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The article discusses the importance of photocatalytic hydrogen production in achieving carbon neutrality and the progress that has been made in this field. It highlights the development of the SrTiO3 and BiVO4 Z-scheme, which has increased the efficiency of solar energy photocatalytic hydrogen production. The article also discusses recent advancements in understanding the charge transfer mechanism in photocatalysts, including the use of surface photovoltage microscopy and time-resolved photoemission electron microscopy. These studies provide valuable insights into the driving force for charge separation in photocatalyst particles. Overall, this research contributes to the development of efficient and industrially scalable photocatalysts for hydrogen production, which is crucial for achieving carbon neutrality. [Extracted from the article]

As an extraordinarily lightweight and porous functional nanomaterial family, aerogels have attracted considerable interest in academia and industry in recent decades. Despite the application scopes, the modest mechanical durability of aerogels makes their processing and operation challenging, in particular, for situations demanding intricate physical structures. "Bottom-up" additive manufacturing technology has the potential to address this drawback. Indeed, since the first report of 3D printed aerogels in 2015, a new interdisciplinary research area combining aerogel and printing technology has emerged to push the boundaries of structure and performance, further broadening their application scope. This review summarizes the state-of-the-art of printed aerogels and presents a comprehensive view of their developments in the past 5 years, and highlights the key near- and mid-term challenges. [ABSTRACT FROM AUTHOR]

Under the vision of "carbon peaking and carbon neutrality", the global energy system is facing a deep restructuring. One representative advancement is the successful construction of the SrTiO SB 3 sb and BiVO SB 4 sb Z-scheme by Professor K. Domen from the University of Tokyo, Japan, which has increased the solar energy photocatalytic hydrogen production efficiency to >1% [[1]]. [Extracted from the article]

Highlights from the article: Guest Editors Yann Garcia and Bao-Lian Su highlight the great interest in the field of inorganic nanomaterials and present an overview of the topics discussed in this special issue. In analogy to TiO SB 2 sb anatase nanocubes discussed by Tremel I et al. i , the same team present in a second contribution, the synthesis of SnO SB 2 sb microplates displaying photocatalytic and antibacterial properties. In this context, Wong Chi Man I et al. i prepared new mesoporous hybrid organosilica materials from organosilanes, whereas Blin I et al. i investigate the stability of dual mesostructured silica and of a macro-mesostructured silica.

The article discusses the Fischer-Tropsch (FT) synthesis, a process used to convert synthesis gas into hydrocarbons. The precise mechanistic steps of this reaction are still debated, but recent research has reported periodic rate-and-selectivity oscillations in the FT reaction over a Co/Ce-oxide powder catalyst. These oscillations were accompanied by temperature variations and were attributed to Arrhenius factors associated with C-O bond breaking. The findings suggest the possibility of generating self-sustained oscillatory behavior in the FT reaction, which could lead to enhanced reaction rates and selectivity. This research has the potential to inspire further investigation into kinetic instabilities in complex catalytic reactions and the development of dynamic catalyst design strategies. [Extracted from the article]

AuPtbimetallicnanoparticlesinside/ on the surface of the hollow structures exhibited a broader absorbance region under visible light than monometallic, through the influence of strong metal-metal interactions, as shown in Fig. The situation of AuPt bimetallic nanoparticles inside/on the surface (AuPt@HMZS and AuPt/HMZS) of the hollow structures depends on the order of metal loading andshellcoating. The heatgeneratedbylightscatteringandthe photothermal effect of plasmonic AuPt nanoparticles is usually weakened via electron-photon scattering to reach the system equilibrium. [Extracted from the article]

[Display omitted] Type 1 diabetes mellitus is an auto-immune disease causing the T -cell mediated destruction of insulin-producing β-cells, resulting in chronic hyperglycemia. Current treatments such as insulin replacement therapy or the transplantation of pancreas or pancreatic islets present major disadvantages such as the constant need of drugs, as well as a shortage of donor organs. In this review, we discuss a sustainable solution to overcome these limitations combining the use of β-cells, derived from stem cells, and their encapsulation within a protective matrix. This article provides an exhaustive overview of currently investigated stem cell sources including embryonic, mesenchymal as well as induced pluripotent stem cells in combination with various up to date encapsulation methods allowing the formation of immuno-protective devices. In order to identify current limitations of this interdisciplinary therapeutic approach and to find sustainable solutions, it is essential to consider key aspects from all involved domains. This includes biological parameters such as the stem cell origin but also the different aspects of the encapsulation process, the used materials and their physico-chemical properties such as elasticity, porosity and permeability cut-off as well as the best implantation sites allowing efficient and self-autonomous control of glycemia by the transplanted encapsulated cells. [ABSTRACT FROM AUTHOR]

Abstract: The submicron scale hybrid hollow silica spheres have been fabricated by employing phosphorylated polyethyleneimine as template/scaffold/catalysis in a mild self-assembly biomineralization approach. The highly phosphorylated polyethyleneimine was shown to be a necessary prerequisite for in vitro formation of hollow silica spheres. In the presence of a neutral phosphate buffer, the monovalent anions H2PO4 − and divalent anions HPO4 2− acted not only as the buffer ions but also as ligands, regulating the shape and morphology of the PEI aggregation, which resulted in the final hollow morphology of silica. The hollow silica particles were very uniform in size, with a diameter of 0.8–1.0μm and a shell thickness of ~70nm. [Copyright &y& Elsevier]

Abstract: Unusual partially crystalline ordered mesoporous zirconosilicate doughnuts with Si/Zr ratio as low as 1.5 were synthesized from the aqueous polymerisation of a single source molecular precursor Zr[OSi(Ot-BuO)3]4 without the use of any templating agent. A radial homogenous mesoporosity (4nm) was observed inside these very regular sub-micrometric (600nm) doughnuts. These structures were partially crystallized in hydrothermal conditions (100°C) into an analogous zircon (ZrSiO4) framework. The formation mechanism has been investigated. It is evidenced that chlorine anions Cl− concentration and pH value are essential to achieve the process, even if their role is still a matter of investigations. The obtained materials demonstrated even higher catalytic activity, selectivity and stability in the liquid oxidative dehydrogenation of hydroquinone to 1,4-benzoquinone compared to TS-1 zeolite catalysts and amorphous highly ordered mesoporous zirconosilicate materials. [Copyright &y& Elsevier]

