Promoting electrocatalytic carbon monoxide reduction to ethylene on copper-polypyrrole interface.

The renewable energy-powered electroreduction of carbon dioxide or monoxide (CO) has been emerging as an attractive means to decarbonize the emission-intensive chemical manufacturing, which heavily relies on fossil fuels nowadays. One potential approach to promote the activity of electrocatalysts is to construct hybrid interface that can increase the stability of intermediates on electrode surfaces. Herein we developed a copper nanoparticle/polypyrrole (Cu-Ppy) nanowire composite as an efficient electrocatalyst for electrochemical CO reduction reaction. Compared to pure Cu nanoparticles, the Cu-Ppy composite exhibited a dramatically enhanced Faradaic efficiency of converting CO to ethylene (C2H4) from 34% to 69% at -0.78 V vs. reversible hydrogen electrode (RHE) in KOH electrolyte, and an excellent C2H4 partial current density of 276 mA·cm-2 at -1.18 V vs. RHE. Density functional theory calculations showed that the Cu-Ppy composite could bind CO more strongly as compared to pure Cu. As the Ppy coating allowed to stabilize OCCO*, a key intermediate in the C2H4 formation, both the activity and selectivity of Cu-Ppy for CO-to-C2H4 were increased. Our work suggests that constructing rationally designed hybrid interface can tune the local environment of catalyst surface toward enhanced activity and product selectivity.

Double sulfur vacancies by lithium tuning enhance CO2 electroreduction to n-propanol.

Electrochemical CO2 reduction can produce valuable products with high energy densities but the process is plagued by poor selectivities and low yields. Propanol represents a challenging product to obtain due to the complicated C3 forming mechanism that requires both stabilization of *C2 intermediates and subsequent C1-C2 coupling. Herein, density function theory calculations revealed that double sulfur vacancies formed on hexagonal copper sulfide can feature as efficient electrocatalytic centers for stabilizing both CO* and OCCO* dimer, and further CO-OCCO coupling to form C3 species, which cannot be realized on CuS with single or no sulfur vacancies. The double sulfur vacancies were then experimentally synthesized by an electrochemical lithium tuning strategy, during which the density of sulfur vacancies was well-tuned by the charge/discharge cycle number. The double sulfur vacancy-rich CuS catalyst exhibited a Faradaic efficiency toward n-propanol of 15.4 ± 1% at -1.05 V versus reversible hydrogen electrode in H-cells, and a high partial current density of 9.9 mA cm-2 at -0.85 V in flow-cells, comparable to the best reported electrochemical CO2 reduction toward n-propanol. Our work suggests an attractive approach to create anion vacancy pairs as catalytic centers for multi-carbon-products.

Enhanced Nitrate-to-Ammonia Activity on Copper-Nickel Alloys via Tuning of Intermediate Adsorption.

Electrochemical conversion of nitrate (NO3-) into ammonia (NH3) recycles nitrogen and offers a route to the production of NH3, which is more valuable than dinitrogen gas. However, today's development of NO3- electroreduction remains hindered by the lack of a mechanistic picture of how catalyst structure may be tuned to enhance catalytic activity. Here we demonstrate enhanced NO3- reduction reaction (NO3-RR) performance on Cu50Ni50 alloy catalysts, including a 0.12 V upshift in the half-wave potential and a 6-fold increase in activity compared to those obtained with pure Cu at 0 V vs reversible hydrogen electrode (RHE). Ni alloying enables tuning of the Cu d-band center and modulates the adsorption energies of intermediates such as *NO3-, *NO2, and *NH2. Using density functional theory calculations, we identify a NO3-RR-to-NH3 pathway and offer an adsorption energy-activity relationship for the CuNi alloy system. This correlation between catalyst electronic structure and NO3-RR activity offers a design platform for further development of NO3-RR catalysts.

Selective carbon dioxide electroreduction to ethylene and ethanol by core-shell copper/cuprous oxide.

Developing an effective catalyst to reduce carbon dioxide (CO2) to value-added C2+ products is a key challenge for CO2 utilization. Here we report a core-shell copper with native oxide (Cu@Cu2O) catalyst featuring a thin native oxide layer on the surface grown under ambient conditions. The Cu(I) oxide species on Cu@Cu2O surface remained relatively stable against reduction under CO2 electroreduction condition, and the synergism between surface Cu+ and Cu0 in Cu@Cu2O contributed to boosting its efficiency and selectivity toward C2 products. This Cu@Cu2O catalyst achieved an excellent selectivity (∼50% at -1.0 V vs reversible hydrogen electrode) for C2 (ethylene and ethanol) production.

