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Photoelectrochemical (PEC) technology in marine engineering holds significant importance due to its potential to address various challenges in the marine environment. Currently, PEC-type applications in marine engineering offer numerous benefits, including sustainable energy generation, water desalination and treatment, photodetection, and communication. Finding novel efficient photoresponse semiconductors is of great significance for the development of PEC-type techniques in the marine space. Bismuth-based semiconductor materials possess suitable and tunable bandgap structures, high carrier mobility, low toxicity, and strong oxidation capacity, which gives them great potential for PEC-type applications in marine engineering. In this paper, the structure and properties of bismuth binary and mixed-anion semiconductors have been reviewed. Meanwhile, the recent progress and synthetic approaches were discussed from the point of view of the application prospects. Finally, the issues and challenges of bismuth binary and mixed-anion semiconductors in PEC-type photodetection and hydrogen generation are analyzed. Thus, this perspective will not only stimulate the further investigation and application of bismuth binary and mixed-anion semiconductors in marine engineering but also help related practitioners understand the recent progress and potential applications of bismuth binary and mixed-anion compounds. [ABSTRACT FROM AUTHOR]

Semiconductor photocatalysis is a potential solution to meet energy needs with green and inexhaustible solar energy. However, designing efficient and stable photocatalysts is a challenging task due to the limited ability to effectively separate electrons and holes. In this paper, by using a straightforward ethanol dispersion technique, we were able to combine ultrathin layered Cu-TCPP MOFs with g-C3N4 nanosheets, resulting in the creation of an extremely effective nano-composite photocatalyst with exceptional UV-vis activity. CT/CN heterojunctions displayed remarkable photocatalytic efficacy for the production of H2, with 3CT/CN showcasing a five-fold enhancement in photoactivity as compared to the unadorned g-C3N4. Based on the results of photoluminescence spectroscopy, electrochemical impedance spectroscopy, and electrochemical reduction, the considerably improved charge transfer and separation, together with the possible catalytic capability of uniformly distributed metal nodes in Cu-TCPP, are believed to be the underlying reason for the observed exceptional photoactivity. After thorough analysis, a potential process for charge transfer and segregation between g-C3N4 and Cu-TCPP has been suggested. [ABSTRACT FROM AUTHOR]

The activation capacity of molecular oxygen is an important indicator to evaluate the photocatalytic efficiency of photocatalysts. In this paper, WS2 nanosheet was deposited on hyper-crosslinked CTF-1-G (obtained by molecular expansion from covalent triazine framework CTF-1) to form a C-GW heterojunction, which promoted the photodegradation of pollutants and the activation of molecular oxygen. This novel C-GW heterojunction exhibited excellent degradation property for organic pollutants (tetracycline (TC), rhodamine B (RhB)) and activating molecular oxygen under visible light irradiation. Among them, C-GW15 could degrade 98% of 20 ppm TC in 60 min and 99% of 30 ppm RhB in 30 min, and it had the highest hydrogen generation rate and hydrogen production amount in 4 hours, which were 8.74 mmol h−1 g−1 and 34.94 mmol g−1, respectively. Meanwhile, C-GW15 had the strongest 3,3′,5,5′-tetramethylbenzidine oxidation capacity and could generate 1.83 μmol of ˙O2− in 60 min and the production of H2O2 was 20.8 μmol L−1 in 40 min. The results of this study clearly indicated that the combination of WS2 and CTF-1-G can enhance the visible light absorption capacity and photogenerated carrier separation efficiency, thus promoting the photocatalytic performance. Finally, a Z-type photocatalytic mechanism was proposed based on radical capture, molecular oxygen activation experiments and electron spin resonance analysis. These findings will extend the fundamental understanding of the Z-type photocatalytic mechanism and provide new opportunities for the rational design of CTF heterojunctions for the treatment of environmental pollution and clean energy conversion. [ABSTRACT FROM AUTHOR]

The simultaneous production of hydrogen and biomass-based chemicals from biomass-derived feedstock aqueous solutions via photocatalysis is appealing because no additional sacrificial agent is needed. However, limited success has been achieved. This paper reports efficient nori-shaped carbon nitride-based photocatalysts with potassium/oxygen co-doping and cyano group introduction for efficient conversion of biomass-derived monosaccharides to produce lactic acid and hydrogen simultaneously. The obtained photocatalyst has an adjustable bandgap, fast migration/separation rate of photo-generated carriers and displays excellent photocatalytic performance with respect to xylose conversion (∼95.0%), lactic acid selectivity (90.5%) and hydrogen generation (∼33 380 μmol g−1 h−1) in the presence of visible light. The h+, ˙OH, ˙O2− and 1O2 drive xylose conversion and lactic acid production. For biomass-derived pentoses and hexoses, the reaction system also exhibits excellent photocatalytic activity of lactic acid selectivity and hydrogen generation; the reported photocatalyst has excellent reusability. This paper provides a new perspective for hydrogen generation and biorefineries via a photocatalyst. [ABSTRACT FROM AUTHOR]

In this paper, NiCo2S4 was coated on the surface of WS2 of a 1T/2H mixed phase by a two-step hydrothermal method to form an in situ core–shell structure. The unique S-scheme heterojunction of the NiCo2S4@WS2 core–shell composite photocatalyst improved the easy recombination of carriers caused by the narrow band gap of NiCo2S4 and WS2, and improved the photocatalytic hydrogen production performance. The loading ratio of NiCo2S4@WS2, the addition of Eosin Y, and the pH value of TEOA were optimized. Under the optimal conditions, the hydrogen production rate reached 5.814 mmol g−1 h−1, which is about 8.55 times and 3.35 times the hydrogen evolution rates of NiCo2S4 and WS2, respectively. The composite catalyst exhibits excellent charge separation efficiency in photoelectrochemistry, PL and BET tests, carrier transport rate and large specific surface area that can provide more active sites, which are the main factors for the improvement of the hydrogen evolution performance. This paper demonstrates new design strategies to drive efficient photocatalytic hydrogen production by building in situ core–shell structures and optimizing the carrier transport paths, which will yield new insights. [ABSTRACT FROM AUTHOR]

Cocatalysts are usually applied in the photocatalytic water splitting process to accelerate the kinetics of the hydrogen evolution reaction (HER). Specifically, the transition metal nitride (Mo2N) featuring a unique local surface plasmon resonance (LSPR) effect has exhibited great potential to function as a HER cocatalyst. However, the low metallicity of Mo2N hampers its ability to improve charge separation. To address this issue, transition metal atom doping (Co and Cu) engineering was used to modulate the electronic structure of Mo2N nanosheets to achieve a higher electrical conductivity and a lower hydrogen adsorption free energy (‖ΔGH*‖), thereby favoring the HER kinetics. Density functional theory (DFT) calculations and experimental results showed that Co-doping and Cu-doping mainly take place at Mo sites in the crystal structure of Mo2N to form stable structures of Co doped Mo2N (Co–Mo2N) and Cu doped Mo2N (Cu–Mo2N). Compared with pristine Mo2N, both Cu–Mo2N and Co–Mo2N demonstrated a much improved cocatalytic effect over g-C3N4 in promoting charge separation, accelerating HER kinetics and enhancing light absorption. The Co–Mo2N with the highest conductivity and lowest ‖ΔGH*‖ illustrated the best cocatalytic effect, and the H2 production performance (367.8 μmol g−1 h−1) of Co–Mo2N/g-C3N4 achieved was 10 and 5 times higher than those of Mo2N/g-C3N4 and Cu–Mo2N/g-C3N4. This paper provides significant guidance in the design and development of efficient cocatalysts for the HER application. [ABSTRACT FROM AUTHOR]

