Bound-state electrons synergy over photochromic high-crystalline C_(3)N_(5) nanosheets in enhancing charge separation for photocatalytic H_(2) production

Solar-driven water splitting for photocatalytic hydrogen evolution is considered a highly promising and costeffective solution to achieve a stable renewable energy supply.However,the sluggish kinetics of electron-hole pairs’separation poses challenges in attaining satisfactory hydrogen production efficiency.Herein,we synthesized the exceptional performance of highly crystalline C_(3)N_(5)(HC–C_(3)N_(5))nanosheet as a photocatalyst,demonstrating a remarkable hydrogen evolution rate of 3.01 mmol h^(-1)g^(-1),which surpasses that of bulk C_(3)N_(5)(B–C_(3)N_(5))by a factor of 3.27.Experimental and theoretical analyses reveal that HC-C_(3)N_(5)nanosheets exhibit intriguing macroscopic photoinduced color changes,effectively broadening the absorption spectrum and significantly enhancing the generation of excitons.Besides,the cyano groups in HC-C_(3)N_(5)efficiently captures and converts photoexcited electrons into bound states,thereby prolonging their lifetimes and effectively separating electrons and holes into catalytically active regions.This research provides valuable insights into the establishment of bound electronic states for developing efficient photocatalysts.

Performance of a Combined Energy System Consisting of Solar Collector, Biogas Dry Reforming and Solid Oxide Fuel Cell: An Indian Case Study

An energy production system consisting of a solar collector, biogas dry reforming reactor and solid oxide fuel cell (SOFC) was assumed to be installed in Kolkata, India. This study aims to understand the impact of climate conditions on the performance of solar collectors with different lengths of parabolic trough solar collector (dx) and mass flow rate of heat transfer fluid (m). In addition, this study has evaluated the amount of H2 produced by biogas dry reforming (GH2), the amount of power generated by SOFC (PSOFC) and the maximum number of possible households (N) whose electricity demand could be met by the energy system proposed, considering the performance of solar collector with the different dx and m. As a result, the optimum dx was found to be 4 m. This study revealed that the temperature of heat transfer fluid (Tfb) decreased with the increase in m. Tfb in March, April and May was higher than that in other months, while Tfb from June to December was the lowest. GH2, PSOFC and N in March, April and May were higher than those in other months, irrespective of m. The optimum m was 0.030 kg/s.

TiO2-based materials for photocatalytic hydrogen production

Hydrogen, the cleanest and most promising energy vector, can be produced by solar into chemical energy conversion, either by the photocatalytic direct splitting of water into Hand O, or, more efficiently,in the presence of sacrificial reagents, e.g., in the so-called photoreforming of organics. Efficient photocatalytic materials should not only be able to exploit solar radiation to produce electron–hole pairs, but also ensure enough charge separation to allow electron transfer reactions, leading to solar energy driven thermodynamically up-hill processes. Recent achievements of our research group in the development and testing of innovative TiO-based photocatalytic materials are presented here, together with an overview on the mechanistic aspects of water photosplitting and photoreforming of organics. Photocatalytic materials were either（i） obtained by surface modification of commercial photocatalysts, or produced（ii） in powder form by different techniques, including traditional sol gel synthesis, aiming at engineering their electronic structure, and flame spray pyrolysis starting from organic solutions of the precursors, or（iii） in integrated form, to produce photoelectrodes within devices, by radio frequency magnetron sputtering or by electrochemical growth of nanotube architectures, or photocatalytic membranes, by supersonic cluster beam deposition.