Electrochemical N2 fixation by Cu-modified iron oxide dendrites.

The electrochemical nitrogen reduction reaction (NRR) under mild conditions is significantly challenging, due to the extremely high stability of dinitrogen (N2) molecules. The NRR pathway also confronts the competitive water reduction reaction that takes places universally in an aqueous solution. Herein, a Fe2O3/Cu catalyst is demonstrated as an efficient NRR electrocatalyst. The electronic interactions elevate the d-state electron center, enabling strong back-bonding for N2 molecules. The altering of d-electron distribution promotes the adsorption of N2, leading to a high catalytic activity. As a result, the Fe2O3/Cu catalyst exhibits an outstanding ammonia production rate of 15.66 µg·h-1·mgcat.-1 at -0.1 V versus reversible hydrogen electrode (RHE), a Faradaic efficiency of 24.4%, and a good electrochemical stability.

Automated in Vivo Nanosensing of Breath-Borne Protein Biomarkers.

Toxicology and bedside medical condition monitoring is often desired to be both ultrasensitive and noninvasive. However, current biomarker analyses for these purposes are mostly offline and fail to detect low marker quantities. Here, we report a system called dLABer (detection of living animal's exhaled breath biomarker) that integrates living rats, breath sampling, microfluidics, and biosensors for the automated tracking of breath-borne biomarkers. Our data show that dLABer could selectively detect (online) and report differences (of up to 103-fold) in the levels of inflammation agent interleukin-6 (IL-6) exhaled by rats injected with different ambient particulate matter (PM). The dLABer system was further shown to have an up to 104 higher signal-to-noise ratio than that of the enzyme-linked immunosorbent assay (ELISA) when analyzing the same breath samples. In addition, both blood-borne IL-6 levels analyzed via ELISA in rats injected with different PM extracts and PM toxicity determined by a dithiothreitol (DTT) assay agreed well with those determined by the dLABer system. Video recordings further verified that rats exposed to PM with higher toxicity (according to a DTT assay and as revealed by dLABer) appeared to be less physically active. All the data presented here suggest that the dLABer system is capable of real-time, noninvasive monitoring of breath-borne biomarkers with ultrasensitivity. The dLABer system is expected to revolutionize pollutant health effect studies and bedside disease diagnosis as well as physiological condition monitoring at the single-protein level.

Three-dimensional WS2 nanosheet networks for H2O2 produced for cell signaling.

Hydrogen peroxide (H2O2) is an important molecular messenger for cellular signal transduction. The capability of direct probing of H2O2 in complex biological systems can offer potential for elucidating its manifold roles in living systems. Here we report the fabrication of three-dimensional (3D) WS2 nanosheet networks with flower-like morphologies on a variety of conducting substrates. The semiconducting WS2 nanosheets with largely exposed edge sites on flexible carbon fibers enable abundant catalytically active sites, excellent charge transfer, and high permeability to chemicals and biomaterials. Thus, the 3D WS2-based nano-bio-interface exhibits a wide detection range, high sensitivity and rapid response time for H2O2, and is capable of visualizing endogenous H2O2 produced in living RAW 264.7 macrophage cells and neurons. First-principles calculations further demonstrate that the enhanced sensitivity of probing H2O2 is attributed to the efficient and spontaneous H2O2 adsorption on WS2 nanosheet edge sites. The combined features of 3D WS2 nanosheet networks suggest attractive new opportunities for exploring the physiological roles of reactive oxygen species like H2O2 in living systems.

Reversible chemical tuning of charge carriers for enhanced photoelectrochemical conversion and probing of living cells.

A facile, solution method for reversible tuning of oxygen vacancies inside TiO2 nanowires, in which the reducing treatment of TiO2 by NaBH4 leads to 2.4-fold increase of photocurrent density, compared to pristine TiO2 nanowires, is reported. Subsequent oxidizing treatment using KMnO4 or annealing in air can reset the photocurrent density to the original values. The incident photo-to-current conversion efficiency measurement exhibits that the reduced TiO2 nanowires present both enhanced photoactivity in both UV and visible regions. Density functional theory calculations reveal that the oxygen vacancies in the reduced TiO2 cause defect states in the band structure and result in enhanced carrier density and conductivity. In addition, the enhanced solar energy-driven photoelectrochemical conversion allows real-time, sensitive chemical probing of living cells that are directly grown on the TiO2 nanowire photoanodes. As proofs-of-concept, after functionalized with horseradish peroxidase (HRP) on the surface, the reduced TiO2 NWs demonstrate sensitive, real-time monitoring of the H2O2 levels in several distinctive living cell lines, with the lowest detectable H2O2 concentration of 7.7 nM. This reversible tuning of oxygen vacancies suggests a facile means for transition metal oxides, with enhanced photoconversion activity and electrochemical sensitivity.