Abstract: A layer of macrocyclic calix[4]arene derivatives has been grafted on the internal surface of the mesochannels of the ordered mesoporous SBA-15 to develop highly efficient trap for heavy transition metal (HTM) ions. To ensure the successful anchoring of calix[4]arene derivatives on the surface of SBA-15, two different types of calix[4]arene derivatives, one with one trimethoxysilane functional group and another with two trimethoxysilane functional groups have been explored. XRD, N2 adsorption and TEM results provide strong evidence that the mesoporous structure of the supporting materials retain their long range ordering throughout the grafting process. Solid-state NMR, TG and FT-IR spectroscopy indicate that both types of calix[4]arene derivatives can be well-anchored on the surface of the wall of SBA-15. Calix[4]arene derivative with only one trimethoxysilane functional group showed high grafting efficiency compared to that with two trimethoxysilane functional groups due to the intramolecular and intermolecular polycondensation between two trimethoxysilane functional groups. The HTM ions extraction capacity in aqueous solution of macrocycle functionalized SBA-15 nanohybrides for a series of HTM ions has been studied. The obtained materials demonstrated very high HTM ions extraction capacity up to 96% for Pb2+ in aqueous solution. [Copyright &y& Elsevier]

Abstract: Highly sensitive and selective nanosensor for labile iron pool (LIP) determination, has been designed and prepared by immobilization of Fluoresceine–Desferrioxamine (Fl–DFO), a bifunctional fluoro-siderophore probe molecule with great affinity for iron ions (pKf =30.7), into highly ordered mesoporous silica structure. Different immobilization methods of Fl–DFO molecules, such as their encapsulation in surfactant micelles used as templating agents for the synthesis of mesoporous silica, direct impregnation into the mesochannels of as-synthesized mesoporous silica and their surface anchoring by covalent binding with propylamine groups implanted by post-synthesis on the internal surface of mesochannels, have been explored. Each nanohybrid has been fully characterized by small angle XRD, TEM, SEM, solid state 29Si and 13C MAS NMR and N2 adsorption–desorption. The fluorescence properties of nanohybrids obtained have been correlated with the immobilization methods, generating interesting information concerning the localization of Fl–DFO molecules in the channels of mesoporous silica. The leaching of Fl–DFO molecules from mesoporous materials has been investigated. The nanosensor prepared by surface anchoring of Fl–DFO at the internal surface of mesochannels showed high performances with no leaching effect and high sensitivity in regards to its responses to ferric ions. Its fluorescence intensity decreased as soon as first FeIII ions are in contact with this nanosensor. A linear relationship between the fluorescence intensity and the ferric ions concentration was observed in low micromolar range. The selectivity of this nanosensor towards other metal ions has also been tested and shown its high affinity to ferric ions. This study can allow the design of a stable, portable, simple, regenerable and cost-effective nanosensor highly sensitive and selective for iron ions with detection limits in the range of cellular LIP in cells, e.g. lower micromolar range. [Copyright &y& Elsevier]

Abstract: The effect of tetraethoxysilane (TEOS), tetrapropoxysilane (TPOS), tetrabutoxysilane (TBOS) and a mixture of tetramethoxysilane (TMOS) and TEOS as silicon co-reactant on the formation of hierarchically structured meso-macroporous aluminosilicates and the tetrahedral aluminium content in the framework using a single molecular alkoxide precursor, (sec-BuO)2–Al–O–Si(OEt)3, has been intensively investigated. The use of alkoxysilane as a co-reactant and highly alkaline media improves the heterocondensation rates between the highly reactive aluminium-alkoxide part of the single molecular precursor and the added alkoxysilanes, and minimizes the cleavage of the intrinsic Al–O–Si linkage. The very unique hierarchical meso-macroporosity was auto-generated by the hydrodynamic flow of solvents released during the rapid hydrolysis and condensation processes of this double alkoxide and the inorganic silica co-reactant. No external structural agent was required to template these porous structures. The particles obtained featured outstanding macrostructure with regular micrometer-sized macrovoids and displaying 3D interconnections. Importantly, the diameter of the micrometer-sized macrovoids found in the final materials and the thickness of the mesoporous walls separating these voids can be tuned by adjusting the reactivity of alkoxysilanes used as co-reactant. Higher reactivity of alkoxysilanes can improve the tetrahedral aluminium content in the meso-macroporous framework and reduce the cleavage of Al–O–Si linkage of the single molecular precursor. These correlations are of primary importance for targeting advanced materials with well defined meso- and macroporosities and tetrahedral aluminium content. [Copyright &y& Elsevier]

Guest editors Yann Garcia and Bao-Lian Su highlight the great current interest in the field of inorganic nanomaterials and offer a glimpse into the diversity of the topics discussed in this cluster issue. [ABSTRACT FROM AUTHOR]

NiFeCO3 hydrotalcites with Ni/Fe molar ratio of 3 were synthesized by co-precipitation method at constant pH, followed by hydrothermal treatment at various temperatures 85–180°C for 3–360h. The obtained materials were characterized by XRD analysis, FT-IR spectroscopy, SEM and TEM microscopy, TGA and BET techniques. The resulting materials were found to be similar to the hydrotalcite with a well-defined hexagonal morphology of crystallites. The hydrothermal treatment and aging time increases the platelet sizes and decreases the surface area. XRD analysis showed the formation of sharper and intense peaks, which might indicate the larger crystallites size of LDH as well as higher crystallinity. Furthermore, textural studies revealed influence of aging time and temperature on the properties of the crystalline phase. The prolonged time tends to form additional products, identified as NiFe2O4 spinel and NiO nickel oxide. The effect of hydrothermal treatment temperature on the kinetics of dye removal has been explored. It was found that the percentage color removal increases with increasing hydrothermal treatment temperature up to 140°C and aging time up to 4 days. Furthermore, the color removal decreases with increasing hydrothermal treatment temperature up to 140–180°C and prolonged aging time. [Copyright &y& Elsevier]