Controllable design of Zn-Ni-P on g-C_3N_4 for efficient photocatalytic hydrogen production

Synthesizing a stable and efficient photocatalyst has been the most important research goal up to now. Owing to the dominant performance of g-C3N4 (graphitized carbonitride), an ordered assemble of a composite photocatalyst, Zn-Ni-P@g-C3N4, was successfully designed and controllably prepared for highly efficient photocatalytic H2 evolution. The electron transport routes were successfully adjusted and the H2 evolution was greatly improved. The maximum amount of H2 evolved reached about 531.2 μmol for 5 h over Zn-Ni-P@g-C3N4 photocatalyst with a molar ratio of Zn to Ni of 1:3 under illumination of 5 W LED white light (wavelength 420 nm). The H2 evolution rate was 54.7 times higher than that over pure g-C3N4. Moreover, no obvious reduction in the photocatalytic activity was observed even after 4 cycles of H2 production for 5 h. This synergistically increased effect was confirmed through the results of characterizations such as XRD, TEM, SEM, XPS, N2 adsorption, UV-vis DRS, transient photocurrent, FT-IR, transient fluorescence, and Mott-Schottky studies. These studies showed that the Zn-Ni-P nanoparticles modified on g-C3N4 provide more active sites and improve the efficiency of photogenerated charge separation. In addition, the possible mechanism of photocatalytic H2 production is proposed.

Fabricating covalent organic framework/CdS S-scheme heterojunctions for improved solar hydrogen generation

The fabrication of S-scheme heterojunctions has received considerable attention as an effective approach to promote the separation and migration of photoexcited electron/hole pairs and retain strong redox abilities.Herein,an imine-based porous covalent organic framework(COF-LZU1)is integrated with controllably fabricated Cd S hollow cubes,resulting in the formation of an S-scheme heterojunction.When the COF content reaches 1.5 wt%,the COF/Cd S heterostructure(1.5%COF/Cd S)achieves the highest hydrogen generation rate of 8670μmol·h^(-1)·g^(-1),which is approximately 2.1 times higher than that of pure Cd S.The apparent quantum efficiency(AQE)of 1.5%COF/Cd S is approximately 8.9%at 420 nm.Further systematic analysis shows that the intimate contact interface and suitable energy band structures between Cd S and COF can induce the formation of an internal electric field at the heterojunction interface,which can effectively drive the spatial separation of photoexcited charge carriers and simultaneously maintain a strong redox ability,thus enhancing the photocatalytic H_(2) evolution performance.

Nitrate-group-grafting-induced assembly of rutile TiO2 nanobundles for enhanced photocatalytic hydrogen evolution

In this study,an acid-induced assembly strategy for a rutile TiO2 photocatalyst was proposed on the basis of the treatment of lamellar protonated titanate with a concentrated HNO3 solution.Nitrate groups were successfully grafted onto a TiO2 surface and induced the assembly of rutile TiO2 nanorods into uniform spindle-like nanobundles.The resulting TiO2 product achieved a photocatalytic hydrogen evolution rate of 402.4μmol h^?1,which is 3.1 times higher than that of Degussa P25-TiO2.It was demonstrated that nitrate group grafting caused the rutile TiO2 surface to become negatively charged,which is favorable for trapping positive protons and improving charge carrier separation,thereby enhancing photocatalytic hydrogen production.Additionally,surface charges were crucial to structural stability based on electrostatic repulsion.This study not only developed a facile surface modification strategy for fabricating efficient H2 production photocatalysts but also identified an influence mechanism of inorganic acids different from that reported in the literature.

Electrocatalytic conversion of CO_2 to liquid fuels using nanocarbon-based electrodes

