and the multivalent conjugates have small and homogeneous sizes (∼12 nm) near those of full-sized antibodies. Their performance as immunolabels for intracellular antigens is evaluated quantitatively by metrics of microtubule labeling density and connectivity in fixed cells and for cytological identification in fixed brain specimens, comparing results with probes based on spectrally-matched dyes. QD-Fab′ conjugates outperformed QD conjugates of full-sized antibodies and could be imaged with bright signals with 1-photon and 2-photon excitation. The results demonstrate a requirement for smaller bioaffinity agents and site-specific orientation for the success of nanomaterial-based labels to enhance penetration in biospecimens and minimize nonspecific staining.

Quantum dots (QDs) are a class of fluorescent nanocrystals in development as labels for molecular imaging in cells and tissues. Recently, coatings for quantum dots based on multidentate polymers have improved labeling performance in a range of bioanalytical applications, primarily due to reduced probe hydrodynamic size. Now, an ongoing challenge is to eliminate nonspecific binding between these small probes and cellular components that mask specifically labeled molecules. Here, we describe insights into controlling and minimizing intermolecular interactions governing nonspecific binding using multidentate polymers with tunable hydrophilic functional groups that are cationic, anionic, zwitterionic (ZW), or nonionic (oligoethylene glycol; OEG). By fixing surface-binding groups and polymer length, coated colloids have similar sizes but diverse physicochemical properties. We measure binding to globular proteins, fixed cells, and living cells and observe a substantial improvement in nonspecific binding resistance when surfaces are functionalized with a combination of ZW and OEG. The independent underlying effects of counterion adsorption and flexibility appear to synergistically resist adsorption when combined, particularly for fixed cells enriched in both charged and hydrophobic moieties. We further show that ZW-OEG QDs are stable under diverse conditions and can be self-assembled with antibodies to specifically label surface antigens on living cells and cytoplasmic proteins in fixed cells. This surface engineering strategy can be adopted across the diverse range of colloidal materials currently in use and in development for biomedical applications to optimize their molecular labeling specificity.

Chemical functionalization is demonstrated to enhance the p-type electrical performance of two-dimensional (2D) layered tungsten diselenide (WSe2) field-effect transistors (FETs) using a one-step dipping process in an aqueous solution of ammonium sulfide [(NH4)2S(aq)]. Molecularly resolved scanning tunneling microscopy and spectroscopy reveal that molecular adsorption on a monolayer WSe2surface induces a reduction of the electronic band gap from 2.1 to 1.1 eV and a Fermi level shift toward the WSe2valence band edge (VBE), consistent with an increase in the density of positive charge carriers. The mechanism of electronic transformation of WSe2by (NH4)2S(aq) chemical treatment is elucidated using density functional theory calculations which reveal that molecular “SH” adsorption on the WSe2surface introduces additional in-gap states near the VBE, thereby, inducing a Fermi level shift toward the VBE along with a reduction in the electronic band gap. As a result of the (NH4)2S(aq) chemical treatment, the p-branch ON-currents (ION) of back-gated few-layer ambipolar WSe2FETs are enhanced by about 2 orders of magnitude, and a ∼6× increase in the hole field-effect mobility is observed, the latter primarily resulting from the p-doping-induced narrowing of the Schottky barrier width leading to an enhanced hole injection at the WSe2/contact metal interface. This (NH4)2S(aq) chemical functionalization technique can serve as a model method to control the electronic band structure and enhance the performance of devices based on 2D layered transition-metal dichalcogenides.