Abstract: Two novel and simple synthesis pathways, one surfactant-assisted and one template-free, have recently been developed for the formation of aluminosilicate macrochannels with mesoporous walls. These thermally stable materials are made of straight tubular macrochannels separated by wormhole-like mesopores. This paper gives a comparative study of the materials obtained by both ways in order to determine the role played by the surfactant. High specific surface area materials with homogeneous tubular macrochannels are spontaneously formed without needing any templating procedure. The use of a non-ionic surfactant favors the incorporation of Al atoms in tetrahedral sites and also controls the homogeneity of the mesopores. The formation of the macrochannels is believed to result from the spontaneous and strong release of alcohol molecules due to high hydrolysis and condensation rates of the inorganic sources, which creates a hydrodynamic flow, thus channels of the solvent. The mesopores are generated by interparticular voids. [Copyright &y& Elsevier]

Abstract: The hydrothermal genesis of AlPO4-5, in the presence of four different organic templates, viz., methyldicyclohexylamine (MCHA), triethylamine (TEA), tripropylamine (TPA), and tetraethylammonium hydroxide (TEAOH), has been monitored by XRD. It is shown that TEAOH has the best templating ability to the formation of AlPO4-5 structure under the different synthesis conditions considered in this study. Density functional calculations on periodic models of AlPO4-5 indicate the strongest nonbonding interaction energy between the template and the framework in the case of TEAOH. Therefore, a new approach correlating the nonbonding interaction energy to the template ability to form a porous structure is proposed as a step toward a better understanding of the role of the organic template in the synthesis of porous molecular sieves. [Copyright &y& Elsevier]

Abstract: Acidic properties of H-CHA, H-ZOL-C, and H-ZOL-N have been investigated using periodic density functional calculations to understand the effect of organic moiety incorporation on their acidities. Results from NH3 adsorption energy, deprotonation energy, and relative nucleophilicity calculations are consistent and show that the relative Brønsted acid site strength decreases in the order H-CHA>H-ZOL-C>H-ZOL-N. The geometrical parameters of the optimized structures indicate the easier incorporation of NH rather than CH2 in the chabazite framework. Moreover, the basicity of the lattice O, N, and C atoms increases in the order C

Abstract: The oxidizing and reducing character of various exchanged L zeolites has been studied by EPR spectroscopy via the formation of perylene and tetracyanoethylene ion radicals, respectively, and correlated with the acido-basic properties of zeolites. In the series of alkaline L forms the reducing character increases from LiL to CsL in parallel with the calculated framework average negative charge on oxygen atoms (oxygen basicity). An opposite variation is obtained for the oxidizing properties. The exchange of K+ ions by H+, enhancing the acidity of zeolites, decreases the reducing and increases the oxidizing properties. The present work reveals the links which exist between the acidity of zeolites with oxidizing centers on one hand and the basicity with reducing character on the other hand. This observed parallelism between the redox properties and the acido-basicity of zeolites could be of great importance to explain reliably the catalytic behaviour of L zeolites as support. The first attempt has been made concerning the correlations between the changes in the redox properties and the selectivity for the aromatization of n-hexane on Pt alkaline L zeolite and the sulphur resistance of Pt/acidic or basic zeolites. [Copyright &y& Elsevier]

Abstract: The reactivity and behavior of phenol (phenol-d 5) on NaX zeolite at different temperatures have been studied by 1H MAS NMR and FT-IR techniques. An interaction between hydroxyl of phenol and zeolite framework oxygen atoms has been revealed, favouring the transfer of H(D) atoms of phenolic hydroxyl to zeolite framework to give phenolate ions. In phenol, the isotope exchange between H(D) atoms of phenolic hydroxyl and those of ring occurs mainly at ortho and para positions. The formation of phenolate ions changes the isotope exchange to meta position. The formation of phenol to phenolate ions is enhanced on NaX zeolite, explaining the high O-alkylation selectivity observed in phenol alkylation with methanol. [Copyright &y& Elsevier]

Abstract: The present review outlines the research work realized during last the 10 years in our laboratory in the field of the conception of new nanostructured porous materials, from mesoporous silicas and metal oxides to hierarchical meso–macroporous compounds with various compositions (single and binary metal oxides and aluminosilicates, aluminophosphates and silicoaluminophosphates). An accent was especially made on the evolution in the development of new synthesis strategies for the introduction of a hierarchy in one solid body with and without surfactant molecules. To cite this article: B.-L. Su and al, C. R. Chimie 8 (2005). [Copyright &y& Elsevier]

Alkylation of benzene with pure propane under flow condition has been investigated on a series of monometal gallium and bimetal gallium-platinum modified H-ZSM-5 zeolites with different acidity. The catalysts have been intensively characterized by XRD, XPS, TPR and IR spectroscopy. The chemical states of Ga and Pt have been studied and correlated with catalytic performances of these materials. The coke deposition on catalysts has been evaluated. It was found that the catalytic activity, product distribution and reaction path depend strongly on zeolite acidity and Pt content. With increasing the Si/Al ratio, the benzene conversion decreases and products distribution changes. Main reaction products for high acidity catalysts (lower Si/Al ratio) are toluene, ethylbenezene (EB) and xylenes, indicating that the cracking of propane is favored over its dehydrogenation. For the samples with low acidity, the formation of cumene and propylbenzenes (PrBz) is enhanced. Bimetal GaPt samples show high catalytic activity and selectivity to cumene. Pt promoted Ga-ZSM-5 catalysts show low concentration of coke like polyolefines and polycondensed aromatics, because platinum has a role of the entrance for hydrogen spillover which prevents or moderates coke deposition. Bimetal GaPt samples could be very efficient catalysts for cumene production from benzene alkylation using propane as alkylating agent. It is established that part of platinum in the bimetal samples is in zero valent state and most probably form big metal particles. [Copyright &y& Elsevier]