Compared with the noble metal Pt, the non-noble metal Cu as a cocatalyst exhibits a low hydrogen-evolution activity owing to its weak Cu–H bond (11 kcal mol−1), which inhibits hydrogen adsorption on Cu atoms for the hydrogen-evolution reaction of photocatalysts. Considering that the introduction of Ni with a strong Ni–H bond into Cu is beneficial for strengthening the H-adsorption ability of Cu, in this paper, the low-cost transition-metal Ni was directly introduced into Cu to form CuNi alloy nanodots as photocatalytic cocatalysts to enhance the hydrogen-evolution rate of TiO2. The CuNi alloy nanodots (2–3 nm) were photodeposited on the surface of a reduced graphene oxide (rGO)-modified TiO2 photocatalyst to generate CuNi-rGO/TiO2 by the pre-adsorption of Cu2+ and Ni2+ ions on graphene oxide (GO). Photocatalytic hydrogen-production data manifested that the CuNi-rGO/TiO2 photocatalyst achieved the highest hydrogen-production rate (10 411 μmol h−1 g−1), which was 53.7, 38.7, 1.8, and 2.2 times higher than that of pure TiO2, rGO/TiO2, Cu-rGO/TiO2, and Ni-rGO/TiO2, respectively. Density-functional-theory (DFT) calculations and mechanistic investigation showed that the introduction of Ni into Cu to form CuNi alloy nanodots improved the H-adsorption ability of Cu and optimized the H-adsorption free energy close to zero (0.046 eV) for boosting the hydrogen production rate of TiO2. This research presents a promising design of bimetallic alloy structures as H2-production cocatalysts for efficient photocatalysts. [ABSTRACT FROM AUTHOR]

Element doping and construction of heterojunction composites are the most common ways to enhance g-C3N4, which are very attractive in achieving high photocatalytic activity. In this study, 2D nanosheet structured BCN was obtained by doping B atoms with graphite carbon nitride. Subsequently, Ti MOFs were loaded on BCN to obtain a Z-scheme heterojunction composite TBCN through calcination. Under simulated sunlight, the photocatalytic hydrogen production rate of the TBCN heterostructure was 1242 μmol h−1 g−1, which was 2.2 times higher than that of BCN and 9.34 times higher than that of bulk graphite carbon nitride (GCN). Experimental results showed that the construction of a Z-scheme heterojunction composite (TBCN) could effectively adjust the material band gap position, expand the light absorption range, enhance electron transfer and inhibit electron–hole recombination, which are crucial for efficient photocatalysis. This study not only provides a strategy for constructing heterojunction composites in the field of g-C3N4 photocatalytic hydrogen evolution, but also deeply analyzes the electron migration direction and the reasons for enhancing carrier separation in the Z-type heterojunction scheme, thus providing potential guidance for future research. [ABSTRACT FROM AUTHOR]

Exploring efficient non-noble metal catalysts for the hydrogen evolution reaction (HER) will contribute to the development of clean and green energy technologies. Herein, we adopted a "waste utilization" strategy by using readily available and inexpensive coconut shell waste as a carbon source to synthesize carbon materials anchored with a Cu7Co alloy (Cu7Co/C) as a potential electrocatalyst for the hydrogen evolution reaction (HER). Utilizing a combination of hydrothermal and pyrolysis methods, the synthesized Cu7Co/C catalyst showcases superior HER electrocatalytic performance in alkaline solutions, with an overpotential of 134 mV at 10 mA cm−2 and a Tafel slope of 94 mV dec−1. The alloying of Cu and Co within Cu7Co/C markedly improves charge transfer capabilities, enhancing HER electrocatalysis. This research underscores the exceptional catalytic performance and stability of Cu7Co/C nanocomposites in alkaline media for the HER, attributed to a synergistic effect between the carbon derived from coconut shells and the bimetallic Cu7Co alloy. [ABSTRACT FROM AUTHOR]

NaBH4 is an attractive candidate for closed-loop hydrogen generation in small practical applications owing to its ambient condition hydrogen release mechanism, non-toxic byproduct, ability to regenerate, and stability at ambient conditions. The hydrolysis of NaBH4 requires a catalyst to accelerate the hydrogen generation process and cobalt oxide is one such promising catalyst in this reaction. The surface species and crystalline phases of cobalt oxide catalysts play an important role in determining the hydrogen generation rate and overall hydrolysis process. In this study, cobalt oxide nanoparticles are synthesized by a thermal plasma route. The two crystalline phases, namely c-CoO and Co3O4, are tuned using thermal plasma operating conditions. The catalysts so obtained have been thoroughly characterized using analytical techniques like XRD, XPS, HR-TEM, etc. Furthermore, the catalyst was used for hydrogen production in the hydrolysis process of NaBH4. The ex situ X-ray photoelectron spectra recorded at different stages of the hydrolysis process have been extensively used to understand surface modifications occurring at the surface of the catalyst. The Co+3/Co+2 ratio and attachment of other species during hydrolysis analyzed using XPS are correlated with the overall hydrolysis reaction before and after catalysis. It was concluded that the presence of the c-CoO (i.e. initial Co+2 species presence) phase brings stability to hydrogen production in that cycle. [ABSTRACT FROM AUTHOR]

Electrocatalytic hydrogen generation in alkaline medium has become widely used in a variety of sectors. However, the possibility for additional performance improvement is hampered by slow kinetics. Because of this restriction, careful control over processes such as water dissociation, hydroxyl desorption and hydrogen recombination is required. Covalent organic frameworks (COFs) based on porphyrin and polyoxometalates (POMs) show encouraging electrocatalytic performance, offering a viable route for effective and sustainable hydrogen generation. Their specific architectures lead to increased electrocatalytic activity, which makes them excellent choices for developing water electrolysis as a clean energy conversion method in the alkaline medium. In this regard, TTris@ZnPor and Lindqvist POM were coordinated to create a new eco-friendly and highly active covalent organic framework (TP@VL-COF). In order to describe TP@VL-COF, extensive structural and morphological investigations were carried out through FTIR, 1H NMR, elemental analysis, SEM, fluorescence, UV-visible, PXRD, CV, N2-adsorption isotherm, TGA and DSC analyses. In an alkaline medium, the electrocatalytic capability of 20%C/Pt, TTris@ZnPor, Lindqvist POM and TP@VL-COF was explored and compared for the hydrogen evolution reaction (HER). The TP@VL-COF showed the best catalytic efficiency for HER in an alkaline electrolyte, requiring just a 75 mV overpotential to drive 10 mA cm−2 and outperforming 20%C/Pt, TTris@ZnPor, Lindqvist POM and other reported catalysts. The Tafel slope value also indicates faster kinetics for TP@VL-COF (114 mV dec−1) than for 20%C/Pt (182 mV dec−1) TTris@ZnPor (116 mV dec−1) and Lindqvist POM (125 mV dec−1). [ABSTRACT FROM AUTHOR]

