Iron-promoted zirconia-alumina supported Ni catalyst for highly efficient and cost-effective hydrogen production via dry reforming of methane.

Developing cost-effective and high-performance catalyst systems for dry reforming of methane (DRM) is crucial for producing hydrogen (H2) sustainably. Herein, we investigate using iron (Fe) as a promoter and major alumina support in Ni-based catalysts to improve their DRM performance. The addition of iron as a promotor was found to add reducible iron species along with reducible NiO species, enhance the basicity and induce the deposition of oxidizable carbon. By incorporating 1 wt.% Fe into a 5Ni/10ZrAl catalyst, a higher CO2 interaction and formation of reducible "NiO-species having strong interaction with support" was observed, which led to an ∼80% H2 yield in 420 min of Time on Stream (TOS). Further increasing the Fe content to 2wt% led to the formation of additional reducible iron oxide species and a noticeable rise in H2 yield up to 84%. Despite the severe weight loss on Fe-promoted catalysts, high H2 yield was maintained due to the proper balance between the rate of CH4 decomposition and the rate of carbon deposit diffusion. Finally, incorporating 3 wt.% Fe into the 5Ni/10ZrAl catalyst resulted in the highest CO2 interaction, wide presence of reducible NiO-species, minimum graphitic deposit and an 87% H2 yield. Our findings suggest that iron-promoted zirconia-alumina-supported Ni catalysts can be a cheap and excellent catalytic system for H2 production via DRM.

Microwave-assisted organic acids and green hydrogen production during mixed culture fermentation.

BACKGROUND: The integration of anaerobic digestion into bio-based industries can create synergies that help render anaerobic digestion self-sustaining. Two-stage digesters with separate acidification stages allow for the production of green hydrogen and short-chain fatty acids, which are promising industrial products. Heat shocks can be used to foster the production of these products, the practical applicability of this treatment is often not addressed sufficiently, and the presented work therefore aims to close this gap. METHODS: Batch experiments were conducted in 5 L double-walled tank reactors incubated at 37 °C. Short microwave heat shocks of 25 min duration and exposure times of 5-10 min at 80 °C were performed and compared to oven heat shocks. Pairwise experimental group differences for gas production and chemical parameters were determined using ANOVA and post-hoc tests. High-throughput 16S rRNA gene amplicon sequencing was performed to analyse taxonomic profiles. RESULTS: After heat-shocking the entire seed sludge, the highest hydrogen productivity was observed at a substrate load of 50 g/l with 1.09 mol H2/mol hexose. With 1.01 mol H2/mol hexose, microwave-assisted treatment was not significantly different from oven-based treatments. This study emphasised the better repeatability of heat shocks with microwave-assisted experiments, revealing low variation coefficients averaging 29%. The pre-treatment with microwaves results in a high predictability and a stronger microbial community shift to Clostridia compared to the treatment with the oven. The pre-treatment of heat shocks supported the formation of butyric acid up to 10.8 g/l on average, with a peak of 24.01 g/l at a butyric/acetic acid ratio of 2.0. CONCLUSION: The results support the suitability of using heat shock for the entire seed sludge rather than just a small inoculum, making the process more relevant for industrial applications. The performed microwave-based treatment has proven to be a promising alternative to oven-based treatments, which ultimately may facilitate their implementation into industrial systems. This approach becomes economically sustainable with high-temperature heat pumps with a coefficient of performance (COP) of 4.3.

Efficient Water Reforming of Biomass to H2 via Well-Organized Redox-Neutral Cleavage of C-C, O-H and C-H Bonds.

Hydrogen (H2) is a clean and environmentally friendly energy carrier. The depletion of fossil fuels makes renewable H2 production highly desirable. Water reforming of renewable biomass to hydrogen, with a relay of natural photosynthesis to biomass, would be an indirect pathway to realize the ideal but extremely challenging photocatalytic overall water splitting to hydrogen, with favorable thermodynamics. Since the seminal work of water reforming of biomass in 1980, great endeavors have been made. Nevertheless, hitherto, the entire kinetic pathway has been elusive, which seriously limits the reforming processes. Using a designed well-organized redox-neutral cleavage of C-C, O-H and C-H bonds enabled by photoelectrocatalysis, here, we show the efficient water reforming of biomass to hydrogen at room temperature, with a yield up to 93%. The clear insights into the kinetic pathway with oxidation of carbon radicals to carbon cations as the indicated rate-determining step, would cast brightness for efficient and sustainable hydrogen production to accelerate the hydrogen economy.