A simple one-step hydrothermal reaction among TiO2 powders and alkaline solution has been developed to synthesize low-dimensional titanate nanostructures. The morphologies of the obtained nanomaterials depend on the process parameters: the structure of raw material, the nature and concentration of alkaline solution, reaction temperature and time, which suggests that the nanostructure synthesis could be controllable. Trititanate nanotubes with the diameters of about 10 nm were synthesized via the hydrothermal reaction of TiO2 crystals of either anatase or rutile phase and NaOH solution in the temperature range of 100–160 °C. Nanofibers with an interlinked structure were formed when amorphous TiO2 or commercial TiOSO4 was treated with NaOH at 100–160 °C. Pentatitanate nanoribbons with high aspect ratio were obtained by autoclaving of either crystalline or amorphous TiO2 in NaOH solution at the temperature above 180 °C. Octatitanate nanowires with the diameters of 5–10 nm were prepared from TiO2 particles treated with KOH solution. These nanostructures were analyzed by a range of methods including powder X-ray diffraction (XRD), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDX) and infrared spectroscopy (IR). [Copyright &y& Elsevier]

Mesoporous silicas with ordered hexagonal MCM-41 structure were synthesized under mildly alkaline condition at room temperature in the presence of the surfactant cetylpyridinium chloride. Low-temperature post-synthesis treatment of these silicas in ammonia solution was investigated. The pore size was expanded from 2 to 4 nm by post-treatment at temperatures lower than 373 K, accompanied by a subtle change of morphology, and could be fine-tuned by varying the post-treatment temperature. A bimodal mesopore system with an interconnected three-dimensional was obtained, when the post-treatment occurred at 373 K. The control of the pore system and the creation of larger secondary mesopores, leading the unidimensional channels interconnected, are important and useful for catalysis. The role of ammonia in the extension of the pore size during low-temperature treatment and the possible generation of the secondary pore system by the decomposition of the thermally unstable cetylpyridinium surfactant are discussed in detail. The present work can serve as an excellent example for pore system engineering. [Copyright &y& Elsevier]

A new mesoporous form of crystalline β-FeOOH (akaganeite) was successfully prepared by a technology of surfactant-assisted nanoparticle assembly in the presence of a nonionic PEO-surfactant. The synthesized mesoporous β-FeOOH has a high surface area of 228 m2/g and a pore size of 4.3 nm with a hierarchical scaffold-like structure formed through the aggregation and intergrowth of akaganeite nano-rods. To our knowledge, this is first known report of mesostructured crystalline akaganeite material. Thermal treatment at 200 °C afforded the retention of the akaganeite structure. A complete transformation to hematite occurred after calcination at 300 °C with structural collapse. [Copyright &y& Elsevier]

The Bro¨nsted acidity of a series of protonated zeolites with different structures and Si/Al ratios such as HY (Si/Al=2.4), H(Na)EMT (3.6), HMOR (9.5), HZSM-5 (21.7) and HBeta (12.5) have been studied at room temperature and at various temperatures by means of in situ FT-IR spectroscopy using chloromethane as probe molecule. CH3Cl was found to interact by its negatively charged chlorine atom with the polarised hydrogen atoms of hydroxyls of zeolites through hydrogen bonding, causing the red-shift of the hydroxyls vibration. The extent of the red-shift supplies important information on the strength of Bro¨nsted acidity of zeolites which ranks in the order: HBeta>HMOR≈HZSM-5>H(Na)EMT≥HY. The study made at various temperatures revealed that the interaction of chloromethane with hydroxyls of zeolites was dependent on the temperature, reflecting the strength and the heterogeneity of acidic hydroxyls of zeolites. This temperature-dependent study confirms also the acid strength ranking obtained on the basis of the extent of the red-shift. The direct conversion of CH3Cl was carried out in the temperature range of 200–500 °C. The intrinsic activity of the five investigated zeolites has been compared with and was found to vary in the sense as acid strength. The selectivity of products of chloromethane conversion was also correlated with the Bro¨nsted acid strength of the zeolites. [Copyright &y& Elsevier]

Designing efficient, inexpensive, and stable photocatalysts to degrade organic pollutants and antibiotics has become an effective way for environmental remediation. In this work, we successfully performed in situ growth of CdS QDs on the surface of elliptical BiVO4 to try to show the advantage of the binary heterojuncted photocatalyst (BVO@CdS) for the photocatalytic degradation of tetracycline (TC). The In situ growth of CdS QDs can provide a large number of reactive sites and also generate a larger contact area with BiVO4. In addition, compared with mechanical composite materials, in situ growth can significantly reduce the energy barrier at the interface between BiVO4 and CdS, providing more channels for the separation and migration of photogenerated charge carriers, and further improving reaction activity. As a result, BVO@CdS-0.05 shows the best degradation efficiency, with a degradation rate of 88% after 30 min under visible light. The TC photodegradation follows a pseudo-second-order reaction with a dynamic constant of 0.472 min−1, which is 6.47 times that of pure BiVO4, 7.24 times that of pure CdS QDs and 2 times that of the mechanical composite. The degradation rate of BVO@CdS-0.05 decreases to 77.8% with a retention rate of 88.5% after four cycles, demonstrating excellent stability. Through liquid chromatography-mass spectrometry (LC-MS) analysis, two possible pathways for TC degradation are proposed. Through free radical capture experiments, electron spin resonance measurements, and photoelectrochemical comprehensive analysis, it is confirmed that BVO@CdS composites have constructed an efficient Z-scheme heterojunction via in situ growth, thereby highly enhancing the separation and transport efficiency of charge carriers. [ABSTRACT FROM AUTHOR]