In this work, CoV-LDH/ZnIn2S4 (CoV-LDH/ZIS) nanocomposites were synthesized through a self-assembly process in order to investigate the influence of CoV-LDH addition on the rate of hydrogen production. XRD and TEM measurements confirmed the effective preparation of CoV-LDH/ZIS nanocomposites. Among all the nanocomposite photocatalysts, 2.0%-CoV-LDH/ZIS showed the best photocatalytic performance with a hydrogen production rate of 1397.3 μmol g−1 h−1, approximately 2.2 times that of pure ZnIn2S4 (ZIS). The X-ray photoelectron spectroscopy (XPS) measurement indicated that there is a strong interfacial interaction between ZIS and CoV-LDH, indicating that more than simple mechanical mixing had occurred. The steady-state fluorescence spectroscopy (PL) and time-resolved photoluminescence (TRPL) spectroscopy results showed that the electron and hole recombination in CoV-LDH/ZIS is significantly reduced and that efficient interface charge transfer and separation are achieved. This work sheds light on the interfacial electron transfer between two semiconductor materials, which promotes the separation of photogenerated carriers and thus enhances photocatalytic hydrogen production activity. [ABSTRACT FROM AUTHOR]

In this paper, a novel pristine carbon nitride (np-CN) with hollow capsule-like morphology was facilely prepared by the thermal polymerization of melamine and cyanuric chloride at 550 1C in air for 4 h. Then, modified carbon nitride (CN-P4mg) micro-flakes with zigzag edges were synthesized by the copolymerization of melamine, cyanuric chloride, and triaminotriphenylamine with a mass fraction of 0.13%. Analysis of the microstructure, surface state, porosity, and optoelectronic properties of the two samples indicates that CN-P4mg has a larger specific surface area and a lower bandgap than np-CN. Under visible light, CN-P4mg displays enhanced photocatalytic performance for the generation of hydrogen compared to that of np-CN and bulk graphite carbon nitride (g-C3N4). The photocatalytic hydrogen evolution rate of CN-P4mg reaches 16897.3 mmol g-1 h-1, which is 1.84 times that of np-CN and 72 times that of bulk g-C3N4. The experimental results confirm that the addition of triaminotriphenylamine provides a modified design for developing metal-free carbon nitride derivatives and a new route to study efficient photocatalytic materials. [ABSTRACT FROM AUTHOR]

Finding efficient photocatalysts is the key to achieving sustainable hydrogen production. In this work, a rational design of Cd2+-doped Zn3In2S6 (ZIS) and a heterojunction structure with g-C3N4 (GCN) was carried out to form a GCN/Cd/ZIS composite. The synergistic effect of Cd2+ doping and heterojunction construction in the photocatalytic hydrogen production process was probed. The results showed that doping Cd2+ modified the bandgap structure of ZIS and improved the photocatalytic activity. The heterojunction construction between Cd/ZIS and GCN also effectively promoted the separation and migration of photogenerated carriers, which significantly improved the hydrogen production performance of the GCN/Cd/ZIS composite. The hydrogen production rate of 15% Cd/ZIS and 5% GCN/Cd/ZIS was 2.45 mmol g−1 h−1, 3.34 mmol g−1 h−1, which was 4.3 and 5.9 times higher than that of ZIS (0.57 mmol g−1 h−1), respectively. This study provides strong evidence that doping and heterojunction construction can synergistically improve photocatalytic activity. [ABSTRACT FROM AUTHOR]

Hydrazine borane (HB) has been considered to be an excellent medium for hydrogen storage, but the development of efficient catalysts for controllable and complete hydrolytic dehydrogenation of HB remains a severe challenge. In this study, a novel catalyst consisting of Ni0.6Pt0.4 nanoparticles supported on phosphorus-doped reduced graphene oxide (P-rGO) is readily obtained via a simple co-reduction method and serves as a highly efficient and stable catalyst toward the complete hydrolytic dehydrogenation of HB. Compared with Ni0.6Pt0.4/rGO, the as-prepared Ni0.6Pt0.4/P-rGO catalyst exhibits much higher catalytic activity for HB dehydrogenation, providing a total turnover frequency (TOF) value of 2419.4 h−1 at 323 K, which surpasses that of the majority of reported catalysts. Meanwhile, it also exhibits lower activation energy (Ea) and better recycle stability. The reason for the outstanding catalytic performance of Ni0.6Pt0.4/P-rGO could be attributed to the combined influence of small particle sizes, the enhanced synergistic effects of NiPt nanoparticles and the P-rGO substrate, the electronic interaction between Ni and Pt, and the NaOH promotion effect. This work provides an innovative approach to construct highly efficient and robust catalyst systems using simple and controllable methods. [ABSTRACT FROM AUTHOR]

Developing highly active and stable non-noble-metal cocatalyst-decorated semiconductors is desirable for the practical application of photocatalysis, which remains an open question. Herein, we report transition-metal nitride (Ni3FeN) loaded cadmium sulfide (CdS) nanorods prepared through a simple hydrothermal method and surface treatment with NH3. The as-prepared photocatalyst Ni3FeN (3 wt%)/CdS showed a hydrogen evolution rate of 4.6 mmol g−1 h−1, which was 23.8 and 6.8 fold higher than those of CdS and Pt (1 wt%)/CdS, respectively. The Ni3FeN/CdS sample exhibited remarkable stability for seven consecutive cycles of photocatalytic tests lasting 21 hours. It was confirmed through Kelvin probe measurements that a Schottky junction between Ni3FeN and CdS gave rise to the inhibited recombination of photogenerated carriers, which benefited the photocatalytic HER performance. [ABSTRACT FROM AUTHOR]

This study developed an efficient photocatalyst for hydrogen production, consisting of CdS nanorods and the CoTPPBr4 co-catalyst. The synthesized photocatalyst was characterized using a suite of techniques including X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), photoluminescence (PL) spectroscopy, and ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS). Additionally, transient photocurrent response and electrochemical impedance spectroscopy (EIS) were carried out to further probe the material's properties. Our findings demonstrate that the CoTPPBr4 co-catalyst significantly enhances the photocatalytic H2 evolution efficiency under visible light irradiation. Notably, among the tested photocatalysts, a 12.5% CoTPPBr4/CdS composite exhibited the most superior photocatalytic performance, achieving a hydrogen production rate of 41.3 mmol g−1 h−1, which is 4.1 times higher than that of pristine CdS. The introduction of CoTPPBr4 effectively facilitates charge transfer within CdS, enhances the separation efficiency of light-induced electron–hole pairs, and boosts the surface H2-evolution kinetics. This research not only introduces a promising photocatalyst for visible light-driven hydrogen production but also provides a way for the development of highly efficient and stable CdS-based hybrid semiconductor nanocomposites suitable for diverse photocatalytic applications. [ABSTRACT FROM AUTHOR]

The development of high-performance and highly stable electrocatalysts is crucial and challenging for the hydrogen evolution reaction (HER). MOFs complexed with SnS2 can form complexes with inserted structures, and their large specific surface area and numerous pores favor mass transfer, exposing the S active sites to more SnS2, improving the utilisation of the active sites and enhancing the catalytic activity for the HER. Structural collapse can be hindered to improve the stability of the HER composites. Herein, six different kinds of SnS2 were synthesized by a hydrothermal method under discrete conditions, and SI8-SnS2 was screened out to have optimal morphology and electrocatalytic performance. Two innovative SnS2@Ni-MOF and SnS2@HKUST-1 as efficient electrocatalysts were synthesized by a facile grinding method for hydrogen generation. SnS2@Ni-MOF and SnS2@HKUST-1 catalysts showed lower overpotentials of 117 mV and 142 mV at 10 mA cm−2 (η10) and smaller Tafel slopes (58 mV dec−1 and 93 mV dec−1) than six different kinds of SnS2, Ni-MOF and HKUST-1 in 0.5 M H2SO4. Meanwhile, the Cdl values for SnS2@Ni-MOF and SnS2@HKUST-1 were estimated to be 11.5 mF cm−2 and 8.0 mF cm−2, and the stabilities of SnS2, Ni-MOF, HKUST-1, SnS2@Ni-MOF, and SnS2@HKUST-1 were tested at a current density of 10 mA cm−2. The current densities of SnS2@Ni-MOF and SnS2@HKUST-1 were stable over 8 h compared to the pure samples, and SEM, XPS tests were run after the HER test, indicating that the materials have excellent electrocatalytic stability. The syntheses of SnS2@Ni-MOF and SnS2@HKUST-1 enhance their intrinsic catalytic activity, and the porous structure promotes mass transfer efficiency, thereby improving the HER performance, which will guide the development of new and promising electrocatalysts for HER. [ABSTRACT FROM AUTHOR]

