Iron-copper bimetallic photo-Fenton system promoted photothermal-hydrogen peroxide production for efficient low-temperature wastewater treatment.

Enhancing the velocity of the oxidation-reduction cycle is crucial for improving the catalytic efficiency of Fenton processes. Therefore, the development of an effective strategy for wastewater degradation at low temperatures is essential. In this context, we present the preparation of an NH2-MIL-88B (Fe)/CuInS2 S-scheme heterojunction. Specifically, CuInS2 nanoparticles are introduced onto the Ferro-organic skeleton, resulting in the exposure of a significant number of active surface sites. Furthermore, NH2-MIL-88B (Fe)/CuInS2 demonstrates an extended photoresponse into the long-wavelength region, which contributes to its excellent photothermal properties. Notably, the degradation rate of tetracycline in low-temperature aqueous environments reaches as high as 99.7 %, several times higher than that of the original sample. Additionally, the hydrogen production of NH2-MIL-88B (Fe)/CuInS2 is 2.23 times that of single NH2-MIL-88B (Fe) and 3.46 times that of single CuInS2. Moreover, the system exhibits good H2O2 evolution performance, forming an efficient photo-Fenton system. The charge transfer process in S-scheme heterojunction is confirmed using in-situ X-ray photoelectron spectroscopy and electron paramagnetic resonance. Both transient photoluminescence and photo electrochemical tests further validate the enhanced photoelectrochemical properties of the NH2-MIL-88B (Fe)/CuInS2 S-scheme heterojunction. The exceptional performance of this system can be attributed to the synergistic effects of the S-scheme heterojunction and the bimetallic codoped photo-Fenton system. This research presents a novel approach for the breakdown of low-temperature wastewater using an improved photocatalytic Fenton system.

Synthesis of CuInS2 Quantum Dots Modified with Alanine for Sensitive and Selective Detection of Pb2+ and Cysteine.

In this study, a novel fluorescent probe based on CuInS2 quantum dots modified with alanine (Ala-CuInS2 QDs) was developed for the detection of lead ions and cysteine (Pb2+ and Cys). Ala-CuInS2 QDs were synthesized through a one-step hydrothermal method exhibiting uniform size, good stability and water solubility. The QDs were then utilized as an "on-off-on" fluorescence sensor to detect Pb2+ and Cys in the ranges of 0-20 µM and 0-55 µM respectively, with detection limits of 0.29 µM and 0.66 µM. The mechanism of fluorescence quenching and recovery processes was also explored. Furthermore, Ala-CuInS2 QDs have been successfully applied to detect Pb2+ in tap and river water and detect cysteine in serum.

Multimodal Temperature Readout Boosts the Performance of CuInS2/ZnS Quantum Dot Nanothermometers.

Fluorescent nanothermometers are positioned to revolutionize research into cell functions and provide strategies for early diagnostics. Fluorescent nanostructures hold particular promise to fulfill this potential if nontoxic, stable varieties allowing for precise temperature measurement with high thermal sensitivities can be fabricated. In this work, we investigate the performance of micelle-encapsulated CuInS2/ZnS core/shell colloidal quantum dots (QDs) as fluorescent nanothermometers. We demonstrate four temperature readout modes, which are based on variations in the photoluminescence intensity, energy, and lifetime and on a specific ratio of excitation efficiencies. We further leverage this multimodal readout to construct a fifth, multiparametric thermometer calibration based on the multiple linear regression (MLR) model. We show that the MLR approach boosts the thermometer sensitivity by up to 7-fold while reducing the readout error by about a factor of 3. As a result, our QDs offer the highest sensitivities among semiconducting QDs emitting in the first biological window. The obtained results indicate that CuInS2/ZnS QDs are excellent candidates for intracellular in vivo thermometry and provide guidelines for further optimization of their performance.

Origin of Enhanced Photoelectrochemical Activity of the n-CdS/p-type Semiconductor Interface: Homojunction or Heterojunction?