Catalytic oxidative desulfurization (ODS) using titanium silicate catalysts has emerged as an efficient technique for the complete removal of organosulfur compounds from automotive fuels. However, the precise control of highly accessible and stable-framework Ti active sites remains highly challenging. Here we reveal for the first time by using density functional theory calculations that framework hexa-coordinated Ti (TiO6) species of mesoporous titanium silicates are the most active sites for ODS and lead to a lower-energy pathway of ODS. A novel method to achieve highly accessible and homogeneously distributed framework TiO6 active single sites at the mesoporous surface has been developed. Such surface framework TiO6 species exhibit an exceptional ODS performance. A removal of 920 ppm of benzothiophene is achieved at 60°C in 60 min, which is 1.67 times that of the best catalyst reported so far. For bulky molecules such as 4,6-dimethyldibenzothiophene (DMDBT), it takes only 3 min to remove 500 ppm of DMDBT at 60°C with our catalyst, which is five times faster than that with the current best catalyst. Such a catalyst can be easily upscaled and could be used for concrete industrial application in the ODS of bulky organosulfur compounds with minimized energy consumption and high reaction efficiency. [ABSTRACT FROM AUTHOR]

[Display omitted] Solar-light driven oxidation of benzylic alcohols over photocatalysts endows significant prospects in value-added organics evolution owing to its facile, inexpensive and sustainable process. However, the unsatisfactory performance of actual photocatalysts due to the inefficient charge separation, low photoredox potential and sluggish surface reaction impedes the practical application of this process. Herein, we developed an innovative Z-Scheme Cs 3 BiBr 9 nanoparticles@porous C 3 N 4 tubes (CBB-NP@P-tube-CN) heterojunction photocatalyst for highly selective benzyl alcohol oxidation. Such composite combining increased photo-oxidation potential, Z-Scheme charge migration route as well as the structural advantages of porous tubular C 3 N 4 ensures the accelerated mass and ions diffusion kinetics, the fast photoinduced carriers dissociation and sufficient photoredox potentials. The CBB-NP@P-tube-CN photocatalyst demonstrates an exceptional performance for selective photo-oxidation of benzylic alcohol into benzaldehyde with 19, 14 and 3 times higher benzylic alcohols conversion rate than those of C 3 N 4 nanotubes, Cs 3 Bi 2 Br 9 and Cs 3 Bi 2 Br 9 @bulk C 3 N 4 photocatalysts, respectively. This work offers a sustainable photocatalytic system based on lead-free halide perovskite toward large scale solar-light driven value-added chemicals production. [ABSTRACT FROM AUTHOR]

Mixed‐halide perovskites show promising applications in tandem solar cells owing to their adjustable bandgap. One major obstacle to their commercialization is halide phase segregation, which results in large open‐circuit voltage deficiency and J‐V hysteresis. However, the ambiguous interplay between structural origin and phase segregation often results in aimless and unspecific optimization strategies for the device's performance and stability. An atomic scale is directly figured out the abundant Ruddlesden‐Popper anti‐phase boundaries (RP‐APBs) within a CsPbIBr2 polycrystalline film and revealed that phase segregation predominantly occurs at RP‐APB‐enriched interfaces due to the defect‐mediated lattice strain. By compensating their structural lead halide, such RP‐APBs are eliminated, and the decreasing of strain can be observed, resulting in the suppression of halide phase segregation. The present work provides the deciphering to precisely regulate the perovskite atomic structure for achieving photo‐stable mixed halide wide‐bandgap perovskites of high‐efficiency tandem solar cell commercial applications. [ABSTRACT FROM AUTHOR]

Excessive emission of CO2 into the atmosphere has severely impacted the global ecological environment. Converting CO2 into valuable chemicals and fuels is of great significance for sustainable development. However, low activity and undesirable selectivity often result from the inherent inertness of CO2. Herein, K- or/and Zn-modified Fe-based catalysts were prepared by an incipient-wetness impregnation method for CO2 hydrogenation via a cascade reaction. The results indicate that K species exist as K2O while Zn species exist as ZnFe2O4. In the CO2 hydrogenation pathway, K2O facilitates the adsorption of CO2 and restrains the adsorption of H2, accelerating the transformation of CO2 into C2–C4 olefins rather than paraffins while Zn species promote the dispersion of Fe species, leading to improved activity. Synergistically, a K- and Zn-modified Fe-based catalyst (2Zn–10K–Fe/Al) shows excellent catalytic CO2 hydrogenation activity, achieving a CO2 conversion of 77% which is 1.8 times that (42%) of the unmodified Fe-based catalyst (Fe/Al). Our catalyst also shows a significantly promoted selectivity to C2–C4 olefins of 17% in comparison with the Fe/Al catalyst (0%). It is envisioned that such a binary effect of elements might contribute to the low-cost and industrial production of Fe-based catalysts for selective CO2 conversion. [ABSTRACT FROM AUTHOR]

[Display omitted] The conversion of CO 2 into syngas, a mixture of CO and H 2 , via photocatalytic reduction, is a promising approach towards achieving a sustainable carbon economy. However, the evolution of highly adjustable syngas, particularly without the use of sacrifice reagents or additional cocatalysts, remains a significant challenge. In this study, a step-scheme (S-scheme) 0D ZnGa 2 O 4 nanodots (∼7 nm) rooted g-C 3 N 4 nanosheets (denoted as ZnGa 2 O 4 /C 3 N 4) heterojunction photocatalyst was synthesized vis a facial in-situ growth strategy for efficient CO 2 -to-syngas conversion. Both experimental and theoretical studies have demonstrated that the polymeric nature of g-C 3 N 4 and highly distributed ZnGa 2 O 4 nanodots synergistically contribute to a strong interaction between metal oxide and C 3 N 4 support. Furthermore, the desirable S-scheme heterojunction in ZnGa 2 O 4 /C 3 N 4 efficiently promotes charge separation, enabling strong photoredox ability. As a result, the S-scheme ZnGa 2 O 4 /C 3 N 4 exhibited remarkable activity and selectivity in photochemical conversion of CO 2 into syngas, with a syngas production rate of up to 103.3 μ mol g−1 h−1, even in the absence of sacrificial agents and cocatalyst. Impressively, the CO/H 2 ratio of syngas can be tunable within a wide range from 1:4 to 2:1. This work exemplifies the effectiveness of a meticulously designed S-scheme heterojunction photocatalyst for CO 2 -to-syngas conversion with adjustable composition, thus paving the way for new possibilities in sustainable energy conversion and utilization. [ABSTRACT FROM AUTHOR]