The prevention and treatment of cardiovascular diseases (CVD) has largely focused on lowering circulating LDL cholesterol, yet a significant burden of atherosclerotic disease remains even when LDL is low. Recently, microRNAs (miRNAs) have emerged as exciting therapeutic targets for cardiovascular disease. miRNAs are small noncoding RNAs that post-transcriptionally regulate gene expression by degradation or translational inhibition of target mRNAs. A number of miRNAs have been found to modulate all stages of atherosclerosis, particularly those that promote the efflux of excess cholesterol from lipid-laden macrophages in the vessel wall to the liver. However, one of the major challenges of miRNA-based therapy is to achieve tissue-specific, efficient, and safe delivery of miRNAs in vivo. We sought to develop chitosan nanoparticles (chNPs) that can deliver functional miRNA mimics to macrophages and to determine if these nanoparticles can alter cholesterol efflux and reverse cholesterol transport in vivo. We developed chNPs with a size range of 150–200 nm viathe ionic gelation method using tripolyphosphate (TPP) as a cross-linker. In this method, negatively charged miRNAs were encapsulated in the nanoparticles by ionic interactions with polymeric components. We then optimized the efficiency of intracellular delivery of different formulations of chitosan/TPP/miRNA to mouse macrophages. Using a well-defined miRNA with roles in macrophage cholesterol metabolism, we tested whether chNPs could deliver functional miRNAs to macrophages. We find chNPs can transfer exogenous miR-33 to naïve macrophages and reduce the expression of ABCA1, a potent miR-33 target gene, both in vitroand in vivo, confirming that miRNAs delivered viananoparticles can escape the endosomal system and function in the RISC complex. Because miR-33 and ABCA1 play a key role in regulating the efflux of cholesterol from macrophages, we also confirmed that macrophages treated with miR-33-loaded chNPs exhibited reduced cholesterol efflux to apolipoprotein A1, further confirming functional delivery of the miRNA. In vivo, mice treated with miR33-chNPs showed decreased reverse cholesterol transport (RCT) to the plasma, liver, and feces. In contrast, when efflux-promoting miRNAs were delivered viachNPs, ABCA1 expression and cholesterol efflux into the RCT pathway were improved. Over all, miRNAs can be efficiently delivered to macrophages viananoparticles, where they can function to regulate ABCA1 expression and cholesterol efflux, suggesting that these miRNA nanoparticles can be used in vivoto target atherosclerotic lesions.

Three-dimensional (3D) orientations of individual anisotropic plasmonic nanoparticles in aggregates were observed in real time by integrated light sheet super-resolution microscopy (iLSRM). Asymmetric light scattering of a gold nanorod (AuNR) was used to trigger signals based on the polarizer angle. Controlled photoswitching was achieved by turning the polarizer and obtaining a series of images at different polarization directions. 3D subdiffraction-limited super-resolution images were obtained by superlocalization of scattering signals as a function of the anisotropic optical properties of AuNRs. Varying the polarizer angle allowed resolution of the orientation of individual AuNRs. 3D images of individual nanoparticles were resolved in aggregated regions, resulting in as low as 64 nm axial resolution and 28 nm spatial resolution. The proposed imaging setup and localization approach demonstrates a convenient method for imaging under a noisy environment where the majority of scattering noise comes from cellular components. This integrated 3D iLSRM and localization technique was shown to be reliable and useful in the field of 3D nonfluorescence super-resolution imaging.

Nanostructures of metal sulfides are conventionally prepared viachemical techniques and patterned using self-assembly. This poses a considerable amount of challenge when arbitrary shapes and sizes of nanostructures are desired to be placed at precise locations. Here, we describe an alternative approach of nanoscale patterning of zinc sulfide (ZnS) directly using a spin-coatable and electron beam sensitive zinc butylxanthate resist without the lift-off or etching step. Time-resolved electron beam damage studies using micro-Raman and micro-FTIR spectroscopies suggest that exposure to a beam of electrons leads to quick disappearance of xanthate moieties most likely viathe Chugaev elimination, and further increase of electron dose results in the appearance of ZnS, thereby making the exposed resist insoluble in organic solvents. Formation of ZnS nanocrystals was confirmed by high-resolution transmission electron microscopy and selected area electron diffraction. This property was exploited for the fabrication of ZnS lines as small as 6 nm and also enabled patterning of 10 nm dots with pitches as close as 22 nm. The ZnS patterns fabricated by this technique showed defect-induced photoluminescence related to sub-band-gap optical transitions. This method offers an easy way to generate an ensemble of functional ZnS nanostructures that can be arbitrarily patterned and placed in a precise way. Such an approach may enable programmable design of functional chalcogenide nanostructures.