Tuning Electronic and Proton Transfer Properties on Amino-Functionalized Co-Based MOF for Efficient Photocatalytic Hydrogen Evolution.

Efficient hydrogen (H2) production through photocatalytic water splitting was achieved by using an amino-functionalized azolate/cobalt-based metal-organic framework (MOF). While previous reports highlighted the amino group's role only as a substituent group for enabling light absorption of MOFs in the visible region, our present study revealed its dual role. The amino substituent not only acts as an electron donor to increase the electron availability at the active Co sites but also provides hydrogen-hopping sites within the pore channel, facilitating proton (H+) diffusion along the framework. This dual functionality significantly boosts the performance of this Co-MOF as a hydrogen evolution cocatalyst. When combined with fluorescein and triethylamine as the photosensitizer and sacrificial agent, respectively, the Co-MOF achieved a remarkable H2 production rate of 27 mmol g-1 over 4 h. Notably, this performance surpasses those of benchmark platinum (Pt) and titanium dioxide (TiO2) cocatalysts.

Coupling Photocatalytic Hydrogen Production with Key Oxidation Reactions.

Hydrogen represents a clean and sustainable energy source with wide applications in fuel cells and hydrogen energy storage systems. Photocatalytic strategies emerge as a green and promising solution for hydrogen production, which still reveals several critical challenges in enhancing the efficiency and stability and improving the whole value. This review systematically elaborates on various coupling approaches for photocatalytic hydrogen production, aiming to improve both efficiency and value through different oxidation half-reactions. Firstly, the fundamental mechanism is discussed for photocatalytic hydrogen production. Then, the advances, challenges, and opportunities are expanded for the coupling of photocatalytic hydrogen production, which focuses on the integration of value-added reactions including O2 production, H2O2 production, biomass conversion, alcohol oxidation, and pollutants treatment. Finally, the challenges and outlook of photocatalytic H2 production technology are analyzed from the aspects of coupling hydrogen production value, photocatalyst design and reaction system construction. This work presents a holistic view of the field, emphasizing the synergistic benefits of coupled reactions and their practical application potential, rather than focusing on catalysts or single reaction systems. This review provides valuable references for the development and application of photocatalytic hydrogen production in energy conversion and environmental conservation through sustainable, eco-friendly and economic pathways.

Zinc Vaporization Induced Formation of Desired Ni Nanoparticles Coated with Ultrathin Carbon Shells for Efficient Electrocatalytic H2 Production Coupling with Methanol Upgrading.

The integration of the hydrogen evolution reaction (HER) with the methanol oxidation reaction (MOR) has been demonstrated to be a viable strategy for the energy-saving generation of H2 and value-added formate, which relies primarily on highly active and cost-effective bifunctional electrocatalysts. Herein, an efficient electrocatalyst consisting of controllable Ni nanoparticles (NPs) coated with ultrathin graphitic carbon shells was obtained by the pyrolysis of a Ni-Zn metal-organic framework. Intriguingly, we found that zinc vaporization not only resulted in the relatively small Ni NPs but also ultrathin carbon shells (≤3 layers). The density functional theory simulations confirmed that these ultrathin carbon shells significantly influenced electrocatalytic activity by facilitating electron transfer from the Ni core to the carbon shell. The optimized Ni1(Zn)@C demonstrated high catalytic activity for both HER and MOR, and only a low potential of 97 mV at 10 mA cm-2 was required for HER and 1.48 V at 30 mA cm-2 for MOR. In a two-electrode electrocatalytic cell measurement, a cell voltage of 1.63 V was observed at 10 mA cm-2 in the presence of methanol, 240 mV lower than that without methanol.

Boosting the Production of Hydrogen from an Overall Urea Splitting Reaction Using a Tri-Functional Scandium-Cobalt Electrocatalyst.