Surface engineering of photoelectrodes is considered critical for achieving efficient photoelectrochemical (PEC) cells, and various p-type materials have been investigated for use as photoelectrodes. Among these, the p-type semiconductor/n-type CdS heterojunction is the most successful photocathode structure because of its enhanced onset potential and photocurrent. However, it is determined that the main contributor to the enhanced activity is the Cd-doped layer and not the CdS layer. In this study, a Cd-doped n+p-buried homojunction of a CuInS2 photocathode is first demonstrated without a CdS layer. The homojunction exhibited a more active and stable PEC performance than the CdS/CuInS2 heterojunction. Moreover, it is confirmed that Cd doping is effective for other p-type materials. These results strongly suggest that the effects of Cd doping on photocathodes should be carefully investigated when designing CdS/p-semiconductor heterojunction photoelectrodes. They also indicate that the Cd-doped layer has great potential to replace the CdS layer in future photoelectrode designs.

High-Performance CuInS2 Quantum Dot Sensitized Solar Cells Through I-/MPA Dual-Ligands Passivation.

High-efficiency quantum dot sensitized solar cells (QDSSCs) can be received by increasing quantum dot (QD) loading and mitigating QD surface trap states. Herein, the surface state of CuInS2 QDs is optimized through an I-/MPA dual-ligands passivation strategy. The steric hindrance and electrostatic repulsion between QDs can be effectively reduced, thereby enabling an increased QD loading capacity. Meanwhile, the I-/MPA dual-ligands passivation strategy can further lower the surface trap density, leading to substantially enhanced charge transfer efficiency of the solar cells. Interestingly, various iodized salts, including TBAI, MAI, and KI, are proved to possess comparable property, underscoring the versatility and broad applicability of this I-/MPA dual-ligands passivation strategy. Eventually, CuInS2 QDSSCs based on the NH4I/MPA dual-ligands exhibit a noteworthy enhancement in photovoltaic conversion efficiency, surpassing the benchmark of 5.71 % to reach 7.03 %.

Microwave-assisted synthesis of ZnS@CuInxSy for photocatalytic degradation of coloured and non-coloured pollutants.

Copper indium sulfide (CuInS2) exhibits strong visible light absorption and thus has the potential for good photocatalytic activity; however, rapid charge recombination limits its practical usage. An intriguing strategy to overcome this issue is to couple CuInS2 with another semiconductor to form a heterojunction, which can improve the charge carrier separation and, hence, enhance the photocatalytic activity. In this study, photocatalysts comprising CuInS2 with a secondary CuS phase (termed CuInxSy) and CuInxSy loaded with ZnS (termed ZnS@CuInxSy) were synthesized via a microwave-assisted method. Structural and morphological characterization revealed that the ZnS@CuInxSy photocatalyst comprised tetragonal CuInS2 containing a secondary phase of hexagonal CuS, coupled with hexagonal ZnS. The effective band gap energy of CuInxSy was widened from 2.23 to 2.71 as the ZnS loading increased from 0 to 30%. The coupling of CuInxSy with ZnS leads to long-lived charge carriers and efficient visible-light harvesting properties, which in turn lead to a remarkably high activity for the photocatalytic degradation of brilliant green (95.6% in 5 h) and conversion of 4-nitrophenol to 4-nitrophenolate ions (95.4% in 5 h). The active species involved in these photocatalytic processes were evaluated using suitable trapping agents. Based on the obtained results, photocatalytic mechanisms are proposed that emphasize the importance of h+, O2•-, and OH- in photocatalytic processes using ZnS@CuInxSy.

A Comparison of Common Quantum Dot Alternatives to Cadmium-Based Quantum Dots on the Basis of Liver Cytotoxicity.