The article discusses the limitations of lithium-ion batteries (LIBs) and the growing interest in aqueous batteries as a sustainable alternative. Aqueous batteries are attractive due to their low cost and high safety, but their energy density and cycling performance need improvement for industrial applications. The optimization of electrode materials and electrolytes is a focus of research in aqueous batteries. The article also explores the voltage matching principle, different types of electrochemical reactions, and measures to enhance the energy density of aqueous batteries. The nature of the electrolyte and practical considerations for aqueous batteries are also discussed. While current aqueous batteries have met the demand for energy storage systems to some extent, further development in electrode and electrolyte engineering is expected to make next-generation aqueous batteries commercially viable. [Extracted from the article]

[Display omitted] Manipulation of light has been proved to be a promising strategy to increase light harvesting in solar-to-chemical energy conversion, especially in photocatalysis. Inverse opal (IO) photonic structures are highly promising for light manipulation as their periodic dielectric structures enable them to slow down light and localize it within the structure, thereby improving light harvesting and photocatalytic efficiency. However, slow photons are confined to narrow wavelength ranges and hence limit the amount of energy that can be captured through light manipulation. To address this challenge, we synthesized bilayer IO TiO 2 @BiVO 4 structures that manifested two distinct stop band gap (SBG) peaks, arising from different pore sizes in each layer, with slow photons available at either edge of each SBG. In addition, we achieved precise control over the frequencies of these multi-spectral slow photons through pore size and incidence angle variations, that enabled us to tune their wavelengths to the electronic absorption of the photocatalyst for optimal light utilization in aqueous phase visible light photocatalysis. This first proof of concept involving multi-spectral slow photon utilization enabled us to achieve up to 8.5 times and 2.2 times higher photocatalytic efficiencies than the corresponding non-structured and monolayer IO photocatalysts respectively. Through this work, we have successfully and significantly improved light harvesting efficiency in slow photon-assisted photocatalysis, the principles of which can be extended to other light harvesting applications. [ABSTRACT FROM AUTHOR]

The catalytic oxidative desulfurization (ODS) technique is able to remove sulfur compounds from fuels, conducive to achieving deep desulfurization for the good of the ecological environment. Ti-based metal–organic frameworks (Ti-MOFs) possessing good affinity to organic reactants and considerable numbers of Ti active sites are promising catalysts for ODS. However, current Ti-MOFs suffer from severe diffusion limitations caused by the size mismatch between sole micropores and bulky sulfur compounds, leading to poor ODS performance. Here, a facile method of intraparticle ripening without any additive is developed to obtain hierarchically meso–microporous Ti-MIL-125 single crystals (Meso-Ti-MIL-125) for the first time. Such Meso-Ti-MIL-125 shows a BET surface area of 1401 m2 g−1 and a mesoporous volume that is 1.7 times as high as that of the conventional Ti-MIL-125. Our novel Meso-Ti-MIL-125 exhibits excellent catalytic performance in the ODS of a series of bulky thiophenic sulfur compounds, completely removing benzothiophene (BT), dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (DMDBT) from model fuels, which is, respectively, 2.4 times, 1.5 times, and 6.7 times higher than the removal achieved with conventional Ti-MIL-125. Such a facile synthetic strategy is envisioned to be applied in many kinds of crystalline materials, such as zeolites, for industrial production. [ABSTRACT FROM AUTHOR]

H2‐free semi‐hydrogenation at room temperature shows great advantage for replacing the thermocatalytic process in industry owing to the high energy and resource saving, however, remains great challenges. Herein, a tree‐like Pd dendrites array decorated Pd membrane was constructed as the core device in an electrochemistry assisted gas‐fed membrane reactor for butadiene semi‐hydrogenation. It reveals that hydrogen atomic sieving effect of this Pd‐based membrane under electrochemical condition was the key for semi‐hydrogenation. The configuration study of Pd nanostructured membrane demonstrates that the penetration of hydrogen atoms through Pd membrane from electrochemical side to chemical side is affected by the consumption of hydrogen atom in semi‐hydrogenation step. Such atomic sieving property of nanostructured Pd membrane with 5.1 times increase in catalytic active surface area brings above 14 times higher in butadiene conversion than that of bare Pd foil, with ≈90 % of butenes selectivity at butadiene conversion ≈98 % over 300 h of H2‐free reaction under 15 mA cm−2. [ABSTRACT FROM AUTHOR]

H2‐free semi‐hydrogenation at room temperature shows great advantage for replacing the thermocatalytic process in industry owing to the high energy and resource saving, however, remains great challenges. Herein, a tree‐like Pd dendrites array decorated Pd membrane was constructed as the core device in an electrochemistry assisted gas‐fed membrane reactor for butadiene semi‐hydrogenation. It reveals that hydrogen atomic sieving effect of this Pd‐based membrane under electrochemical condition was the key for semi‐hydrogenation. The configuration study of Pd nanostructured membrane demonstrates that the penetration of hydrogen atoms through Pd membrane from electrochemical side to chemical side is affected by the consumption of hydrogen atom in semi‐hydrogenation step. Such atomic sieving property of nanostructured Pd membrane with 5.1 times increase in catalytic active surface area brings above 14 times higher in butadiene conversion than that of bare Pd foil, with ≈90 % of butenes selectivity at butadiene conversion ≈98 % over 300 h of H2‐free reaction under 15 mA cm−2. [ABSTRACT FROM AUTHOR]

An introduction is presented in which the editor discusses various reports within the issue on topics including doping of titania catalytic with vanadium oxide, photocatalysis and relevance of multi-faceted morphology of various microparticles.