The creation of highly efficient and economical electrocatalysts is essential to the massive electrolysis of water to produce clean energy. The ability to use urea reaction of oxidation (UOR) in place of the oxygen/hydrogen evolution process (OER/HER) during water splitting is a significant step toward the production of high-purity hydrogen with less energy usage. Empirical evidence suggests that the UOR process consists of two stages. First, the metal sites undergo an electrochemical pre-oxidation reaction, and then the urea molecules on the high-valence metal sites are chemically oxidized. Here, the use of scandium-doped CoTe supported on carbon nanotubes called Sc@CoTe/CNT is reported and CoTe/CNT as a composite to efficiently promote hydrogen generation from highly durable and active electrocatalysts for the OER/UOR/HER in urea and alkali solutions. Electrochemical impedance spectroscopy indicates that the UOR facilitates charge transfer across the interface. Furthermore, the Sc@CoTe/CNT nanocatalyst has high performance in KOH and KOH-containing urea solutions as demonstrated by the HER, OER, and UOR (215 mV, 1.59, and 1.31 V, respectively, at 10 mA cm-2 in 1 m KOH) and CoTe/CNT shows 195 mV, 1.61 and 1.3 V, respectively. Consequently, the total urea splitting system achieves 1.29 V, whereas the overall water splitting device obtaines 1.49 V of Sc@CoTe/CNT and CoTe/CNT shows 1.54, 1.48 V, respectively. This work presents a viable method of combining HER with UOR for maximally effective hydrogen production.

Iridium Single-Atom-Ensembles Stabilized on Mn-Substituted Spinel Oxide for Durable Acidic Water Electrolysis.

Exploring single-atom-catalysts for the acidic oxygen evolution reaction (OER) is of paramount importance for cost-effective hydrogen production via acidic water electrolyzers. However, the limited durability of most single-atom-catalysts and Ir/Ru-based oxides under harsh acidic OER conditions, primarily attributed to excessive lattice oxygen participation resulting in metal-leaching and structural collapse, hinders their practical application. Herein, an innovative strategy is developed to fabricate short-range Ir single-atom-ensembles (IrSAE) stabilized on the surface of Mn-substituted spinel Co3O4 (IrSAE-CMO), which exhibits excellent mass activity and significantly improved durability (degradation-rate: ≈2 mV h-1), outperforming benchmark IrO2 (≈44 mV h-1) and conventional Irsingle-atoms on pristine-Co3O4 for acidic OER. First-principle calculations reveal that Mn-substitution in the octahedral sites of Co3O4 substantially reduces the migration energy barrier for Irsingle-atoms on the CMO surface compared to pristine-Co3O4, facilitating the migration of Irsingle-atoms to form strongly correlated IrSAE during pyrolysis. Extensive ex situ characterization, operando X-ray absorption and Raman spectroscopies, pH-dependence activity tests, and theoretical calculations indicate that the rigid IrSAE with appropriate Ir-Ir distance stabilized on the CMO surface effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, thereby mitigating Ir-dissolution and structural collapse, boosting the stability in an acidic environment.

Tailoring Copper Single-Atoms-Stabilized Metastable Transition-Metal-Dichalcogenides for Sustainable Hydrogen Production.

Unconventional 1T' phase transition metal dichalcogenides (TMDs) show great potential for hydrogen evolution reaction (HER). However, they are susceptible to transitioning into the stable 2H phase, which reduces their catalytic activity and stability. Herein, we present a scalable approach for designing thermally stable 1T'-TMDs hollow structures (HSs) by etching Cu1.94S templates from pre-synthesized Cu1.94S@TMDs heterostructures, including 1T'-MoS2, MoSe2, WS2, and WSe2 HSs. Furthermore, taking 1T'-MoS2 HSs as an example, the etched Cu ions can be firmly adsorbed on their surface in the form of single atoms (SAs) through Cu-S bonds, thereby elevating the phase transition temperature from 149 ºC to 373 ºC. Due to the advantages conferred by the 1T' phase, hollow structure, and synergistic effect between Cu SAs and 1T'-MoS2 supports, the fabricated 1T'-MoS2 HSs demonstrate superior HER performance. Notably, their high-phase stability enables continuous operation of designed 1T'-MoS2 HSs for up to 200 hours at an ampere-level current density without significant activity decay. This work provides a universal method for synthesizing highly stable 1T'-TMDs electrocatalysts, with a particular focus on the relationship between their phase and catalytic stability.

Dynamic Reconstruction of Yttrium Oxide-Stabilized Cobalt-Loaded Carbon-Based Catalysts During Thermal Ammonia Decomposition.