Fluorescent nanoparticles known as quantum dots (QDs) have unique properties that make them useful in biomedicine. Specifically, CdSe/ZnS QDs, while good at fluorescing, show toxicity. Due to this, safer alternatives have been developed. This study uses a tetrazolium dye (XTT) viability assay, reactive oxygen species (ROS) fluorescent imaging, and apoptosis to investigate the effect of QD alternatives InP/ZnS, CuInS2/ZnS, and nitrogen-doped carbon dots (NCDs) in liver cells. The liver is a possible destination for the accumulation of QDs, making it an appropriate model for testing. A cancerous liver cell line known as HepG2 and an immortalized liver cell line known as THLE-2 were used. At a nanomolar range of 10-150, HepG2 cells demonstrated no reduced cell viability after 24 h. The XTT viability assay demonstrated that CdSe/ZnS and CuInS2/ZnS show reduced cell viability in THLE-2 cells with concentrations between 50 and 150 nM. Furthermore, CdSe/ZnS- and CuInS2/ZnS-treated THLE-2 cells generated ROS as early as 6 h after treatment and elevated apoptosis after 24 h. To further corroborate our results, apoptosis assays revealed an increased percentage of cells in the early stages of apoptosis for CdSe/ZnS-treated (52%) and CuInS2/ZnS-treated (38%) THLE-2. RNA transcriptomics revealed heavy downregulation of cell adhesion pathways such as wnt, cadherin, and integrin in all QDs except NCDs. In conclusion, NCDs show the least toxicity toward these two liver cell lines. While demonstrating less toxicity than CdSe/ZnS, the metallic QDs (InP/ZnS and CuInS2/ZnS) still demonstrate potential concerns in liver cells. This study serves to explore the toxicity of QD alternatives and better understand their cellular interactions.

Synthesis of Sulfur Vacancy-Bearing In2S3/CuInS2 Microflower Heterojunctions via a Template-Assisted Strategy and Cation-Exchange Reaction for Photocatalytic CO2 Reduction.

The synthesis of the accurate composition and morphological/structural design of multielement semiconductor materials is considered an effective strategy for obtaining high-performance hybrid photocatalysts. Herein, sulfur vacancy (Vs)-bearing In2S3/CuInS2 microflower heterojunctions (denoted Vs-In2S3/CuInS2) were formed in situ using In2S3 microsphere template-directed synthesis and a metal ion exchange-mediated growth strategy. Photocatalysts with flower-like microspheres can be obtained using hydrothermally synthesized In2S3 microspheres as a template, followed by Ostwald ripening growth during the metal cation exchange of Cu+ and In3+. The optimal heterostructured Vs-In2S3/CuInS2 microflowers exhibited CO and CH4 evolution rates of 80.3 and 11.8 µmol g-1 h-1, respectively, under visible-light irradiation; these values are approximately 4 and 6.8 times higher than those reported for pristine In2S3, respectively. The enhanced photocatalytic performance of the Vs-In2S3/CuInS2 catalysts could be attributed to the synergistic effects of the following factors: (i) the constructed heterojunctions accelerate charge-carrier separation; (ii) the flower-like microspheres exhibit highly uniform morphologies and compositions, which enhance electron transport and light harvesting; and (iii) the vs. may trap excited electrons and, thus, inhibit charge-carrier recombination. This study not only confirms the feasibility of the design of heterostructures on demand, but also presents a simple and efficient strategy to engineer metal sulfide photocatalysts with enhanced photocatalytic performance.

Enhancing Photocatalytic Activities for Sustainable Hydrogen Evolution on Structurally Matched CuInS2/ZnIn2S4 Heterojunctions.