Designing cost-effective catalysts with the structural features and necessary functionality to drive ammonia borane hydrolysis for hydrogen generation remains a challenge. In this work, a close heterojunction of Fe3O4--Ni2P uniformly embedded in amorphous carbon material (Fe3O4--Ni2P@C) has been prepared via surface phosphorization. The catalyst displays superior activity with a turnover frequency (TOF) of 92.8 min-1 and favorable durability for ammonia borane hydrolysis, making it superior to most reported nickel-based catalysts. The theoretical studies show a high electron density on the Fe3O4--Ni2P heterojunction. Combining the theoretical and experimental results, the dual active sites at the heterojunction are beneficial to the adsorption of reactant molecules and the reduction of the reaction barrier. This strategy of constructing an appropriate heterojunction to maximize synergistic effects may open a new avenue for non-precious metal catalysis. [ABSTRACT FROM AUTHOR]

The designing of efficient electrocatalysts for hydrogen generation is essential for the practical application of water-splitting devices. With numerous electrochemical advantages, transition metal sulphides are regarded as the most promising candidates for catalysing the hydrogen evolution reaction (HER) in acidic media. In the present study, Ru-doped cobalt sulphide nanosheets, termed Co9S8/Ru@t (t = 24 h, 48 h, and 72 h), were obtained by varying the reaction time from 24 h to 72 h from a RuCo-PBA precursor. The role of the time period for the synthesis of Co9S8/Ru@48h is vital in increasing the number of electroactive sites and optimising the hydrogen adsorption–desorption phenomena leading to an increment in the HER activity. The electrochemical outcomes demonstrate that the optimized Co9S8/Ru@48h requires a low overpotential of just 94 mV to produce 10 mA cm−2 current density, and also exhibits a lower Tafel slope value of 84 mV dec−1 defining its faster reaction kinetics. The as-synthesized Co9S8/Ru@48h was stable for up to 20 h of constant electrolysis signifying its outstanding durability. The optimized synthetic approach and impressive electrochemical results make Co9S8/Ru@48h a suitable alternative to noble-metal-based electrocatalysts for the HER. [ABSTRACT FROM AUTHOR]

Water-splitting coupled with the hydrazine oxidation reaction (HzOR) is a remarkably important strategy for H2 production, but remains a challenge. Herein, a Fe-doped Ni2P-Co2P-Zn3P2 heterogeneous electrocatalyst with a nanoneedle-assembled nanosphere structure and abundant defects was fabricated on Ni foam (Fe-NiCoZnP/NF). The introduction of Fe can tune the electron structure of NiCoZnP/NF, leading to a modulation of the d-band center towards the Fermi level, hence optimizing the free energy of hydrogen (ΔGH*) and dehydrogenation behavior of hydrazine, and thereby realizing splendid HER and HzOR activities. The fabricated Fe-NiCoZnP/NF catalyst displays outstanding HER and HzOR activity and durability, with potentials of 121 and 13 mV vs. RHE to drive 1000 mA cm-2 and Tafel slopes of 31.2 and 11.9 mV dec-1, respectively, and a long durability of 120 h to achieve 100 mA cm-2. Impressively, overall water-hydrazine electrolysis employing Fe-NiCoZnP/NF as the anodic and cathodic electrodes only requires low voltages of 1.92 and 2.67 V to achieve 100 and 1000 mA cm-2, respectively, with a high stability for 120 h operation time during overall hydrazine splitting (OHzS). This work offers a justification for the design of high-efficiency bifunctional catalysts, and promotes energy-saving industry-level hydrogen generation. [ABSTRACT FROM AUTHOR]

Metal halide perovskites, such as iodine methylamine lead (MAPbI3), have received extensive attention in the field of photocatalytic decomposition of HI for hydrogen evolution, due to their excellent photoelectric properties. In this paper, a new MAPbI3-based composite, MoC/MAPbI3, was synthesized. The results show that 15 wt% MoC/MAPbI3 has the best hydrogen production performance (38.4 μmol h−1), which is approximately 24-times that of pure MAPbI3 (1.61 μmol h−1). With the extension of the catalytic time, the hydrogen production rate of MoC/MAPbI3 reached 165.3 μmol h−1 after 16 h due to the effective separation and transfer of charge carriers between MoC and MAPbI3, showing excellent hydrogen evolution rate performance under visible light. In addition, the cycling stability of MoC/MAPbI3 did not decrease in multiple 4 h cycle tests. This study used the non-precious metal promoter MoC to modify MAPbI3, and provides a new idea for the synthesis of efficient MAPbI3-based composite catalysts. [ABSTRACT FROM AUTHOR]

Strontium titanate (SrTiO3) with a perovskite structure is widely applied to hydrogen production by photolysis water splitting. However, the existing preparation techniques cannot make uniform high-purity strontium titanate without causing pollution under simple conditions. Therefore, a preparation technique that can mass-produce uniform high-purity and environmentally friendly strontium titanate at low temperatures is particularly important. In this paper, a sol–gel method is used to coat strontium carbonate with a TiO2 precursor. The core–shell structure formed by this structure increases the contact area between the reactants, which is beneficial to the diffusion between elements and promotes the kinetic process of the reaction, and pure-phase nano-strontium titanate can be made at low temperatures. The microstructure of the samples before and after calcination at 800 °C is analyzed by FT-IR. The chemical composition and the valence state of the calcined samples at 800 °C are analyzed by XPS. The structure of the samples at different heat treatment temperatures is observed and the structure of the samples at the same heat treatment temperatures with different heat treatment times is observed by XRD and transmission electron microscopy. TGA-DSC is used to monitor the changes in mass and heat during the reaction. The transformation mechanism and nucleation process of the material are analyzed from the perspective of thermodynamics and kinetics. In addition, the UV-visible absorption spectrum is used to calculate the forbidden band width. Finally, the activity of the hydrogen produced by water-splitting the sample under different heat treatment conditions is measured. The results showed that strontium titanate was produced at the contact interface at 600 °C, and the pure phase of strontium titanate was produced at 800 °C with a size of 34 nm. The reaction process conforms to the nucleation-growth model and the grain grows with the driving force of grain boundary and the temperature increase. The forbidden band width of the pure-phase strontium titanate produced after calcination at 800 °C is 3.173 eV, with the best photocatalytic performance, and its hydrogen production rate is 2.40 μmol g−1 mol−1. This work provides a new preparation process for nano-strontium titanate and may be highly applied to hydrogen production by photolysis water splitting. [ABSTRACT FROM AUTHOR]