Recent advances on the use of nanocarbon-based electrodes for the electrocatalytic conversion of gaseous streams of CO2 to liquid fuels are discussed in this perspective paper. A novel gas-phase electrocatalytic cell, different from the typical electrochemical systems working in liquid phase, was developed. There are several advantages to work in gas phase, e.g. no need to recover the products from a liquid phase and no problems of CO2 solubility, etc. Operating under these conditions and using electrodes based on metal nanoparticles supported over carbon nanotube （CNT） type materials, long C-chain products （in particular isopropanol under optimized conditions, but also hydrocarbons up to C8-C9） were obtained from the reduction of CO2. Pt-CNT are more stable and give in some cases a higher productivity, but Fe-CNT, particular using N-doped carbon nanotubes, give excellent properties and are preferable to noble-metal-based electrocatalysts for the lower cost. The control of the localization of metal particles at the inner or outer surface of CNT is an importact factor for the product distribution. The nature of the nanocarbon substrate also plays a relevant role in enhancing the productivity and tuning the selectivity towards long C-chain products. The electrodes for the electrocatalytic conversion of CO2 are part of a photoelectrocatalytic （PEC） solar cell concept, aimed to develop knowledge for the new generation artificial leaf-type solar cells which can use sunlight and water to convert CO2 to fuels and chemicals. The CO2 reduction to liquid fuels by solar energy is a good attempt to introduce renewables into the existing energy and chemical infrastructures, having a higher energy density and easier transport/storage than other competing solutions （i.e. H2）.

ZnxCd1–xS quantum dot with enhanced photocatalytic H2-production performance

H2 is an important energy carrier for replacing fossil fuel in the future due to its high energy density and environmental friendliness.As a sustainable H2-generation method,photocatalytic H2 production by water splitting has attracted much interest.Here,oil-soluble ZnxCd1-xS quantum dot(ZCS QD)with a uniform particle size distribution were prepared by a hot-injection method.However,no photocatalytic H2-production activity was observed for the oil-soluble ZCS QD due to its hydrophobicity.Thus,the oil-soluble ZCS QD was converted into a water-soluble ZCS QD by a ligand-exchange method.The water-soluble ZCS QD exhibited excellent photocatalytic H2-production performance in the presence of glycerin and Ni^2+,with an apparent quantum efficiency of 15.9%under irradiation of 420 nm light.Further,the photocatalytic H2-generation activity of the ZCS QD was~10.7 times higher than that of the ZnxCd1-xS relative samples prepared by the conventional co-precipitation method.This work will inspire the design and fabrication of other semiconductor QD photocatalysts because QD exhibits excellent separation efficiency for photogenerated electron-hole pairs due to its small crystallite size.

Building surface defects by doping with transition metal on ultrafine TiO_2 to enhance the photocatalytic H_2 production activity

Inefficient charge separation and limited light absorption are two critical issues associated with high‐efficiency photocatalytic H2production using TiO2.Surface defects within a certain concentration range in photocatalyst materials are beneficial for photocatalytic activity.In this study,surface defects(oxygen vacancies and metal cation replacement defects)were induced with a facile and effective approach by surface doping with low‐cost transition metals(Co,Ni,Cu,and Mn)on ultrafine TiO2.The obtained surface‐defective TiO2exhibited a3–4‐fold improved activity compared to that of the original ultrafine TiO2.In addition,a H2production rate of3.4μmol/h was obtained using visible light(λ>420nm)irradiation.The apparent quantum yield(AQY)at365nm reached36.9%over TiO2‐Cu,significantly more than the commercial P25TiO2.The enhancement of photocatalytic H2production activity can be attributed to improved rapid charge separation efficiency andexpanded light absorption window.This hydrothermal treatment with transition metal was proven to be a very facile and effective method for obtaining surface defects.

N-doped NaTaO3 synthesized from a hydrothermal method for photocatalytic water splitting under visible light irradiation

NaTaONcatalysts were synthesized by a hydrothermal（H） and a solid-state（S） methods in this study.The H-and S-NaTaONsamples were characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）, transmission electron microscopy（TEM）, UV–visible（UV–vis） diffuse reflectance spectroscopy, and photoluminescence（PL） spectroscopy. The XRD patterns of the H-and S-samples showed peaks indexed to the pure phase of perovskite NaTaOand minor peaks assignable to TaNat various synthesis temperatures. Substitution of oxygen by nitrogen ions causes the light absorption of the H-and S-NaTaONsamples to be extended to the 600–650 nm region, thus making the samples visible-light active. The NaTaONsamples exhibited photocatalytic activity for Hand Oevolution from aqueous methanol and silver nitrate solutions under visible-light irradiation. The UV–vis and PL spectra of the Hand S-catalysts revealed the presence of cationic vacancies and reduced metallic species, which acted as recombination centers. These results demonstrated that the preparation method plays a critical role in the formation of defect states, thereby governing the photocatalytic activity of the NaTaONcatalysts.