Hydrogen production from the decomposition of ammonia is considered an effective approach for addressing challenges associated with hydrogen storage and transportation. However, their relatively high energy consumption and low efficiency hinder practical multi-scenario applications. In this study, Y2O3-stabilized catalysts with Co-loaded onto porous nitrogen-doped carbon (Y2O3-Co/NC) are synthesized by pyrolysis of Y(NO3)3-modified ZIF-67 under an inert atmosphere, followed by annealing in a reducing environment. The introduction of Y2O3 enhanced the recombination and desorption of N atoms and facilitated the gradual dehydrogenation of NHx on the catalyst surface, resulting in improved catalytic activity for the thermal decomposition of ammonia. Benefitting from the electron-donating properties of Y2O3 and N-doped carbon, the optimized catalyst achieved a remarkable NH3 conversion efficiency of 92.3% at a high gas hourly space velocity of 20 000 cm3· g cat - 1 ${\mathrm{g}}_{{\mathrm{cat}}}^{ - {\mathrm{1}}}$ ·h-1 with an encouraging H2 production rate of 20.6 mmol· g cat - 1 ${\mathrm{g}}_{{\mathrm{cat}}}^{ - {\mathrm{1}}}$ ·min-1 at 550 °C. Moreover, the synthesized catalyst undergoes a fast-dynamic reconstruction process, resulting in exceptionally stable catalytic activity during the thermal decomposition of ammonia, rendering it a promising candidate for carbon-free energy thermocatalytic conversion technology.

General synthesis of single-crystalline Ta2O5 nanorods towards enhanced photocatalytic H2 production activity.

As a potential candidate for photocatalytic H2 production from water splitting, Ta2O5 catalyst presents suitable conduction and valence band positions, but suffers from poor charge transfer ability, which seriously limits its photocatalytic performance enhancement. Here, a facile and eco-friendly hydrothermal method was developed for the fabrication of one-dimensional (1D) Ta2O5 nanorods using the freshly precipitated tantalic acids as the precursors. An oriented attachment mechanism was proposed for the growth of Ta2O5 nanorods. Moreover, the present synthetic approach was further extended to direct synthesis of nine kinds of alkaline tantalates and alkaline-earth tantalates nanostructures, suggesting its general applicability. A significant increase in activity in photocatalytic H2 production was revealed on 1D Ta2O5 nanorods. The improved photocatalytic H2 production activity of Ta2O5 nanorods was mainly attributed to its 1D nanorods structure with high crystallization and large specific surface areas as well as excellent charge transfer efficiency.

Copper-surface-mediated synthesis of sp2 carbon-conjugated covalent organic framework photocathodes for photoelectrochemical hydrogen evolution.

Sp2-carbon (sp2-c) covalent organic frameworks (COFs), featuring distinctive π-conjugated network structures, facilitate the migration of photo-generated carriers, rendering them exceptionally appealing for applications in photoelectrochemical water splitting. However, owing to the powdery nature of COFs, leaving anchor the sp2-c COFs powder tightly onto a conductive substrate challenging. Here, we propose a method for preparing photoactive substance-conductive substrate integrated photocathodes through copper surface-mediated knoevenagel polycondensation (Cu-SMKP), this approach results in a uniform and stable sp2-c COF film, directly grown on commercial copper foam (COFTh-Cu). The COFTh-Cu demonstrates a high H2-evolution photocurrent density of 56 µA cm-2 at 0.3 V versus RHE, sustaining stability for 12 hours. The as-prepared COFTh-Cu represents a 4.5-fold increase in current density compared to traditional spin-coating methods and outperforms most COF photocathodes without cocatalysts. This innovative copper surface-mediated approach for preparing photocathodes opens up a crucial pathway towards the realization of highly active COF photocathodes.

Assembly strategies for microbe-material hybrid systems in solar energy conversion.

Microbe-material hybrid systems which facilitate the solar-driven synthesis of high-value chemicals, harness the unique capabilities of microbes, maintaining the high-selectivity catalytic abilities, while concurrently incorporating exogenous materials to confer novel functionalities. The effective assembly of both components is essential for the overall functionality of microbe-material hybrid systems. Herein, we conducted a critical review of microbe-material hybrid systems for solar energy conversion focusing on the perspective of interface assembly strategies between microbes and materials, which are categorized into five types: cell uptake, intracellular synthesis, extracellular mineralization, electrostatic adsorption, and cell encapsulation. Moreover, this review elucidates the mechanisms by which microbe-material hybrid systems convert elementary substrates, such as carbon dioxide, nitrogen, and water, into high-value chemicals or materials for energy generation.