The author discusses the highlights of a symposium on mesostructured materials held in Namur, Belgium in September 2008 and was jointly organized by the Laboratory of Inorganic Materials Chemistry at the University of Namur in Belgium and the Laboratory of Controlled Porosity Materials at the University of Haute-Alsace in France, under the auspices of the International Mesostructured Materials Association. The symposium addressed oxide mesostructured materials, non-oxide mesostructured materials and hierarchical mesostructured materials, among others.

[Display omitted] • A CNTs interconnected yolk-shell Si/C anode (YS-Si@CoNC) is designed via the chelation competition-induced polymerization (CCIP) for LIBs. • The CNTs and carbon shell provide an excellent electronically conductive network for the fast diffusion of electrons and Li+. • The unique yolk-shell structure greatly reduces the volume expansion of SiNPs in the cycling. • The YS-Si@CoNC anode presents outstanding electrochemical performances and structural stability. As a viable replacement to commercial graphite anodes, silicon (Si) anodes have gained much attention from academics because of their considerable theoretical specific capacity and appropriate reaction voltage. Nevertheless, some limitations still exist in developing silicon anodes, including significant volume expansion and poor electrical conductivity. Herein, the carbon nanotubes (CNTs) interconnected yolk-shell silicon/carbon anodes (YS-Si@CoNC) were prepared via the chelation competition induced polymerization (CCIP) approach. The YS-Si@CoNC anode, designed in this study, demonstrates improved performance. At the current density of 0.5 A g−1 and 1 A g−1, a capacity of 1001 mAh g−1 and 956.5 mAh g−1 can be achieved after 150 cycles and after 300 cycles, respectively. In particular, at the current density of 5 A g−1, the reversible specific capacity of 688 mAh g−1 is realized. The exceptional outcomes are mainly attributed to the internal voids that adequately alleviate the volumetric expansion and the CNTs and carbon shells that provide an efficient conducting matrix to fasten the diffusion of electrons and lithium-ions. Our research presents a convenient way of designing Si/C anode materials with a yolk-shell structure to guarantee impressive electrical conductivity and robust structural integrity for high-performance LIBs. [ABSTRACT FROM AUTHOR]

Ammonium‐ion batteries (AIBs) have recently attracted increasing attention in the field of aqueous batteries owing to their high safety and fast diffusion kinetics. The NH4+ storage mechanism is quite different from that of spherical metal ions (e.g. Li+, Na+, K+, Mg2+, and Zn2+) because of the formation of hydrogen bonds between NH4+ and host materials. Although many materials have been proposed as electrode materials for AIBs, their performances hardly meet the requirement of future electrochemical energy storage devices. It is thus urgent to design and exploit advanced materials for AIBs. This review highlights the state‐of‐the‐art research on AIBs. The insights into the basic configuration, operating mechanism and recent progress of electrode materials and corresponding electrolytes for AIBs have been comprehensively outlined. The electrode materials are classified and compared according to different NH4+ storage behaviour in the structure. The challenges, design strategies and perspectives are also discussed for the future development of AIBs. [ABSTRACT FROM AUTHOR]

Ammonium‐ion batteries (AIBs) have recently attracted increasing attention in the field of aqueous batteries owing to their high safety and fast diffusion kinetics. The NH4+ storage mechanism is quite different from that of spherical metal ions (e.g. Li+, Na+, K+, Mg2+, and Zn2+) because of the formation of hydrogen bonds between NH4+ and host materials. Although many materials have been proposed as electrode materials for AIBs, their performances hardly meet the requirement of future electrochemical energy storage devices. It is thus urgent to design and exploit advanced materials for AIBs. This review highlights the state‐of‐the‐art research on AIBs. The insights into the basic configuration, operating mechanism and recent progress of electrode materials and corresponding electrolytes for AIBs have been comprehensively outlined. The electrode materials are classified and compared according to different NH4+ storage behaviour in the structure. The challenges, design strategies and perspectives are also discussed for the future development of AIBs. [ABSTRACT FROM AUTHOR]

Biomass, a naturally abundant, sustainable and clean resource has great potential as an alternative to replace the limited fossil feedstock for value‐added chemicals and fuels. Biomass with abundant reductive functional groups could theoretically act as electron donor to consume photogenerated holes and/or active free radicals. Biomass photoreforming over semiconductor photocatalysts using solar light as energy input attracts much attention in this context. However, biomass photoreforming still suffers low conversion efficiency and product selectivity due to its structural complexity, poor solubility and unclear reaction mechanism. Owing to the advanced features of mass diffusion of biomass derivatives and adjustable surface properties, hierarchically porous photocatalysts with desired active sites at each length scale of porosity have shown their superiority in boosting the conversion efficiency and selectivity of biomass photoreforming. Herein, a critical review is presented on selective biomass photoreforming for simultaneous H2 and value‐added chemicals co‐production on hierarchically porous photocatalysts. The fundamentals of biomass photoreforming and current bottleneck of biomass valorization by photocatalytic process are presented and analyzed. The rational photocatalyst design with hierarchically porous structure to improve the biomass conversion and product selectivity by boosting mass transfer is highlighted. Finally the challenges and opportunities for photocatalytic biomass valorization are presented in the perspective ssection. [ABSTRACT FROM AUTHOR]