Dual-pore mesoporous carbon@silica composite core-shell nanospheres for multidrug delivery.

Monodispersed mesoporous phenolic polymer nanospheres with uniform diameters were prepared and used as the core for the further growth of core-shell mesoporous nanorattles. The hierarchical mesoporous nanospheres have a uniform diameter of 200 nm and dual-ordered mesopores of 3.1 and 5.8 nm. The hierarchical mesostructure and amphiphilicity of the hydrophobic carbon cores and hydrophilic silica shells lead to distinct benefits in multidrug combination therapy with cisplatin and paclitaxel for the treatment of human ovarian cancer, even drug-resistant strains.

Photoelectrochemical detection of glutathione by IrO2-hemin-TiO2 nanowire arrays.

We have developed sensitive detection of glutathione using the IrO2-hemin-TiO2 nanowire arrays. Single-crystalline TiO2 nanowires are synthesized by a hydrothermal reaction, followed by surface functionalization of ~3 nm thick hemin and ~1-2 nm diameter IrO2 nanoparticles. The IrO2-hemin-TiO2 nanowire arrays offer much enhanced photocurrent with ∼100% increase compared to the pristine TiO2 nanowires and allow for label-free, real-time, sensitive photoelectrochemical detection of glutathione. The sensitivity achieved is ~10 nM in buffer, comparable to or better than most of the existing glutathione detection methods. Furthermore, cell extracts containing glutathione are robustly detected, with ~8000 cells/mL for HeLa cells and ~5000 cells/mL for human embryonic kidney 293T cells. This nanowire PEC sensor assay exhibits excellent selectivity and stability, suggesting a potential detection platform for analyzing the glutathione level in biosamples.

MnO nanoparticle@mesoporous carbon composites grown on conducting substrates featuring high-performance lithium-ion battery, supercapacitor and sensor.

We demonstrate a facile, two-step coating/calcination approach to grow a uniform MnO nanoparticle@mesoporous carbon (MnO@C) composite on conducting substrates, by direct coating of the Mn-oleate precursor solution without any conducting/binding reagents, and subsequent thermal calcination. The monodispersed, sub-10 nm MnO nanoparticles offer high theoretical energy storage capacities and catalytic properties, and the mesoporous carbon coating allows for enhanced electrolyte transport and charge transfer towards/from MnO surface. In addition, the direct growth and attachment of the MnO@C nanocomposite in the supporting conductive substrates provide much reduced contact resistances and efficient charge transfer. These excellent features allow the use of MnO@C nanocomposites as lithium-ion battery and supercapacitor electrodes for energy storage, with high reversible capacity at large current densities, as well as excellent cycling and mechanical stabilities. Moreover, this MnO@C nanocomposite has also demonstrated a high sensitivity for H2O2 detection, and also exhibited attractive potential for the tumor cell analysis.

Carbon nanodots featuring efficient FRET for real-time monitoring of drug delivery and two-photon imaging.

A FRET-based carbon nanodot (CDot) drug delivery platform has been developed. These CDots offer excellent biocompatibility, stable fluorescence, and efficient FRET between CDots and the attached fluorescent drug molecules, such as doxorubicin, enabling enhanced drug delivery, convenient cell imaging, and real-time monitoring of drug release. Moreover, the FRET-based two-photon imaging and drug tracking in deep tissues are also demonstrated.

Nanowire biosensors for label-free, real-time, ultrasensitive protein detection.

Sensitive and quantitative analysis of proteins is central to disease diagnosis, drug screening, and proteomic studies. Among recent research advances exploiting new nanomaterials for biomolecule analysis, silicon nanowires (SiNWs), which are configured as field-effect transistors (FETs), have emerged as one of the most promising and powerful platforms for label-free, real-time, and highly sensitive electrical detection of proteins as well as many other biological species. Here, we describe a detailed protocol for realizing SiNW biosensors for protein detection that includes SiNW synthesis, FET device fabrication, surface receptor functionalization, and electrical sensing measurements. Moreover, incorporating both p-type and n-type SiNWs in the same sensor array provides a unique means of internal control for sensing signal verification.