Synergistically-mediated highly-efficient visible-light-driven hydrogen evolution activity using Ohmic/Schottky-type dual-junctions and sulfur vacancy.

Enabling highly-efficient multiplex-optimization photocatalysts is critical to overcome the bottlenecks of hydrogen evolution reaction efficiency and photostability. Herein, novel CoS/Sv-ZnIn2S4/MoS2 composites are successfully synthesized through an in situ technique. Taking advantage of the synergistic effect of sulfur vacancy, Schottky-type MoS2/Sv-ZnIn2S4 junction and Ohmic-type CoS/Sv-ZnIn2S4 junction, the light absorption, electron/hole separation efficiency, charge transfer rate and hydrogen reduction reaction dynamic can be significantly enhanced. As a result, an impressive photocatalytic hydrogen evolution rate of 18.43 mmol g-1 h-1 is achieved under the visible-light irradiation. Furthermore, apparent quantum efficiencies of 72.14 % and 9.91 % are also achieved under 350 and 420 nm monochromatic light irradiation. This work presents an in situ perspective to design multiplex-optimization photocatalytic system for highly-efficient hydrogen production.

Enhancing deep visible-light photoelectrocatalysis with a single solid-state synthesis: Carbon nitride/TiO2 heterointerface.

Visible-light responsive, stable, and abundant absorbers are required for the rapid integration of green, clean, and renewable technologies in a circular economy. Photoactive solid-solid heterojunctions enable multiple charge pathways, inhibiting recombination through efficient charge transfer across the interface. This study spotlights the physico-chemical synergy between titanium dioxide (TiO2) anatase and carbon nitride (CN) to form a hybrid material. The CN(10%)-TiO2(90%) hybrid outperforms TiO2 and CN references and literature homologs in four photo and photoelectrocatalytic reactions. CN-TiO2 achieved a four-fold increase in benzylamine conversion, with photooxidation conversion rates of 51, 97, and 100 % at 625, 535, and 465 nm, respectively. The associated energy transfer mechanism was elucidated. In photoelectrochemistry, CN-TiO2 exhibited 23 % photoactivity of the full-spectrum measurement when using a 410 nm filter. Our findings demonstrate that CN-TiO2 displayed a band gap of 2.9 eV, evidencing TiO2 photosensitization attributed to enhanced charge transfer at the heterointerface boundaries via staggered heterojunction type II.

Ni-Based Materials for Industrial Alkaline Hydrogen Production.

Hydrogen has been recognized as a green energy carrier, which can relieve energy shortage and environmental pollution. Currently, alkaline water electrolysis (AWE) driven by renewable energy to produce large-scale green hydrogen is a mainstream technology. However, tardy cathodic hydrogen evolution reaction (HER) and stability issue of catalysts make it challenging to meet the industrial requirements. Ni-based materials have attracted wide attention, thanks to their low cost and rich tuning possibilities, and many efforts have focused on their activity and stability. However, due to the significant discrepancy between laboratory and industrial conditions, these catalysts have not been widely deployed in industrial AWE. In this review, we first introduce the differences between laboratory and industrial stage, especially concerning equipment, protocols and evaluation metrics. To shorten these gaps, some strategies are proposed to improve the activity and stability of the Ni-based catalysts. Besides, some key issues related to the catalysts in industrial AWE device are also emphasized, including reverse-current and foreign ions in the electrolyte. Finally, the challenges and outlooks on the industrial alkaline AWE are discussed.

Photocatalytic Reforming of Ethanol in the Liquid Phase Using a Ternary Composite of Rh/TiO2/g-C3N4 as a Catalyst.

Photocatalytic reforming of ethanol provides an effective way to produce hydrogen energy using natural and nontoxic ethanol as raw material. Developing highly efficient catalysts is central to this field. Although traditional semiconductor/metal heterostructures (e.g., Rh/TiO2) can result in relatively high catalyst performance by promoting the separation of photoinduced hot carriers, it will still be highly promising to further improve the catalytic performance via a cost-effective and convenient method. In this study, we developed a highly efficient photocatalyst for ethanol reformation by preparing a ternary composite structure of Rh/TiO2/g-C3N4. Hydrogen is the main product, and the reaction rate could reach up to 27.5 mmol g-1 h-1, which is ∼1.41-fold higher than that of Rh/TiO2. The catalytic performance here is highly dependent on the wavelength of the light illumination. Moreover, the photocatalytic reforming of ethanol and production of hydrogen were also dependent on the Rh loading and g-C3N4:TiO2 ratio in Rh/TiO2/g-C3N4 composites as well as the ethanol content in the reaction system. The mechanism of the enhanced hydrogen production in Rh/TiO2/g-C3N4 is determined as the improvement in the separation of photoinduced hot carriers. This work provides an effective photocatalyst for ethanol reforming, largely expanding its application in the field of renewable energy and interface science.