Effective charge separation and migration pose a critical challenge in the field of solar-driven hydrogen production. In this work, a Z-scheme structured CuInS2/ZnIn2S4 heterojunction was successfully fabricated through a two-step hydrothermal synthesis method to significantly enhance the efficiency of solar-to-hydrogen energy conversion. Structural characterization revealed that the lattice-matched CuInS2/ZnIn2S4 heterojunction exhibits an enlarged interfacial contact area, which facilitates the transfer and separation of photogenerated charges. Microscopic analysis indicated that the CuInS2/ZnIn2S4 composite material has a tightly interwoven interface and a morphology resembling small sugar cubes. Photoelectrochemical spectroscopy analysis demonstrated that the heterojunction structure effectively enhances visible light absorption and charge separation efficiency, leading to an improvement in photocatalytic activity. Hydrogen production experimental data indicated that the CuInS2/ZnIn2S4 heterojunction photocatalyst prepared with a CuInS2 content of 20 wt% exhibits the highest hydrogen evolution rate, reaching 284.9 µmol·g-1·h-1. Moreover, this photocatalyst maintains robust photocatalytic stability even after three consecutive usage cycles. This study demonstrated that the Z-scheme CuInS2/ZnIn2S4 heterojunction photocatalyst exhibits enhanced hydrogen evolution efficiency, offering an effective structural design for harnessing solar energy to obtain hydrogen fuel. Therefore, this heterojunction photocatalyst is a promising candidate for practical applications in solar hydrogen production.

Combinational Intercalation-Conversion-Intercalation reaction of CuInS2@PPy anode for Sodium-Ion batteries.

Polypyrrole-coated CuInS2 (CuInS2@PPy) composite was prepared through the chemical vapor transport method and subsequent in situ polymerized coating strategy. In this unique nanoarchitecture, the PPy coating layer plays a crucial role in improving the conductivity of the composite, suppressing the volume change of CuInS2, and maintaining the structural integrity of electrode material upon cycling. In addition, the electrochemical reaction mechanism and kinetics of CuInS2@PPy were investigated in-depth. Benefitting from the synergism of its combinational intercalation-conversion-intercalation reaction mechanism and the high conductivity of the PPy coating layer, CuInS2@PPy electrode exhibits superior rate capability and cycling stability for sodium-ion batteries, with a capacity of 404.8 mA h g-1 at 4 A g-1 over 2500 cycles.

In-situ construct CuInS2/Bi/Bi2MoO6 S-scheme/Schottky dual heterojunctions catalyst for enhanced photocatalytic degradation of diclofenac sodium.

In this paper, the S-scheme/Schottky heterojunction photocatalyst (CuInS2/Bi/Bi2MoO6, CIS/Bi/BMO) was successfully constructed via a facile in-situ solvothermal method, aimed at enhancing its photocatalytic performance. The results of the study on the photocatalytic degradation of diclofenac sodium (DCF) under simulated solar light irradiation revealed that the as-prepared composite exhibited remarkable catalytic efficiency in comparison to the pristine Bi2MoO6 and CuInS2. The plasmonic bismuth (Bi) was formed during the solvothermal process. Subsequently, CuInS2 and Bi were grown on the surface of Bi2MoO6 leading to forming CIS/BMO S-scheme heterojunction, along with a Schottky junction between Bi and Bi2MoO6. The use of ethylene glycol as a support was the main reason for the significant improvement in photocatalytic efficiency in the degradation of DCF. Moreover, the probable photocatalytic mechanisms for the degradation of DCF had been proposed based on the active species quenching experiments. The eleven degradation products were detected by HPLC-MS, and the degradation reaction pathway of DCF was deduced. Additionally, the CIS/Bi/BMO photocatalyst exhibited a consistently high removal rate after four cycles. This study proposes a new strategy for designing efficient S-scheme/Schottky heterojunction photocatalysts for solar energy conversion.

Fabrication of p-n Heterostructured Photocatalysts with Triazine-Based Covalent Organic Framework and CuInS2 for High-Efficiency CO2 Reduction.