In the photocatalytic processes of ferroelectric semiconductor materials, how to induce a depolarized electric field (Edp) by polarization to reduce the electron–hole recombination rate is still a big problem. Here, the ABO3-type K0.5Na0.5NbO3 (KNN) material is modified by Nd and Ni elements at A/B sites to narrow the band gap and maintain the room-temperature ferroelectric behavior. The 0.96KNN–0.04NdNiO3 sample shows the narrowed band gap (∼2.75 eV) and high residual polarization value (∼11.56 μC cm−2). After high-field poling, the hydrogen production rate of the sample in the full spectrum reaches 926.28 μmol g−1 h−1, indicating an increase of approximately 5 times compared to the 170.45 μmol g−1 h−1 of the unpoled sample. The improved performance of photocatalytic hydrogen production mainly results from the reduction of band gap and the formation of Edp after polarization. The change in the position of the top of the valence band after sample polarization reveals that high-field poling can improve charge transport efficiency by energy band bending. [ABSTRACT FROM AUTHOR]

Visible-light-driven hydrogen evolution from water represents a green and sustainable technology to convert solar energy into chemical energy. Covalent organic frameworks (COFs) are the most competitive platforms among the variety of photocatalysts. Herein, a novel benzotrifuran-based donor–acceptor material (COF-JLU42) was constructed using a Schiff base polycondensation reaction by introducing electron-rich benzotrifuran and deficient triazine moieties into the framework. The new COF features high crystallinity and permanent porosity with a large surface area and proves to be a photoactive semiconductor with efficient visible-light harvesting capacity. Importantly, COF-JLU42 exhibits a superior photocatalytic activity with a hydrogen evolution rate of over 40 000 μmol g−1 h−1 under visible-light illumination, which is 2.5 times higher than that of the isomorphic benzotrithiophene-based COFs under the same conditions. These findings suggest the huge application prospect of benzotrifuran-based framework materials as metal-free and solid photocatalysts in solar-energy conversion and storage. [ABSTRACT FROM AUTHOR]

Improving the separation efficiency of photo-generated electron–hole pair is a key issue in the field of photocatalytic hydrogen production. In this work, we successfully improved the efficiency of photo-generated carrier separation using the synergistic action of sulfur (S) vacancies and a Ni2P co-catalyst. Vs-Zn0.5Cd0.5S (Vs-ZCS) with S vacancies was designed and constructed, and Vs-ZCS/Ni2P photocatalysts were prepared with non-precious metal Ni2P as a co-catalyst. Among all the produced materials, Vs-ZCS/Ni2P-5% has a photocatalytic characteristic of 40.81 mmol g−1 h−1, which is 7.88, 3.08 and 3.75 times greater than those of ZCS (5.18 mmol g−1 h−1), Vs-ZCS (13.25 mmol g−1 h−1) and ZCS/Ni2P-5% (10.88 mmol g−1 h−1), respectively. The results of transient photo-current, electrochemical impedance spectroscopy, photoluminescence and time-resolved fluorescence show that the synergistic effect of S vacancies and Ni2P significantly promotes the separation and transfer efficiency of photo-generated carriers, as well as the photocatalytic hydrogen production reaction. Superoxide radicals and electrons are the active species for photocatalytic hydrogen generation, which is confirmed by active species capture tests and EPR. This study presents an innovative approach for developing photocatalysts with low cost and good catalytic performance. [ABSTRACT FROM AUTHOR]

At present, the rational design and facile synthesis of highly active and low-cost photocatalysts are still facing great challenges. Herein, a series of Zn0.5Cd0.5S/NiS (x mol%) composite photocatalysts have been synthesized via a simple and mild one-pot hydrothermal method. Compared with pure Zn0.5Cd0.5S, the NiS-loaded samples exhibit enhanced photocatalytic hydrogen generation performance, in which the Zn0.5Cd0.5S/NiS-5% sample has the highest H2 production rate of 10 855 ± 461 μmol h−1 g−1 with a quantum yield of 11.82% at 365 nm, which is almost 6.3 times higher than that of pristine Zn0.5Cd0.5S. The high activity of the Zn0.5Cd0.5S/NiS nanosheets may be attributed to their distinct nanostructure, including a short transfer distance of photoinduced charge carriers, a large number of unsaturated surface atoms, and a large surface area. Moreover, the added NiS nanoparticles served as an effective cocatalyst to promote photoinduced electron transfer and enhance the surface kinetics of H2 evolution. Our work provides a simple and effective route for the preparation of sulphur-based photocatalysts, which can significantly improve the efficiency of hydrogen production from water. [ABSTRACT FROM AUTHOR]

NiFe-LDH/g-C3N4 (LDH/CN) heterostructures with different amounts of NiFe-LDH (LDH) were prepared by a hydrothermal method and characterized using different experimental techniques. Their photocatalytic properties were investigated using the degradation of tetracycline hydrochloride (TC) and the production of hydrogen from water splitting. Experimental results showed that the hydrogen production rate (780.5 μmol g−1 h−1) was 2.29 times that of pristine CN, and the TC removal rate (76.3%) of 1.8LDH/CN was 3.71 times that of CN. According to the detailed study of the structural, optical, and photoelectrochemical properties, a type II charge transfer mechanism was proposed to explain the improved photocatalytic performance of LDH/CN. [ABSTRACT FROM AUTHOR]

Natural photosynthetic biosystems, with elaborate spatial structures, possess substantial specific surface areas and strong light-scattering abilities and provide a blueprint for the fabrication of photocatalysts for efficiently capturing and utilizing solar energy. However, mimicking sophisticated natural structures by a rational design is a great challenge. Herein, we report a facile and universal symbiosis hydrothermal synthesis strategy for obtaining biomimetic volvox-like double-core nested hollow materials. The nested hollow materials possessed the special notched "mother–twin" core–shell structure and the core numbers could be well controlled by adjusting the amount of precursor. The notched double-core hollow ZnO/CdS (mother–twin HZC) was facilely constructed by the direct chemical deposition of CdS nanosheets on the double-core hollow ZnO (mother–twin HZ). The notched complex spatial heterostructure possessed a multiple light-reflection capability (improving the utilization of solar energy), tight interfacial contact (favoring charge migration), and a high surface-to-volume ratio (providing sufficient active sites for H2 production). Both the Z-scheme ZnO/CdS heterostructures and the special nested hollow structure could synergistically enable achieving a remarkable hydrogen generation rate (up to 18.70 mmol g−1 h−1) under visible-light irradiation, exceeding that of the reported similar ZnO/CdS heterostructure without co-catalysts. [ABSTRACT FROM AUTHOR]

Developing novel catalysts with excellent photocatalytic hydrogen evolution activity is crucial for expediting current research on solar-chemical energy conversion. In the present study, unique Sn3O4/CdS composites were carefully designed and prepared using a facile hydrothermal method to achieve outstanding photocatalytic H2 production activity. Various techniques were employed to determine the crystalline structure, chemical composition, microstructure, and optical and electrochemical characteristics of the prepared samples. The experimental results indicate that zero-dimensional (0D) CdS quantum dots were tightly attached to the surface of three-dimensional (3D) Sn3O4 nanoflowers. Furthermore, enhanced light-absorbing capacity and accelerated electron–hole separation and transfer were achieved after incorporating CdS quantum dots into Sn3O4 nanoflowers. The generation rate of hydrogen using the optimal sample (Sn3O4/CdS QDs-2) was about 20.74 μmol g−1 h−1, which was 2.86 and 3.16 times those of pure Sn3O4 and CdS, respectively. In addition, the possible photocatalytic H2 production mechanism of Sn3O4/CdS nanocomposites was also revealed. This work is highly desirable to provide valuable inspiration for rational design and preparation of efficient photocatalysts for H2 evolution. [ABSTRACT FROM AUTHOR]