Photocatalytic H2 Evolution on TiO2 Assembled with Ti3C2 MXene and Metallic 1T-WS2 as Co-catalysts

The biggest challenging issue in photocatalysis is efficient separation of the photoinduced carriers and the aggregation of photoexcited electrons on photocatalyst’s surface.In this paper,we report that double metallic co-catalysts Ti3C2 MXene and metallic octahedral(1T)phase tungsten disulfide(WS2)act pathways transferring photoexcited electrons in assisting the photocatalytic H2 evolution.TiO2 nanosheets were in situ grown on highly conductive Ti3C2 MXenes and 1T-WS2 nanoparticles were then uniformly distributed on TiO2@Ti3C2 composite.Thus,a distinctive 1T-WS2@TiO2@Ti3C2 composite with double metallic co-catalysts was achieved,and the content of 1T phase reaches 73%.The photocatalytic H2 evolution performance of 1T-WS2@TiO2@Ti3C2 composite with an optimized 15 wt%WS2 ratio is nearly 50 times higher than that of TiO2 nanosheets because of conductive Ti3C2 MXene and 1T-WS2 resulting in the increase of electron transfer efficiency.Besides,the 1T-WS2 on the surface of TiO2@Ti3C2 composite enhances the Brunauer–Emmett–Teller surface area and boosts the density of active site.

Synergistic effect of Co（Ⅱ）-hole and Pt-electron cocatalysts for enhanced photocatalytic hydrogen evolution performance of P-doped g-C3N4

g-C3N4 is a metal-free semiconductor and a potential candidate for photocatalytic H2 production,however,the drawbacks,rapid recombination rate and limited migration efficiency of photogenerated carriers,restrict its photocatalytic activity.Herein,Co(II)as a hole cocatalyst modified P-doped g-C3N4 were successfully prepared to ameliorate the separation efficiency of photoinduced carriers and enhance the photocatalytic hydrogen production.The photocatalytic results demonstrated that the P-doped g-C3N4(PCN)exhibited higher photocatalytic activity compared with pure g-C3N4,while Co(II)/PCN photocatalyst exhibited further enhancement of photocatalytic performance.The proposed possible mechanism based on various characterizations is that P-doping can modulate the electronic structure of g-C3N4 to boost the separation of photogenerated-e-and h+;while the synergistic effect of both Co(II)(as hole cocatalyst)and Pt(as electron cocatalyst)can not only lead to the directional shunting of photogenerated e+-h?pairs,but further accelerate the photogenerated electrons transfer to Pt in order to join the photocatalytic reduction process for hydrogen evolution.As a result,the transportation and separation of photoinduced carriers were accelerated to greatest extent in the Pt/Co(II)/PCN photocatalyst.

Slow photons for solar fuels

Converting solar energy into hydrogen and hydrocarbon fuels through photocatalytic H2production and CO2photoreduction is a highly promising approach to address growing demand for clean andrenewable energy resources.However,solar‐to‐fuel conversion efficiencies of current photocatalysts are not sufficient to meet commercial requirements.The narrow window of solar energy that can be used has been identified as a key reason behind such low photocatalytic reaction efficiencies.The use of photonic crystals,formed from multiple material components,has been demonstrated to be an effective way of improving light harvesting.Within these nanostructures,the slow‐photon effect,a manifestation of light‐propagation control,considerably enhances the interaction between light and the semiconductor components.This article reviews recent developments in the applications of photonic crystals to photocatalytic H2production and CO2reduction based on slow photons.These advances show great promise for improving light harvesting in solar‐energy conversion technologies.