[Display omitted] • Glucose conversion assisted photocatalytic water splitting technology avoid the use of sacrificial agents while realizing co-product of H 2 and high value-added chemicals. • Both hierarchical 3DOM structure and type Ⅱ heterojunction are conducive to the absorption and utilization of light and the separation and transmission of carriers. • The 3DOM CTO-ZCS photocatalyst simultaneously has high photocatalytic H 2 production performance (2.81 mmol g-1h−1) and high glucose conversion (85.57 %). • The conversion of glucose to lactic acid is a two-step reaction and the control reaction step is gluconic acid to lactic acid. Glucose conversion assisted photocatalytic water splitting technology to simultaneously produce H 2 and high value-added chemicals is a promising method for alleviating the energy shortage and environmental crisis. In this work, we constructing type II heterojunction by in-situ coupling Zn 0.3 Cd 0.7 S quantum dots (ZCS QDs) on three-dimensionally ordered microporous CaTiO 3 (3DOM CTO) for photocatalytic H 2 production and glucose conversion. The DFT calculations demonstrate that substitution of Zn on the Cd site improves the separation and transmission of photogenerated carriers. Therefore, 3DOM CTO-ZCS composite exhibits best H 2 production performance (2.81 mmol g-1h−1) and highest apparent quantum efficiency (AQY) (5.56 %) at 365 nm, which are about 47 and 18 times that of CTO nanoparticles (NPs). The improved catalytic performance ascribed to not only good mass diffusion and exchange, highly efficient light harvesting of 3DOM structure, but also the efficient charges separation of type Ⅱ heterojunction. The investigation on photocatalytic mechanism indicates that the glucose is mainly converted to gluconic acid and lactic acid, and the control reaction step is gluconic acid to lactic acid. The selectivity for gluconic acid on 3DOM CTO-ZCS is 85.65 %. Our work here proposes a green sustainable method to achieve highly efficient H 2 production and selective conversion of glucose to gluconic acid. [ABSTRACT FROM AUTHOR]

[Display omitted] Periodic structures with alternating refractive indices such as inverse opal photonic crystals are capable of reducing the group velocity of light such that this slowed light can be more efficiently harvested for highly enhanced solar energy conversion. However, the generation, the manipulation and, in particular, the practical applications of these slow photons remain highly challenging. Here, we report the first proof of concept on the ability to control, in an inverse opal TiO 2 -BiVO 4 hetero-composite, the transfer of slow photons generated from the inverse opal photonic structure to the photocatalytically active BiVO 4 nanoparticles for highly enhanced visible light photoconversion. Tuning the slow photon frequencies, in order to accommodate the electronic band gap of BiVO 4 for slow photon transfer and for significantly improved light harvesting, was successfully achieved by varying the structural periodicity (pore size) of inverse opal and the light incidence angle. The photocatalytic activity of BiVO 4 in all inverse opal structures, promoted by slow photon effect, reached up to 7 times higher than those in the non-structured compact films. This work opens new avenues for the practical utilization of slow photon effect under visible light in photocatalytic energy-related applications like water splitting and carbon dioxide reduction and in photovoltaics. [ABSTRACT FROM AUTHOR]

Coupling polymer and ionic liquids with electrodes for catalysis is a promising tool for optimization of electrocatalytic CO2 reduction reaction (CO2RR). Here, block copolymer ionic liquids BCPILs were synthesized via controlled radical polymerization and nucleophilic post-substitution to introduce imidazole moieties. We show that, thanks to these PIL functionalities, the BCPIL/Re@HPC/GDL electrode can keep the selectivity toward CO when a higher amount of water is present in the electrolyte than the raw Re@HPC/GDL system. Our results help to understand the development of solid-state ionic liquids for enhanced CO2RR in water-based electrolyte. [ABSTRACT FROM AUTHOR]

For the first time, we demonstrate a Ti-MOF (Ti-metal organic framework) single-crystal featuring an intracrystal macro–microporous hierarchy (Hier-NTU-9) by a vapor-assisted polymer-templated method. This Hier-NTU-9 possesses macropores (100–1000 nm) derived from polymer templates and enhanced transport ability of bulky molecules, exhibiting almost double the desulfurization activity compared to the conventional NTU-9. [ABSTRACT FROM AUTHOR]

Photorefining of biomass and its derivatives to value-added chemicals is an alternative solution to address the global energy shortage and environmental issues. Herein, efficient and selective oxidation of 5-hydroxymethylfurfural (HMF, 91.1% conversion) to 2,5-diformylfuran (DFF, 99.4% selectivity) is demonstrated by visible light-driven photocatalysis over cocatalyst-free ZnIn2S4 nanosheets with crystal facet engineering. The spatial accumulation of photogenerated electrons and holes on the (110) and (102) crystal facets triggers a two-electron oxygen reduction reaction (2e-ORR) for H2O2 generation and HMF oxidation into DFF, respectively. The severe attenuation of photostability is caused by the irreversible photocorrosion of Zn–S with the formation of Zn–O chemical bonds by the formation of ˙OH from the in situ decomposition of H2O2. Spontaneous substitution of oxygen with sulfur has been proven to efficiently improve the photostability of ZnIn2S4. This present work provides insights into improving the durability of ZnIn2S4 and sheds new light on biomass valorization via photorefinery. [ABSTRACT FROM AUTHOR]

Bifunctional catalysts are widely applied for many important reactions as the synergetic effect of two types of active sites remarkably improves catalysis performance. However, their bifunctionality has not been fully exploited since the proximity of bifunctional catalysts is hard to control. Herein, we demonstrate a bifunctional ZSM-5@Al 2 O 3 catalyst with a core-shell structure and a nano-scale proximity by in-situ growth of γ-Al 2 O 3 nanosheets on the surface of ZSM-5 crystals for methanol conversion. The nano-scale proximity endows the catalyst with higher reaction activity and C 2 –C 3 olefins yield (53 %) in comparison to the catalysts with micro-scale proximity (20 %) and millimeter-scale proximity (27 %), which can be attributed to the fluent transport of the reaction intermediates between two types of active sites. This strategy for constructing bifunctional catalysts with nano-scale proximity is conducive to understanding the relationship between proximity and catalytic performance in methanol conversion. [Display omitted] • Bifunctional ZSM-5@Al 2 O 3 catalysts with core-shell structure were synthesized. • The proximity of dual-active sites was precisely controlled. • The nano-scale proximity enabled catalysts with superb performance. [ABSTRACT FROM AUTHOR]