As a two-dimensional (2D) nanomaterial, bulk g-C3N4 (CNB) has a low specific surface area and weak electron transport ability, which limit its application in photocatalysis. In this paper, ultrathin porous g-C3N4 nanosheets (CNS) have been synthesized by thermal oxidation etching of CNB. Compared with CNB, CNS possess a larger surface area of 234.65 m2 g−1, good dispersity in water and a high electron transfer rate. As a co-catalyst, ultra-small Pt nanoparticles (NPs) with high dispersity are successfully loaded on the surface of CNS. It is found that changing the loading method of Pt NPs in the preparation step remarkably alters the efficiency for hydrogen production. The Pt/CNS-CR photocatalyst fabricated by the chemical reduction (CR) method shows a much higher efficiency for H2 evolution from water splitting, compared to the Pt/CNS-PR photocatalyst obtained by the loading of Pt NPs by the traditional photo-reduction (PR) method. When triethanolamine (TEOA) is used as a hole sacrificial agent, the hydrogen production rate of 2.0%-Pt/CNS-CR is 7862.5 μmol g−1 h−1, which is 6.92 times higher than that of 2.0%-Pt/CNS-PR (1136.8 μmol g−1 h−1). The valence states of the Pt element in the Pt/CNS-CR and Pt/CNS-PR nanocomposites have been analyzed by X-ray photoelectron spectroscopy, respectively. At the same time, the effects of the loading amount of Pt and different sacrificial reagents on the photocatalytic H2 generation activity have also been systematically investigated. [ABSTRACT FROM AUTHOR]

In the present work, a ternary composite MoS2/soluble g-C3N4/CdS was synthesized using a facile one-pot hydrothermal reaction and conventional reflux reaction method. The composition, morphology, and properties of the ternary composite were characterized. The photocatalytic performance of the ternary composite was evaluated for hydrogen generation under LED lamp irradiation (450 nm < λ < 465 nm) with lactic acid (LA) used as a sacrificial reagent. The results demonstrated that the maximum hydrogen production reached 4869.6 μmol under the optimal hydrogen production conditions, including a composition of 20% soluble g-C3N4, 9% MoS2, a solution pH of 1, and an irradiation time of 6 hours. The corresponding hydrogen production rate for the ternary composite was calculated to be 8116 μmol g−1 h−1. Furthermore, a possible electron transfer mechanism of the ternary composite system was briefly explored. The interaction and synergistic effects between MoS2, soluble g-C3N4, and CdS in the ternary composite likely facilitate efficient electron transfer, resulting in enhanced photocatalytic activity for hydrogen production. Mechanistic research showed that the electron transfer pathway represented either a double or single type II heterojunction photocatalytic system. [ABSTRACT FROM AUTHOR]

The development of non-noble metal catalysts that exhibit high performance in the dehydrogenation of ammonia borane has been considered a safe and efficient method for hydrogen generation. In this study, a series of CuxCoy alloy nanoparticles with different ratios were highly dispersed on a core–shell microsphere carrier, and the carrier was prepared using carbon spheres as a template. The catalytic activity for H2 from ammonia borane (NH3BH3, AB) hydrolysis was investigated by adjusting the ratio of Cu2+ to Co2+ doping in the catalyst. The Co1Cu1/C@Cu0.76Co2.24O4 core–shell heterostructure catalyst shows excellent catalytic activity with a high turnover frequency (TOF) value of 82.58 molH2 molcat−1 min−1 and a low activation energy (Ea) of 16.06 kJ mol−1. Detailed analysis indicates that the outstanding activity of AB for hydrolytic dehydrogenation could be attributed to the unique core–shell hetero-structures and high dispersion of the CuCo alloy nanoparticles. [ABSTRACT FROM AUTHOR]

Transition metal-based oxides have been reported as an important family of electrocatalysts for water splitting owing to their possible large-scale applications that are highly desirable for the hydrogen generation industry. Herein, we report a facile method for the preparation of phosphate-decorated NiFe oxides on nickel foam as efficient oxygen evolution reaction (OER) electrocatalysts for water oxidation. The OER electrocatalysts were developed through the pyrolysis of MIL(Fe) metal–organic frameworks (MOFs), which were modified with Ni and P species. It was found that the formation of NiO on the Fe2O3 surface (NiO@Fe2O3) can enrich electrocatalytic active sites for the OER. Meanwhile, the incorporation of P into NiO@Fe2O3 (Px-NiO@Fe2O3) creates abundant oxygen vacancies, which facilitates the surface charge transfer for OER electrocatalysis. Benefiting from the structure and composition advantages, P2.0-NiO@Fe2O3/NF exhibits the best performance for OER electrocatalysis among other prepared electrocatalysts, with an overpotential of 208 mV at the OER current density of 10 mA cm−2 and a small Tafel slope of 69.64 mV dec−1 in 1 M KOH solution. Additionally, P2.0-NiO@Fe2O3/NF shows an outstanding durability for the OER electrocatalysis, maintaining the OER current density above 20 mA cm−2 for more than 100 h. [ABSTRACT FROM AUTHOR]

Elemental doping is an effective and attractive method for improving the photocatalytic performance. Here we synthesized three types of O-doped carbon nitride nanofibers (ACN, CCN, and LCN) through a one-pot simple solvothermal process by using L -arginine, L -cysteine and L -lysine as O dopants into pristine carbon nitride nanofibers (CNF). The three O-doped samples exhibited enhanced light harvesting capacity and satisfactory O2 adsorption and activation ability, which is beneficial for the following H2O2 generation process. The photocatalytic H2O2 generation rates of the optimal ACN, CCN, and LCN samples are 156.9, 166.2 and 107.2 μmol g−1 h−1, which are higher than that of pristine CNF (72.3 μmol g−1 h−1). Especially, CCN shows an apparent quantum efficiency of 4.66% at 420 nm. The results of photocurrent measurements and photoluminescence spectra indicate that the charge carrier recombination was effectively inhibited in the O-doped samples. Our research provides an effective and environmentally friendly strategy to improve the H2O2 generation performance by using common compounds in human life. [ABSTRACT FROM AUTHOR]

The combustion of fossil fuels has brought about serious energy shortages and environmental pollution issues. This study involves the development of green and environment-friendly nonprecious metal photocatalysts with high hydrogen production performance. Hence, a series of CoxSy/Mn0.5Cd0.5S composites was prepared through a simple hydrothermal process. When the loading amount of amorphous CoxSy was 3 wt%, the CoxSy/Mn0.5Cd0.5S composite catalyst showed the best photocatalytic activity under visible light irradiation (λ > 420 nm), giving a hydrogen production rate of 5677.6 µmol g−1 h−1, which is 121.6 times that of pure CdS and 4.8 times that of Mn0.5Cd0.5S. Moreover, the 3 wt%-CoxSy/Mn0.5Cd0.5S catalyst exhibited good photostability. The experimental results demonstrate that the construction of the CoxSy/Mn0.5Cd0.5S heterojunction effectively facilitates the separation of charge carriers, resulting in an enhanced photocatalytic activity. [ABSTRACT FROM AUTHOR]