NiO-CaO materials as promising catalysts for hydrogen production through carbon dioxide capture and subsequent dry methane reforming

In this work, CaO-NiO mixed oxide powders were evaluated as consecutive CO;chemisorbents and catalytic materials for hydrogen production thought the CH;reforming process. Between the NiO impregnated CaO and CaO-NiO mechanical composite, the first one presented better chemical behaviors during the CO;capture and CH;reforming processes, obtaining syngas（H;+ CO） as final product. Results showed that syngas was produced at two different temperature ranges, between 400 and 600 °C and at T > 800 °C, where the first temperature range corresponds to the CH;reforming process but the second temperature range was attributed to a different catalytic reaction process: CH;partial oxidation. These results were confirmed through different isothermal and cyclic experiments as well as by XRD analysis of the final catalytic products, where the nickel reduction was evidenced. Moreover, when a CO-O;flow was used during the carbonation process a triple process was achieved:（i） CO oxidation,（ii） CO;chemisorption and（iii） CH;reforming. Using this gas flow the hydrogen production was always higher than that obtained with CO;.

Fabrication of hierarchical ZnIn2S4@CNO nanosheets for photocatalytic hydrogen production and CO2 photoreduction

Photocatalytic H2 production and CO2 reduction have attracted considerable attention for clean energy development.In this work,we designed an efficient photocatalyst by integrating lamellar oxygen-doped carbon nitride(CNO)nanosheets into ZnIn2S4(ZIS)microflowers by a one-step hydrothermal method.A well-fitted 2D hierarchical hybrid heterostructure was fabricated.Under visible light irradiation,the ZIS@CNO composite with 40 wt%CNO(ZC 40%)showed the highest hydrogen evolution rate from water(188.4μmol·h-1),which was approximately 2.1 times higher than those of CNO and ZIS(88.6 and 90.2μmol·h-1,respectively).Furthermore,the selective CO production rates of ZC 40%(12.69μmol·h-1)were 2.2 and 14.0 times higher than those of ZIS(5.85μmol·h-1)and CNO(0.91μmol·h-1),respectively,and the CH4 production rate of ZC 40%was 1.18μmol·h-1.This enhanced photocatalytic activity of CNO@ZIS is due mainly to the formation of a heterostructure that can promote the transfer of photoinduced electrons and holes between CNO and ZIS,thereby efficiently avoiding recombination of electron-hole pairs.

Systematic study of H2 production from catalytic photoreforming of cellulose over Pt catalysts supported on TiO2

Hydrogen(H2)production from photocatalytic reforming of cellulose is a promising way for sustainable H2 to be generated.Herein,we report a systematic study of the photocatalytic reforming of cellulose over Pt/m-TiO2(i.e.mixed TiO2,80%of anatase and 20%of rutile)catalysts in water.The optimum operation condition was established by studying the effect of Pt loading,catalyst concentration,cellulose concentration and reaction temperature on the gas production rate of H2(r(H2))and CO2(r(CO2)),suggesting an optimum operation condition at 40°C with 1.0 g·L^-1of cellulose and 0.75 g·L^-1of 0.16-Pt/m-TiO2 catalyst(with 0.16 wt%Pt loadting)to achieve a relatively sound photocatalytic performance with rH2=9.95μmol·h^-1.It is also shown that although the photoreforming of cellulose was operated at a relatively mild condition(i.e.with an UV-A lamp irradiation at40°C in the aqueous system),a low loading of Pt at^0.16 wt%on m-TiO2 could promote the H2 production effectively.Additionally,by comparing the reaction order expressed from both r(H2)(a1)and r(CO2)(a2)with respect to cellulose and water,the possible mechanism of H2 production was proposed.