The application of covalent organic frameworks (COFs) for the photocatalytic reduction of CO2 is mostly limited by severe charge recombination and low sunlight utilization. Herein, a triazine-based COF with an electron-rich and large π-conjugated system (TCOF) was employed as a building block and integrated with CuInS2 (CIS) to construct a noble-metal-free and high-efficiency photocatalyst for CO2 reduction. The in situ growth of CIS nanosheets on TCOF creates a p-n heterojunction, named CIS@TCOF. Compared with TCOF, the CIS@TCOF heterostructure exhibits a dramatically boosted photocatalytic performance in the reduction of CO2. The produced HCOOH yield over 10 wt % CIS@TCOF can be up to 171.2 µmol g-1 h-1 under visible light irradiation with good reproducibility, which is about 3 times as high as that over TCOF. Further in-depth studies indicate that the introduction of CIS not only enhances the visible light utilization but also restrains the recombination of photogenerated electron-hole pairs efficiently and facilitates the photoinduced charge transfer via the p-n heterojunction system due to the unique structural and compositional features. This research shows the great potential of COFs as efficient photocatalytic carbon fixation materials and provides a versatile route to construct semiconductor-COF heterostructures for photocatalysis.

Carbon quantum dots(CQDs)-sensitized CdS/CuInS2 heterojunction as a photoelectrochemical biosensing platform for highly sensitive detection of prostate-specific antigen.

Sensitive and quantitative detection of prostate-specific antigen (PSA) has been determined to be indispensable for clinical diagnostics of prostate cancer, whereas such detection is quite challenging due to the extremely low concentration of biomarkers in human serum samples. In this study, a photoelectrochemical (PEC) sensor was effectively developed for the high-sensitivity analysis of prostate-specific antigen (PSA) using a signal amplification method utilizing sensitized carbon quantum dots (CQDs). In this experiment, cadmium sulfide quantum dots were employed as the substrate materials, and indium copper sulfide quantum dots were loaded on their surfaces. Moreover, the efficient matching of energy levels in these two materials contributed to the generation of photocurrents. The aforementioned heterojunction semiconductor QDs were thus combined with CQDs to produce CQDs on their surfaces. As a result of the presence of CQDs, the ability of heterojunction materials to absorb light was remarkably enhanced, increasing the photocurrent by over ten times. Consequently, in this study, CQDs were combined with PEC sensors, and the developed PEC biosensors exhibited excellent optical performance, sensitivity, repeatability, and stability. The results obtained from the analysis of actual samples were satisfactory and have promising application prospects.

Construction of S-scheme CuInS2/ZnIn2S4 heterostructures for enhanced photocatalytic activity towards Cr(VI) removal and antibiotics degradation.

The efficient and ecofriendly removal of pharmaceutical antibiotics and heavy metal Cr(VI) from water sources is a crucial challenge in current environmental management. Photocatalysis presents a viable environmentally friendly solution for eliminating organic contaminants and heavy-metal ions. In this study, a novel S-scheme CuInS2/ZnIn2S4 (CIS/ZIS) heterojunction was developed using a one-pot solvothermal method. The optimized CIS/ZIS heterojunction exhibited considerably improved photocatalytic activity for the removal of antibiotics and Cr(VI), achieving over 90% removal for both tetracycline hydrochloride (TC) (20 mg/L) and Cr(VI) (20 mg/L) under visible light irradiation. The study also delved into the effect of coexisting inorganic anions and assessed the cyclic stability of the composite photocatalysts. This enhancement mechanism can be delineated into three key elements. First, the incorporation of the narrow-gap semiconductor CuInS2 effectively augmented the photoabsorption capacity. Second, the inclusion of ZnIn2S4 caused an increase in surface active sites. Most importantly, the internal electric field at the interface between CuInS2 and ZnIn2S4 expedited the separation of photogenerated carriers. Furthermore, the results revealed that superoxide radical and photogenerated holes are the primary active substance responsible for TC removal, while photogenerated electrons play a central role in the photoreduction of Cr(VI). To gain insights into the transport pathways of photogenerated carriers, we conducted experiments with nitrotetrazolium blue chloride (NBT) and photodeposited gold. This study offers an innovative approach to enhancing the photocatalytic performance of ternary In-based materials by constructing S-scheme heterojunctions.