ScSeI Monolayer for Photocatalytic Water Splitting.

We theoretically identify the ScSeI monolayer as a promising new 2D material for photocatalysis through first-principles calculations. The most notable feature is the significant difference in carrier mobility, with electron mobility in the horizontal direction being 20.66 times higher than hole mobility, minimizing electron-hole recombination. The ScSeI monolayer exhibits a bandgap of 2.51 eV, with the valence band maximum at -6.37 eV and the conduction band minimum at -3.86 eV, meeting the requirements for water splitting. Phosphorus doping lowers the Gibbs free energy by 1.63 eV, enhancing the catalytic activity. The ScSeI monolayer achieves a hydrogen production efficiency of 17%, surpassing the commercial threshold of 10% and shows excellent mechanical, thermal, and dynamic stability, indicating feasibility for experimental synthesis and practical application. Additionally, the monolayer maintains its photocatalytic properties under tensile strain (-6% to 6%) and in aqueous environments, reinforcing its potential as an effective photocatalyst. Based on these findings, we believe the ScSeI monolayer is a highly promising photocatalyst.

Reversible Photochromic Phenomenon of Plasmonic Metal/Semiconductor Heterostructures via Photoinduced Electron Storage.

The transfer and migration process of the photogenerated charge carriers in plasmonic metal/semiconductor heterostructures not only affects their photocatalytic performance but also triggers some captivating phenomena. Here, a reversible photochromic behavior is observed on the Au/CdS heterostructures when they are investigated as photocatalysts for hydrogen production. The photochromism takes place upon excitation of the CdS component, in which the photogenerated holes are rapidly consumed by ethanol, while the electrons are transferred and stored on the Au cores, resulting in the blue shift of their localized surface plasmon resonance. The colloidal solution can restore its initial color after pumping with air, and the photochromic behavior can be cycled five times without obvious degradation. The finding represents great progress toward the photochromic mechanism of metal/semiconductor heterostructures and also reveals the importance of understanding the dynamic process of the photogenerated charge carriers in these heterostructures.

Improved photocatalytic performance of cobalt doped ZnS decorated with graphene nanostructures under ultraviolet and visible light for efficient hydrogen production.

Highly dispersed Cobalt doped ZnS nanostructures were successfully fabricated on the surfaces of graphene sheets via a simple hydrothermal method. X-ray diffraction (XRD), X-ray photocurrent spectroscopy (XPS), Raman spectroscopy (RS), Fourier transform infrared spectroscopy (FTIR) and Scanning electron microscopy (SEM) were utilized to analyze the structural characteristics of the cobalt doped ZnS decorated with graphene Co x Zn 1 - x S rGO nanostructures (NSs). UV-visible optical absorption (UV-vis) studies were conducted to investigate their optical properties. In laboratory studies utilizing water and visible light, the photocatalytic activity of Co x Zn 1 - x S rGO NSs at (x = 0, 1, 2, 4 and 6 atm.%) were evaluated. Graphite Oxide (GO) was successfully transformed into sheets of graphene and Co x Zn 1 - x S rGO NSs possessed a crystalline structure according to the findings of XRD, RS and FTIR analysis. SEM investigation showed graphene sheets enhanced with ZnS NSs possessed cuboidal, spheroidal form of structure and displayed a paper like appearance. UV-vis confirmed a noticeable rapid increase in transmittance along the UV wavelength area and confirmed a highly transparent NSs in the wavelength range of (180-800 nm). Calculations using density functional theory (DFT) revealed that the Co NSs have more negative conduction bands than ZnS, allowing for effective electron transfer from cobalt to ZnS and exhibiting a band gap decrease as Co content increased. The Co 0.04 Zn 0.96 S rGO NSs sample had the highest photocatalytic activity, measured at 7648.9 µ mol h - 1 . A combination of improved dispersion properties, greater surface area, increased absorption and enhanced transfer of photogenerated electrons, Co x Zn 1 - x S rGO NSs increased the photocatalytic hydrogen generation activity.