Microbial Electrolysis Cells for Hydrogen Production

Microbial electrolysis cells(MECs)present an attractive route for energy-saving hydrogen(H2)production along with treatment of various wastewaters,which can convert organic matter into H2 with the assistance of microbial electrocatalysis.However,the development of such renewable technologies for H2 production still faces considerable challenges regarding how to enhance the H2 production rate and to lower the energy and the system cost.In this review,we will focus on the recent research progress of MEC for H2 production.First,we present a brief introduction of MEC technology and the operating mechanism for H2 production.Then,the electrode materials including some typical electrocatalysts for hydrogen production are summarized and discussed.We also highlight how various substrates used in MEC affect the associated performance of hydrogen generation.Finally we presents several key scientific challenges and our perspectives on how to enhance the electrochemical performance.

New progress on MXenes-based nanocomposite photocatalysts

Two-dimensional(2D)materials,especially transition metal carbides and/or nitrides(MXenes),have aroused extensive research interest in the field of photocatalysis.Specifically,the unique properties of high electrical conductivity,abundant surface functional groups,considerable specific surface area,and excellent photo-thermal effect allow MXenes to play versatile roles in photocatalysis.Herein,the latest and encouraging developments in MXenes-based composite materials for photocatalytic applications in recent two years are reviewed.We first briefly describe the roles of MXenes as a support and co-catalyst to promote the distribution of photocatalysts and facilitate the separation of the photogenerated charge carriers,respectively.Then,the design and fabrication of MXenes-based composite materials for various photocatalytic applications including H_(2) evolution,CO_(2) reduction,environmental remediation,and H_(2)O_(2) generation are comprehensively illustrated.Finally,we point out the challenges and prospects for the future development of MXenes-based composite materials.

Prospect of vapor phase catalytic H2O2 production by oxidation of water

Vapor phase catalytic hydrogen peroxide production by oxidation of water is possible by coupling the reaction with oxidation of an organic sacrificial reductant. It is potentially a safer process than direct synthesis from H2 and O2. Based on mechanistic information available mostly for liquid phase catalytic processes, feasible reaction mechanisms for such coupled reactions are proposed based on which desirable catalyst properties are identified. It is found that the surface-adsorbed oxygen bond is an important parameter for identifying desirable catalysts. Thermodynamics can be used to identify the types of organic oxidation reactions that can couple with water oxidation such that H2O2 formation becomes thermodynamically favorable. Reactions such as epoxidation of alkenes and selective oxidation of alkanes to alcohols cannot provide sufficient thermodynamic driving force, whereas oxidation of alcohols to aldehydes and to acids can. Finally, further research is suggested to identify catalytic properties important for H2O2 decomposition and for coupling selective oxidation of organic compounds to oxidation of H2O in order to facilitate development of H2O2 production coupled with selective organic oxidation.

Improvement strategies for Ni-based alcohol steam reforming catalysts

Steam reforming(SR)of fossil methane is already a well-known,documented and established expertise in the industrial sector as it accounts for the vast majority of global hydrogen production.From a sustainable development perspective,hydrogen production by SR of biomass-derived feedstock represents a promising alternative that could help to lower the carbon footprint of the traditional process.In this regard,bio-alcohols such as methanol,ethanol or glycerol are among the attractive candidates that could serve as green hydrogen carriers as they decompose at relatively low temperatures in the presence of water compared to methane,allowing for improved H_(2)yields.However,significant challenges remain regarding the activity and stability of nickel-based catalysts,which are most widely used in alcohol SR processes due to their affordability and ability to break C–C,O–H and C–H bonds,yet are prone to rapid deactivation primarily caused by coke deposition and metal particle sintering.In this state-of-the-art review,a portfolio of strategies to improve the performance of Ni-based catalysts used in alcohol SR processes is unfolded with the intent of pinpointing the critical issues in catalyst development.Close examination of the literature reveals that the efforts tackling these recurring issues can be directed at the active metal,either by tuning Ni dispersion and Ni-support interactions or by targeting synergistic effects in bimetallic systems,while others focus on the support,either by modifying acid-base character,oxygen mobility,or by embedding Ni in specific crystallographic structures.This review provides a very useful tool to orient future work in catalyst development.