Silicon (Si) shows promise as an anode material in lithium-ion batteries due to its very high specific capacity. However, Si is highly brittle, and in an effort to prevent Si from fracturing, the research community has migrated from the use of Si films to Si nanoparticle based electrodes. However, such a strategy significantly reduces volumetric energy density due to the porosity of Si nanoparticle electrodes. Here we show that contrary to conventional wisdom, Si films can be stabilized by two strategies: (a) anchoring the Si films to a carbon nanotube macrofilm (CNM) current collector and (b) draping the films with a graphene monolayer. After electrochemical cycling, the graphene-coated Si films on CNM resembled a tough mud-cracked surface in which the graphene capping layer suppresses delamination and stabilizes the solid electrolyte interface. The graphene-draped Si films on CNM exhibit long cycle life (>1000 charge/discharge steps) with an average specific capacity of ∼806 mAh g–1. The volumetric capacity averaged over 1000 cycles of charge/discharge is ∼2821 mAh cm–3, which is 2 to 5 times higher than what is reported in the literature for Si nanoparticle based electrodes. The graphene-draped Si anode could also be successfully cycled against commercial cathodes in a full-cell configuration.

Molecular level alignment of components and optimum morphology of hybrid materials are of great interest in many applications. Morphology control has been extensively used as a direct tool in the evaluation of interactions and assemblies of components in thin films. It is believed that preparation method and composition are powerful tools to direct the morphology, particularly in self-assembled systems such as fullerene-based hybrid materials. The present report outlines a synergistic self-assembly of fullerenes (C 60) and functionalized poly ( p-phenylene) (PPP) to develop nanofibers with high aspect ratios. Nanostructured PPP−C 60hybrids were prepared by direct casting of the dilute solution on solid substrates and on water under ambient conditions. The formation of whiskers with high aspect ratio and investigation of interesting photophysical properties are discussed. An amphiphilic PPP was used as a template for preparing nanohybrids of C 60at ambient temperature and conditions.

In this work, techniques to create patterned array of multiwalled nanotube (MWNT) microstructures decorated with quantum dots (QDs) were presented. Using aligned array of intertwined MWNTs as the supporting template, a droplet of solution comprising QDs was deposited onto the MWNTs. When the solution evaporated away, QDs were left behind on the MWNT template. Coupled with the technique of laser pruning, a wide variety of QDs-decorated MWNT microstructures were created. In addition, the aligned array of MWNTs was found to be an effective nanosieve that could effectively sort out QDs with a size difference of ∼0.5 nm. In this case, a droplet of solution comprising QDs of different sizes was placed on aligned array of MWNTs. As the solution spread across as well as trickled down the MWNTs, the smaller QDs were found to venture further and deeper into the MWNTs. Again coupled with laser pruning, fluorescence microscopy revealed multicolored MWNT microstructures due to preferential decoration of these QDs with difference sizes. As a result, multicolored/multicomponents hybrid functional materials were achieved.

To deposit an ultrathin dielectric onto WSe2, monolayer titanyl phthalocyanine (TiOPc) is deposited by molecular beam epitaxy as a seed layer for atomic layer deposition (ALD) of Al2O3on WSe2. TiOPc molecules are arranged in a flat monolayer with 4-fold symmetry as measured by scanning tunneling microscopy. ALD pulses of trimethyl aluminum and H2O nucleate on the TiOPc, resulting in a uniform deposition of Al2O3, as confirmed by atomic force microscopy and cross-sectional transmission electron microscopy. The field-effect transistors (FETs) formed using this process have a leakage current of 0.046 pA/μm2at 1 V gate bias with 3.0 nm equivalent oxide thickness, which is a lower leakage current than prior reports. The n-branch of the FET yielded a subthreshold swing of 80 mV/decade.