The hydrogen production rate of TiO2 photocatalytic water splitting is significantly influenced by various doped elements and experimental conditions (i.e., dopant/Ti mole ratio, calcination temperature, and calcination time). A more systematic approach is essential to effectively extract valuable knowledge from large amounts of complex and mismatched data. Herein, we demonstrate a regression fusion model for predicting the hydrogen production rate via a machine learning methodology. In this work, a database of TiO2 photocatalytic water splitting is constructed using simple descriptive features and the stacking method is used to integrate the fusion of LightGBM, XGBoost and random forest to improve the prediction ability of the machine learning model. Cross-validation is used to train the dataset to avoid the randomness of one-time assignments and improve the generalization ability of the model. The stacking model obtains the highest R-squared score and the lowest error. The impact of each factor on the hydrogen production rate is determined using the LightGBM and random forest models. Visualization of the decision tree is used to heuristically obtain high-yield hydrogen properties with an accuracy of 81.7%. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) have great potential for producing photoelectrocatalyzed hydrogen and degrading pollutants, owing to several factors such as high porosity and tunable semiconductor-like properties. Wide band gaps, which restrict their use to only UV light induced reactions, and low efficiencies for the separation of photogenerated charge carriers (electrons and holes) pose significant challenges to the widespread applications of MOFs. In this study, a hierarchical hollow Pt@H-UiO-66-NH2/CdS ternary catalyst was designed and synthesized. The immobilized CdS nanoparticles (NPs) in this catalyst endow the MOF H-UiO-66-NH2 with high visible light absorption ability and the Pt NPs serve as electron sinks to improve charge carrier separation. Furthermore, the hierarchical hollow structure of H-UiO-66-NH2 in the composite contributes to boosting light absorption and shortening the distance for charge transfer. As a proof of principle, Pt@H-UiO-66-NH2/CdS catalyzes methylene blue (MB) degradation with a high rate constant of 1.025 × 10−2 and hydrogen production with a rate of 12 810 μmol g−1 h−1, the latter of which is about 2.3, 11.7 and 173 times higher than those of Pt@UiO-66-NH2/CdS, H-UiO-66-NH2/CdS and Pt@H-UiO-66-NH2, respectively. [ABSTRACT FROM AUTHOR]

The development of an efficient noble-metal-free cocatalyst is the key to photocatalytic hydrogen production technology. In this study, hierarchical Co(OH)2 nanosheet array-graphene (GR) composite cocatalysts are developed. With Eosin Y (EY) as a photosensitizer, the optimal Co(OH)2-10%GR hybrid cocatalyst presents excellent photocatalytic activity with an H2 production rate of 17 539 μmol g−1 h−1, and the apparent quantum yield for hydrogen production can reach 12.8% at 520 nm, which remarkably surpasses that of pure Co(OH)2 and most similar hybrid cocatalyst systems. Experimental investigations demonstrate that the excellent photocatalytic activity of Co(OH)2-GR arises from its unique nanosheet array architecture, which can collaboratively expose rich active sites for photocatalytic hydrogen evolution and facilitate the migration and separation of photogenerated charge carriers. It is desired that this study would supply a meaningful direction for the rational optimization of the constitute and structure of cocatalysts to achieve efficient photocatalytic hydrogen generation. [ABSTRACT FROM AUTHOR]

Piezocatalytic hydrogen evolution has emerged as a promising field for the collection and utilization of mechanical energy, as well as for generating sustainable energy throughout the day. Hexagonal CdS, an established semiconductor photocatalyst, has been widely investigated for its ability to split water into H2. However, its piezocatalytic performance has received less attention, and the relationship between its structure and piezocatalytic activity remains unclear. In this study, we prepared 3D ultrathin CdS nanoflowers with high voltage electrical response and low impedance. In pure water, without the use of any cocatalyst, CdS exhibited a piezoelectric catalytic hydrogen production rate of 1.46 mmol h−1 g−1, which was three times higher than that of CdS nanospheres (0.46 mmol h−1 g−1). Furthermore, the value-added oxidation product H2O2 was produced during the process of piezoelectric catalysis. These findings provide new insights for the design of high-efficiency piezoelectric catalytic hydrogen production. [ABSTRACT FROM AUTHOR]

Biomass is widely acknowledged as a renewable and abundant substitute for fossil fuels that is considered CO2-neutral. Thermal process-based energy extraction without proper carbon capture and storage still dominates biomass utilization and inevitably results in CO2 emission. It is appealing to develop a greener biowaste utilization method. Recently, biomass-derived small molecules were reported to be electrochemically reformed into valuable chemicals in a green process under ambient conditions. However, the reforming of raw biomass is still challenging, owing to its rigid and chemically stable structure. Herein, direct electroreforming of sugarcane bagasse waste for cogeneration of green hydrogen and valuable chemicals is reported. Having suppressed oxygen evolution and thus avoided hydrogen-oxygen mixture formation, our electroreforming process could be directly driven by photovoltaic electricity, presenting a safe and low-carbon route to green hydrogen and chemicals from raw biomass. Additionally, life cycle assessment shows that the electroreforming upcycling process driven by photovoltaic electricity and waste heat affords the lowest global warming potential amongst various process configurations, including conventional waste management methods, promising for decarbonisation and sustainable development. [ABSTRACT FROM AUTHOR]

This paper reports the synthesis of bare TiO2 and various molar concentrations of ruthenium (Ru)-doped TiO2 nanoparticles by the precipitation method. The as-synthesized photocatalysts were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), ultraviolet-visible diffuse reflectance spectroscopy (UV-vis DRS), N2 adsorption/desorption techniques, X-ray photoelectron spectroscopy (XPS), energy dispersive spectroscopy (EDS), Raman spectroscopy, photoluminescence spectroscopy (PL), and electrochemical measurements. The results from the UV-vis spectroscopy clearly indicated a red-shift of the optical response toward the visible region owing to the reduced band gap energy, thus showing an enhancement of the absorption in the visible spectrum. The XRD study showed that the samples were crystallized with the photoactive anatase phase of TiO2. The microstructural study using Raman spectroscopy indicated that the Ru dopant occupied the substitutional sites in the TiO2 lattice. According to the Mott–Schottky analysis, the flat band potential of the Ru-doped TiO2 was shifted to the negative potential. The photocurrent, electrochemical impedance spectroscopy, and photoluminescence revealed a higher photogenerated charge-carriers separation efficiency of the doped sample. The photocatalytic activities of the bare TiO2 and (0.05–0.2 mol%) Ru-doped TiO2 nanoparticles were examined by studying the hydrogen production from water using methanol as a sacrificial reagent and Pt nanoparticles as a cocatalyst under light of λ≥ 320. The optimal iron content was determined to be 0.1 mol% and the corresponding hydrogen production rate was 3400 μmol h−1 in aqueous methanol, which is enhanced by more than 2 times compared to bare TiO2 (1500 μmol h−1) under the same reaction conditions. The higher activity for the doped materials was attributed to the presence of the Ru dopant to facilitate the visible-light-driven activity by introducing the electron donor/acceptor level of ruthenium and the mid-band energy level of defects between the conduction band minimum and valence band maximum of TiO2. [ABSTRACT FROM AUTHOR]

The exploitation of high-performance electrocatalysts to achieve the economic electrocatalytic hydrogen evolution reaction (HER) is significant in generating H2 fuel. Enhancing the activity of the carrier catalyst by modifying trace precious metals is one of the important strategies. Herein, a hybrid material is developed by incorporating trace Ru species into a bimetallic phosphide (NiCoP) matrix on nickel foam (NF), showing a superior catalytic activity for HER. The Ru-NiCoP/NF hybrid material has plenty of heterointerfaces, improved electronic interaction, and small interfacial charge transfer resistance, improving the reaction kinetics of the HER. Remarkable, the Ru-NiCoP/NF provides a low overpotential of 96 mV at the current density of 50 mA cm−2 and high stability in 1.0 M KOH solution presenting a promising potential for hydrogen production. In addition, the Ru-NiCoP/NF sample exhibits the highest TOF value of 0.54 s−1 at an overpotential of 100 mV, which outperforms the commercial Ru/C catalyst. This study offers a promising approach for the synthesis of other precious metal supported hybrid materials. [ABSTRACT FROM AUTHOR]