A signal-on photoelectrochemical aptasensor based on ferrocene labeled triple helix DNA molecular switch for detection of antibiotic amoxicillin.

A sensitive signal-on photoelectrochemical aptasensor for antibiotic determination was constructed based on the energy level matching between ferrocene and CuInS2. P-type CuInS2 microflower was complexed with reduced graphene oxide (CuInS2/rGO) to get photocathode current with good photoelectric conversion efficiency and stability. Then, hairpin DNA (HP) was covalently bonded to the electrode surface. A triple helix DNA (THMS) was used as a molecular switch. After the specific recognition between target and THMS in homogeneous solution, ferrocene labeled probe (Fc-T2) was released. Finally, Fc-T2 was captured by the HP, which leaded the obvious increase of photocurrent for the energy level matching between ferrocene and CuInS2. The increase of the photocurrent signal was proportional to the concentration of target amoxicillin (AMOX), the linear range was 100 fM-100 nM with detection limit of 19.57 fM. Meanwhile, the method has been successfully applied for milk and lake water samples analysis with satisfactory results.

A signal polarity conversion photoelectrochemical immunosensor for neuron-specific enolase detection based on MgIn2S4-sensitized CsPbBr3.

A photoelectrochemical (PEC) immunosensor was designed based on MgIn2S4-decorated inorganic halide perovskite CsPbBr3 combined with the signal polarity conversion strategy for neuron-specific enolase (NSE) detection. CsPbBr3 was applied as the basic photoactive material owing to its excellent optical and electronic properties, which provide a good PEC performance for sensor construction. In order to improve the stability of this perovskite, the three-dimensional flower-like MgIn2S4 with a desirable direct band gap was applied to enhance the PEC response. Also, the excellent structure of MgIn2S4 provides large surface-active sites for CsPbBr3 loaded. For enhancing the detection sensitivity of PEC immunosensor, p-type CuInS2 was used as a signal probe which fixed on detection antibody (Ab2). When the target NSE was present, the photogenerated electrons produced by CuInS2 were transferred to the test solution, and the polarity of PEC signal changes. Based on the above photosensitive materials and signal conversion strategy, the proposed PEC immunosensor showed favorable detection performance, and the linear detection range is 0.0001 ~ 100 ng/mL with a 38 fg/mL of detection limit. The proposed strategy improved the adhibition of CsPbBr3 in the analytical chemistry field as well as provided a reference method for other protein detections.

Dual-mode self-powered photoelectrochemical and colorimetric determination of procalcitonin accomplished by multienzyme-expressed Ni4Cu2 bimetallic hollow nanospheres and spherical nanoflower-MoS2/Cu2ZnSnS4/Bi2S3.

Bacterial infections, viral infections and autoimmune diseases pose a considerable threat to human health. Procalcitonin (PCT) has emerged as a biomarker for the detection of these diseases. To ensure accurate and reliable results, we propose a dual-mode approach that incorporates self-validation and self-correction mechanisms. Herein, we develop a dual-mode self-powered photoelectrochemical (PEC) and colorimetric sensor to determine PCT. The self-powered PEC sensor was constructed with a photoanode of spherical nanoflower-MoS2/Cu2ZnSnS4/Bi2S3 material and a photocathode of CuInS2 material. Ni4Cu2 bimetallic hollow nanospheres (BHNs) possess superoxide dismutase and catalase performance, which facilitate superoxide anion radical (·O2-) and H2O2 circulating generation, promoting the separation of photogenerated electrons and holes to amplify photocurrent signal. Thus Ni4Cu2 BHNs is used as a marker material for PEC sensor. Meanwhile, in colorimetric mode, Ni4Cu2 BHNs converts blue oxTMB to a colourless TMB for colorimetric detection of PCT. Based on this principle, dual-mode determination of PCT with high sensitivity is achieved. The dual-mode method not only demonstrates outstanding properties and practicability, but also presents an effective, highly efficient and reliable method for detecting PCT.