Inflammation is an essential protective biological response involving a coordinated cascade of signals between cytokines and immune signaling molecules that facilitate return to tissue homeostasis after acute injury or infection. However, inflammation is not effectively resolved in chronic inflammatory diseases such as atherosclerosis and can lead to tissue damage and exacerbation of the underlying condition. Therapeutics that dampen inflammation and enhance resolution are currently of considerable interest, in particular those that temper inflammation with minimal host collateral damage. Here we present the development and efficacy investigations of controlled-release polymeric nanoparticles incorporating the anti-inflammatory cytokine interleukin 10 (IL-10) for targeted delivery to atherosclerotic plaques. Nanoparticles were nanoengineered viaself-assembly of biodegradable polyester polymers by nanoprecipitation using a rapid micromixer chip capable of producing nanoparticles with retained IL-10 bioactivity post-exposure to organic solvent. A systematic combinatorial approach was taken to screen nanoparticles, resulting in an optimal bioactive formulation from in vitroand ex vivostudies. The most potent nanoparticle termed Col-IV IL-10 NP22 significantly tempered acute inflammation in a self-limited peritonitis model and was shown to be more potent than native IL-10. Furthermore, the Col-IV IL-10 nanoparticles prevented vulnerable plaque formation by increasing fibrous cap thickness and decreasing necrotic cores in advanced lesions of high fat-fed LDLr–/–mice. These results demonstrate the efficacy and pro-resolving potential of this engineered nanoparticle for controlled delivery of the potent IL-10 cytokine for the treatment of atherosclerosis.

The effect of air exposure on 2H-WSe2/HOPG is determined viascanning tunneling microscopy (STM). WSe2was grown by molecular beam epitaxy on highly oriented pyrolytic graphite (HOPG), and afterward, a Se adlayer was deposited in situon WSe2/HOPG to prevent unintentional oxidation during transferring from the growth chamber to the STM chamber. After annealing at 773 K to remove the Se adlayer, STM images show that WSe2layers nucleate at both step edges and terraces of the HOPG. Exposure to air for 1 week and 9 weeks caused air-induced adsorbates to be deposited on the WSe2surface; however, the band gap of the terraces remained unaffected and nearly identical to those on decapped WSe2. The air-induced adsorbates can be removed by annealing at 523 K. In contrast to WSe2terraces, air exposure caused the edges of the WSe2to oxidize and form protrusions, resulting in a larger band gap in the scanning tunneling spectra compared to the terraces of air-exposed WSe2monolayers. The preferential oxidation at the WSe2edges compared to the terraces is likely the result of dangling edge bonds. In the absence of air exposure, the dangling edge bonds had a smaller band gap compared to the terraces and a shift of about 0.73 eV in the Fermi level toward the valence band. However, after air exposure, the band gap of the oxidized WSe2edges became about 1.08 eV larger than that of the WSe2terraces, resulting in the electronic passivation of the WSe2.

The next generation of deformable and shape-conformable electronics devices will need to be powered by batteries that are not only flexible but also foldable. Here we report a foldable lithium–sulfur (Li–S) rechargeable battery, with the highest areal capacity (∼3 mAh cm–2) reported to date among all types of foldable energy-storage devices. The key to this result lies in the use of fully foldable and superelastic carbon nanotube current-collector films and impregnation of the active materials (S and Li) into the current-collectors in a checkerboard pattern, enabling the battery to be folded along two mutually orthogonal directions. The carbon nanotube films also serve as the sulfur entrapment layer in the Li–S battery. The foldable battery showed <12% loss in specific capacity over 100 continuous folding and unfolding cycles. Such shape-conformable Li–S batteries with significantly greater energy density than traditional lithium-ion batteries could power the flexible and foldable devices of the future including laptops, cell phones, tablet computers, surgical tools, and implantable biomedical devices.

Critical prerequisites for solution-processed/printed field-effect transistors (FETs) and logics are excellent electrical performance including high charge carrier mobility, reliability, high environmental stability and low/preferably room temperature processing. Oxide semiconductors can often fulfill all the above criteria, sometimes even with better promise than their organic counterparts, except for their high process temperature requirement. The need for high annealing/curing temperatures renders oxide FETs rather incompatible to inexpensive, flexible substrates, which are commonly used for high-throughput and roll-to-roll additive manufacturing techniques, such as printing. To overcome this serious limitation, here we demonstrate an alternative approach that enables completely room-temperature processing of printed oxide FETs with device mobility as large as 12.5 cm2/(V s). The key aspect of the present concept is a chemically controlled curing process of the printed nanoparticle ink that provides surprisingly dense thin films and excellent interparticle electrical contacts. In order to demonstrate the versatility of this approach, both n-type (In2O3) and p-type (Cu2O) oxide semiconductor nanoparticle dispersions are prepared to fabricate, inkjet printed and completely room temperature processed, all-oxide complementary metal oxide semiconductor (CMOS) invertors that can display significant signal gain (∼18) at a supply voltage of only 1.5 V.