Subthreshold regime has the optimal sensitivity for nanowire FET biosensors.

Nanowire field-effect transistors (NW-FETs) are emerging as powerful sensors for detection of chemical/biological species with various attractive features including high sensitivity and direct electrical readout. Yet to date there have been limited systematic studies addressing how the fundamental factors of devices affect their sensitivity. Here we demonstrate that the sensitivity of NW-FET sensors can be exponentially enhanced in the subthreshold regime where the gating effect of molecules bound on a surface is the most effective due to the reduced screening of carriers in NWs. This principle is exemplified in both pH and protein sensing experiments where the operational mode of NW-FET biosensors was tuned by electrolyte gating. The lowest charge detectable by NW-FET sensors working under different operational modes is also estimated. Our work shows that optimization of NW-FET structure and operating conditions can provide significant enhancement and fundamental understanding for the sensitivity limits of NW-FET sensors.

Controlled synthesis of millimeter-long silicon nanowires with uniform electronic properties.

We report the nanocluster-catalyzed growth of ultralong and highly uniform single-crystalline silicon nanowires (SiNWs) with millimeter-scale lengths and aspect ratios up to approximately 100,000. The average SiNW growth rate using disilane (Si 2H 6) at 400 degrees C was 31 microm/min, while the growth rate determined for silane (SiH 4) reactant under similar growth conditions was 130 times lower. Transmission electron microscopy studies of millimeter-long SiNWs with diameters of 20-80 nm show that the nanowires grow preferentially along the 110 direction independent of diameter. In addition, ultralong SiNWs were used as building blocks to fabricate one-dimensional arrays of field-effect transistors (FETs) consisting of approximately 100 independent devices per nanowire. Significantly, electrical transport measurements demonstrated that the millimeter-long SiNWs had uniform electrical properties along the entire length of wires, and each device can behave as a reliable FET with an on-state current, threshold voltage, and transconductance values (average +/-1 standard deviation) of 1.8 +/- 0.3 microA, 6.0 +/- 1.1 V, 210 +/- 60 nS, respectively. Electronically uniform millimeter-long SiNWs were also functionalized with monoclonal antibody receptors and used to demonstrate multiplexed detection of cancer marker proteins with a single nanowire. The synthesis of structurally and electronically uniform ultralong SiNWs may open up new opportunities for integrated nanoelectronics and could serve as unique building blocks linking integrated structures from the nanometer through millimeter length scales.

Multiplexed electrical detection of cancer markers with nanowire sensor arrays.

We describe highly sensitive, label-free, multiplexed electrical detection of cancer markers using silicon-nanowire field-effect devices in which distinct nanowires and surface receptors are incorporated into arrays. Protein markers were routinely detected at femtomolar concentrations with high selectivity, and simultaneous incorporation of control nanowires enabled discrimination against false positives. Nanowire arrays allowed highly selective and sensitive multiplexed detection of prostate specific antigen (PSA), PSA-alpha1-antichymotrypsin, carcinoembryonic antigen and mucin-1, including detection to at least 0.9 pg/ml in undiluted serum samples. In addition, nucleic acid receptors enabled real-time assays of the binding, activity and small-molecule inhibition of telomerase using unamplified extracts from as few as ten tumor cells. The capability for multiplexed real-time monitoring of protein markers and telomerase activity with high sensitivity and selectivity in clinically relevant samples opens up substantial possibilities for diagnosis and treatment of cancer and other complex diseases.

Electrical detection of single viruses.

We report direct, real-time electrical detection of single virus particles with high selectivity by using nanowire field effect transistors. Measurements made with nanowire arrays modified with antibodies for influenza A showed discrete conductance changes characteristic of binding and unbinding in the presence of influenza A but not paramyxovirus or adenovirus. Simultaneous electrical and optical measurements using fluorescently labeled influenza A were used to demonstrate conclusively that the conductance changes correspond to binding/unbinding of single viruses at the surface of nanowire devices. pH-dependent studies further show that the detection mechanism is caused by a field effect, and that the nanowire devices can be used to determine rapidly isoelectric points and variations in receptor-virus binding kinetics for different conditions. Lastly, studies of nanowire devices modified with antibodies specific for either influenza or adenovirus show that multiple viruses can be selectively detected in parallel. The possibility of large-scale integration of these nanowire devices suggests potential for simultaneous detection of a large number of distinct viral threats at the single virus level.