Development of a fluorometric and colorimetric dual-mode sensing platform for acid phosphatase assay based on Fe3+ functionalized CuInS2/ZnS quantum dots.

BACKGROUND: The spectral dual-mode response towards analyte has been attracted much attention, benefiting from the higher detection accuracy of such strategy in comparison to single signal readout. However, the currently reported dual-mode sensors for acid phosphatase (ACP) activity are still limited, and most of them more or less exist some deficiencies, such as complicated construction procedure, high-cost, poor biocompatibility, aggregation-caused quenching and limited emission capacity. RESULTS: Herein, we employed Fe3+ functionalized CuInS2/ZnS quantum dots (CIS/ZnS QDs) as nanosensor to develop a novel fluorometric and colorimetric dual-mode assay for ACP activity, combing with ACP-triggered hydrolysis of ascorbic acid 2-phosphate (AAP) into ascorbic acid (AA). The Fe3+ binding to CIS/ZnS QDs can be reduced into Fe2+ during the determination, resulting in the dramatically weakened photoinduced electron transfer (PET) effect and the disappearance of competition absorption. Thus, a highly sensitive ACP assay in the range of 0.22-12.5 U L-1 through fluorescence "turn-on" mode has been achieved with a detection of limit (LOD) of 0.064 U L-1. Meanwhile, the ACP activity can also be quantified by spectrophotometry based on the chromogenic reaction of the formed Fe2+ with 1,10-phenanthroline (Phen). Moreover, the designed nanosensor with good biocompatibility was successfully applied to image and monitor the ACP levels in living cells. SIGNIFICANCE: We believe that the proposed method has remarkable advantages and potential application for ACP assay in terms of the high accuracy, simplicity, low cost, as well as its adequate sensitivity.

High-Density CuInS2 Quantum Dots for Efficient and Stable CO2 Electroreduction.

Electrochemically converting CO2 back into fuels and chemicals is promising in alleviating the greenhouse effect worldwide. Various high-efficiency catalysts have been achieved, yet the unsatisfied structural stability under CO2 electrolysis conditions restricts their practical application. Herein, a sub-5 nm sized CuInS2 quantum dots (CIS-QDs) based electrocatalyst for converting CO2 into CO are developed. Taking advantage of the stable M─Ch (metal-chalcogenide) covalent bonds, and unique p-block metal properties, the as-prepared catalyst exhibits excellent structural stability under large overpotentials and can achieve a high CO Faradaic efficiency (FE) of 86% (total CO2 reduction FE of 89%) at -0.65 V versus reversible hydrogen electrode with long-term durability of 40 h and outstanding current densities of 10.6 mA cm-2 simultaneously. Furthermore, detailed electrochemical analyses revealed that the excellent performance of the as-prepared catalysts shall be attributed to the high-density active sites and fast charge transfer brought by the ultrasmall size of CIS-QDs. This work provides insights into the design of high-density and stable catalytic sites for developing high-performance electrocatalysts.

Temperature- and Size-Dependent Photoluminescence of CuInS2 Quantum Dots.

We present the results of a temperature-dependent photoluminescence (PL) spectroscopy study on CuInS2 quantum dots (QDs). In order to elucidate the influence of QD size on PL temperature dependence, size-selective precipitation was used to obtain several nanoparticle fractions. Additionally, the nanoparticles' morphology and chemical composition were studied using transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The obtained QDs showed luminescence in the visible-near infrared range. The PL energy, linewidth, and intensity were studied within an 11-300 K interval. For all fractions, a temperature decrease led to a shift in the emission maximum to higher energies and pronounced growth of the PL intensity down to 75-100 K. It was found that for large particle fractions, the PL intensity started to decrease, with temperature decreasing below 75 K, while the PL intensity of small nanoparticles remained stable.