In vitrotoxicity assessment of engineered nanomaterials (ENM), the most common testing platform for ENM, requires prior ENM dispersion, stabilization, and characterization in cell culture media. Dispersion inefficiencies and active aggregation of particles often result in polydisperse and multimodal particle size distributions. Accurate characterization of important properties of such polydisperse distributions (size distribution, effective density, charge, mobility, aggregation kinetics, etc.) is critical for understanding differences in the effective dose delivered to cells as a function of time and dispersion conditions, as well as for nano–bio interactions. Here we have investigated the utility of tunable nanopore resistive pulse sensing (TRPS) technology for characterization of four industry relevant ENMs (oxidized single-walled carbon nanohorns, carbon black, cerium oxide and nickel nanoparticles) in cell culture media containing serum. Harvard dispersion and dosimetry platform was used for preparing ENM dispersions and estimating delivered dose to cells based on dispersion characterization input from dynamic light scattering (DLS) and TRPS. The slopes of cell death vsadministered and delivered ENM dose were then derived and compared. We investigated the impact of serum protein content, ENM concentration, and cell medium on the size distributions. The TRPS technology offers higher resolution and sensitivity compared to DLS and unique insights into ENM size distribution and concentration, as well as particle behavior and morphology in complex media. The in vitrodose–response slopes changed significantly for certain nanomaterials when delivered dose to cells was taken into consideration, highlighting the importance of accurate dispersion and dosimetry in in vitronanotoxicology.

Diverse processes that include energy conversion, wettability, lubrication, adhesion, and surface-directed phase separation in mixtures fundamentally depend on the structure and dynamics of materials’ surfaces and interfaces. We report an unusual phenomenon wherein the surface viscosity of polymer nanocomposites of polystyrene (PS), polyvinyl methyl ether (PVME), and PS-coated gold nanoparticles (PS/PVME/PS-Au) is over an order of magnitude smaller than that of the neat miscible PS/PVME blend. Our X-ray photon correlation spectroscopy studies of the surface dynamics also reveal that the polymer chains manifest dynamics associated with two separate average compositional environments: a PVME-rich region, significantly in excess of its bulk concentration, and a separate PS-rich environment, where the dynamics are approximately 2 orders of magnitude slower. The unusually rapid surface dynamics in the PS/PVME/PS-Au nanocomposite are due largely to the excess PVME chains and the polymer/brush-coated nanoparticle interactions at the free surface.

Hierarchical assemblies are repeatedly encountered in nature, and when replicated in synthetic patterns and materials, can enhance their functionality or impart multifunctionality. In order to assemble a hierarchical superstructure that consists of components made up of multiple nanostructures, control over placement and stoichiometry is desirable. Macroscopic arrays that present up to three levels of hierarchy are demonstrated here and are achieved using the self-assembly of soft, collapsible block copolymer nanospheres for the first two levels, followed by directed self-assembly of metal nanospheres for the third. The fabrication approach combines advantages of soft sphere self-assembly to yield non-close-packed and variable array pitch values, with the inherent chemical functionality presented by the polymer-based soft spheres; these assemblies can then be transformed into a range of different materials, including metal or semiconductor nanostructures, or further tailored with an additional level of complexity. Structural investigation shows the superstructure formation to be governed by generic design rules that can be extended across different material combinations.

Semiconductor nanoparticles conjugated with organic- and dye-molecules to yield high efficiency visible photoluminescence (PL) hold great potential for many future technological applications. We show that folic acid (FA)-conjugated to nanosize TiO2and CeO2particles demonstrates a dramatic increase of photoemission intensity at wavelengths between 500 and 700 nm when derivatized using aminopropyl trimethoxysilane (APTMS) as spacer-linker molecules between the metal oxide and FA. Using density-functional theory (DFT) and time-dependent DFT calculations we demonstrate that the strong increase of the PL can be explained by electronic transitions between the titania surface oxygen vacancy (OV) states and the low-energy excited states of the FA/APTMS molecule anchored onto the surface oxygen bridge sites in close proximity to the OVs. We suggest this scenario to be a universal feature for a wide class of metal oxide nanoparticles, including nanoceria, possessing a similar band gap (∼3 eV) and with a large surface-vacancy-related density of electronic states. We demonstrate that the molecule–nanoparticle linker can play a crucial role in tuning the electronic and optical properties of nanosystems by bringing optically active parts of the molecule and of the surface close to each other.