Photocatalytic splitting of water for hydrogen generation is a green and renewable solution for converting solar energy to chemical energy; thus, the development of high-performance and stable photocatalytic materials has emerged as a research hotspot recently. Herein, a heterostructure composite photocatalyst of octahedral CoO uniformly modified with novel nitrogen-doped MXene quantum dots (N-MQDs) is successfully designed using a typical solvothermal approach. The optimum photocatalytic hydrogen evolution efficiency of the prepared N-MQDs@CoO heterojunction composite is 82.54 μmol g−1 h−1 with visible light, which is 16.57 times higher compared to the pure CoO. A series of photoelectrochemical tests were further performed to elucidate the photocatalytic hydrogen evolution mechanism. The remarkable improvement of activity is primarily attributed to the synergistic interaction between the closely spaced interface contacts and energy level matching among high conductivity Ti3C2 MXene quantum dots with CoO octahedra, dramatically hastening the segregation and transfer of photo-generated carriers. This study provides new ideas for the construction of MXene quantum dot-based co-photocatalysts with highly efficient photocatalytic performance and stability toward solar energy conversion applications. [ABSTRACT FROM AUTHOR]

C/Ti3C2/g-C3N4 hollow microspheres (HM) were prepared by the template method to construct Ti3C2/g-C3N4 Schottky junctions on the spherical surface. The C/Ti3C2/g-C3N4 HM Schottky junctions presented excellent photocatalytic properties for producing hydrogen and decomposing organic pollutants simultaneously from wastewater without the addition of a sacrifice agent. The research revealed that the built-in electric field between g-C3N4 and Ti3C2 MXene could decrease the charge transfer resistance, leading to efficient photo charge separation, and the organic pollutant tetracycline (TC) could act as a sacrifice agent for splitting water. The H2 evolution rate of the CN-TCM-3 sample in deionized water with a sacrifice agent reached 105.4 μmol g−1 h−1, and the TC removal rate reached 100% within 120 min. The hydrogen production efficiency of CN-TCM-3 in the natural water of Slender West Lake without or with TC as a sacrifice agent was 2.3 μmol g−1 h−1 and 3.2 μmol g−1 h−1, respectively. The addition of TC improved the hydrogen production efficiency by 39%. This research indicated that the C/Ti3C2/g-C3N4 HM Schottky junctions could be a potential photocatalyst for producing hydrogen and decomposing organic pollutants in sewage simultaneously. [ABSTRACT FROM AUTHOR]

The host–guest chemistry of O,O′-diisopropyl fluorophosphate (DFP), a phosphonofluoridate G-series chemical warfare agent simulant, was investigated in the presence of a number of octanuclear cubic coordination cage hosts. The aim was to demonstrate cage-catalysed hydrolysis of DFP at near neutral pH: however, two octanuclear coordination cages, HPEG (containing water-solubilising PEG groups) and HW (containing water-solubilising hydroxymethyl groups), were actually found to increase the lifetime of DFP in aqueous buffer solution (pH 8.7). Crystallographic analysis of DFP with a structurally related host cage revealed that DFP binds to windows in the cage surface, not in the internal cavity. The phosphorus–fluorine bond is directed into the cavity rather than towards the external environment, with the cage/DFP association protecting DFP from hydrolysis. Initial studies with the chemical warfare agent (CWA) sarin (GB) with HPEG cage in a buffered solution also showed a drastically reduced rate of hydrolysis for sarin when bound in the host cage. The ability of these cages to inhibit hydrolysis of these P–F bond containing organophosphorus guests, by encapsulation, may have applications in forensic sample preservation and analysis. [ABSTRACT FROM AUTHOR]

Solar-driven photocatalytic hydrogen generation via splitting water requires an efficient visible light active photocatalyst. In this work, Ni cocatalysts on a TiO2 composite photocatalyst with different graphene oxide (GO) contents were prepared using a hydrothermal method and characterized by TEM, XRD, UV-vis, Raman and PL spectra. The results show that the synthesized TiO2/GO/Ni nanosheet composites have a large specific surface area and can provide a large number of active sites for a photocatalytic hydrogen production reaction. GO can broaden the optical absorption range of TiO2 and absorb more visible light, thus stimulating more photogenerated electron–hole pairs. At the same time, GO can collect electrons and promote the separation of photogenerated electron–hole pairs. Ni, as a cocatalyst, can be used as an active site for hydrogen ion adsorption, which is conducive to promoting the migration of photogenerated electrons in the system and prolonging the life of photogenerated electrons and holes, thus ensuring the high efficiency of the photocatalytic reaction. [ABSTRACT FROM AUTHOR]

Silicon (Si) is a commercially available semiconductor used for photoelectrochemical (PEC) hydrogen production, which has various advantages of earth-abundant element, non-toxicity, broad absorption of the solar spectrum, high saturation current and industrial applicability. However, it suffers from surface light reflection, short carrier-transport distance, slow charge transfer at the electrode–electrolyte interface, and poor stability in aqueous electrolytes, resulting in decreased photocurrent density and elevated overpotential. In this work, a surface-modified nanoporous Si photocathode, called black Si (b-Si), was fabricated with a large electrochemical surface area for loading of Co(dmgH)2(py)Cl catalyst. Under the illumination of simulated sunlight, the optimal b-Si/[Co] photocathode exhibited a high photocurrent density of −4.15 mA cm−2 (0 VRHE), a value 319 times that of the f-Si electrode under the same conditions. Moreover, the onset potential positively shifted to 0.31 VRHE and the driving force required for H2 production was significantly decreased. The enhanced water splitting was attributed to the rapid transfer of charge across the electrode–electrolyte interface and efficient HER reactivity via the [Co] molecular catalyst. The surface engineering of the nanoporous structure and the deposition of molecular catalyst on the Si electrode have provided insights into the construction of semiconductor/catalyst hybrid photoelectrodes, and were concluded to synchronously improve the charge transfer at the electrode/electrolyte interface, reduce the overpotential, and speed up the PEC water splitting. [ABSTRACT FROM AUTHOR]

ZnIn2S4 is considered one of most promising green catalysts for visible light driven photocatalytic H2 generation, but it suffers from relatively low photocatalytic performance. Here, we for the first time report the design and preparation of an efficient ZnIn2S4-based catalyst using porous ZnWO4 as cocatalyst (denoted ZIS/PZW). ZIS/PZW consists of flower-like microspheres composed of ZnIn2S4 nanosheets embedded with porous ZnWO4 nanoflakelets. The as-synthesized ZIS/PZW showed excellent photocatalytic performance for H2 generation with an optimal hydrogen production rate of 8.86 mmol g−1 h−1. Further investigation revealed that the porous ZnWO4 cocatalyst could lead to the formation of dense contact sites with ZnIn2S4 nanosheets, thus benefiting electron migration. The hydrogen generation rate was found to be 2.15 times higher than that when solid ZnWO4 nanoparticles acted as cocatalyst. Our work highlights the importance of finely designing cocatalysts and provides a new route for the further development of high-efficiency ZnIn2S4-based photocatalysts for H2 generation. [ABSTRACT FROM AUTHOR]