Nanoparticles have shown tremendous potential for effective drug delivery due to their tiny size and cell membrane penetration capabilities. Cellular targeting with nanoparticles is often achieved by surface modifications followed by ligand conjugation. However, the efficiency of the nanoparticles reaching the target cells and getting internalized depends on the stability of targeting ligands and the chemical nature of the ligand nanoparticle binding. Recent advancements in nanobiomaterials research have proven the superoxide dismutase (SOD) mimetic activity of cerium oxide nanoparticles (CNPs) in protecting cells against oxidative stress. Due to their excellent biocompatibility, CNPs can be used as a potential drug carrier that can transport and release drugs to the malignant sites. Here we combine single molecule force spectroscopy (SMFS) and density functional theory (DFT) simulations to understand the interaction between transferrin, a ligand protein overexpressed in cancer cells, and CNPs. SMFS studies demonstrate an increase in the transferrin adhesion to the nanoparticles’ surface with an increase in positive ζ potential of CNPs. Binding energy values obtained from DFT calculations predict an increase in bond strength between the transferrin and CNPs upon surface protonation and charge modification. Transferrin-conjugated CNPs were tested for their binding stability and preferential cellular uptake efficiency by incubating them with human lung cancer cells (A549) and normal embryo lung cells (WI-38). The results demonstrate the importance of tuning the surface properties of nanoparticles for better ligand adsorption and cellular uptake.

Silver nanoparticles (Ag-np) are being used increasingly in wound dressings, catheters, and various household products due to their antimicrobial activity. The toxicity of starch-coated silver nanoparticles was studied using normal human lung fibroblast cells (IMR-90) and human glioblastoma cells (U251). The toxicity was evaluated using changes in cell morphology, cell viability, metabolic activity, and oxidative stress. Ag-np reduced ATP content of the cell caused damage to mitochondria and increased production of reactive oxygen species (ROS) in a dose-dependent manner. DNA damage, as measured by single cell gel electrophoresis (SCGE) and cytokinesis blocked micronucleus assay (CBMN), was also dose-dependent and more prominent in the cancer cells. The nanoparticle treatment caused cell cycle arrest in G2/M phase possibly due to repair of damaged DNA. Annexin-V propidium iodide (PI) staining showed no massive apoptosis or necrosis. The transmission electron microscopic (TEM) analysis indicated the presence of Ag-np inside the mitochondria and nucleus, implicating their direct involvement in the mitochondrial toxicity and DNA damage. A possible mechanism of toxicity is proposed which involves disruption of the mitochondrial respiratory chain by Ag-np leading to production of ROS and interruption of ATP synthesis, which in turn cause DNA damage. It is anticipated that DNA damage is augmented by deposition, followed by interactions of Ag-np to the DNA leading to cell cycle arrest in the G2/M phase. The higher sensitivity of U251 cells and their arrest in G2/M phase could be explored further for evaluating the potential use of Ag-np in cancer therapy.

Band structure engineering offers a perfect route to tune the transport properties of electrons and holes independently, especially in semiconductors for water splitting. Here, we explore the possibility of achieving a bias-free single-step solar to chemical energy conversion using gas-phase moisture as the reactant while generating hydrogen as the reaction product. A metal-based superhygroscopic hydrogel scavenges moisture from the ambient environment and serves as the water source. The FeOOH/BiVO4heterojunction works as the photoanode wherein the interface allows the transport of electrons to the outer layer, resulting in an upward band bending. Concomitantly, the negative charges will accumulate on the Cu2O surface in the FeOOH/Cu2O photocathode, inducing a downward band bending. With the use of the hydrogel, photoanode, and photocathode, a device for directly splitting the moisture absorbed from the ambient air is realized, generating a photocurrent of 0.75 mA cm–2under the one-sun intensity of cool daylight without any additional bias. The solar-cell-assisted device can split 6 mg of moisture in 10 h, and the hydrogel can absorb more than 30 mg of moisture in the same period.