Structural Isomerism of Two Ce-BTC for Fabricating Pt/CeO2 Nanorods toward Low-Temperature CO Oxidation.

Metal-organic frameworks (MOFs) have attracted enormous research interest as precursors/templates to prepare catalytic materials. However, the effect of structural isomerism of MOFs on the catalytic performance has rarely been studied. In this contribution, two topologically different Ce-benzene tricarboxylate (Ce-BTC) based on the same ligands and metal centers (viz., "MOF isomers") are prepared and used as porous supports to load Pt nanoparticles (NPs), which shows distinct differences in porosities and loading behaviors of Pt. Strikingly, an irreversible framework transformation from tetragonal Ce-BTC to monoclinic isomer is observed during water soaking treatment. The results give clear evidence that Pt/CeO2 derived from tetragonal Ce-BTC inclines to produce more Pt0 and smaller Pt NPs, which eventually improve the catalytic performance for CO oxidation (T100 = 80 °C). In situ diffuse reflectance infrared Fourier transform spectroscopy analyses demonstrate that the adsorbed CO-Pt0 is the dominant intermediate for CO oxidation, rather than CO-Ptσ + at the low temperature. Furthermore, MOF isomers based on the same structural units are also found in other Ln-MOFs, such as Er-BTC, Eu-BTC, Y-BTC, and Ce/Y-BTC. Overall, this study affords a fundamental understanding of the effect of MOF structural isomers on the catalytic performance of the derived composites.

Synthesis of ZIF-8 Nanocrystals Mediated by CO2 Gas Bubbling: Dissolution and Recrystallization.

Crystal size and morphology of zeolitic imidazolate frameworks (ZIFs) can be generally controlled based on the classical theory of nucleation and growth. Herein, we have developed an alternative method to adjust the nucleation and growth kinetics of microporous ZIF-8 nanocrystals mediated by continuous CO2 gas bubbling. In particular, CO2 bubbling led to the dissolution of ZIF-8 slurry, while the evacuation of CO2 bubbling resulted in the formation of new ZIF-8 nanoparticles with a considerably smaller size. A plausible mechanism of the CO2-mediated synthesis of ZIF-8 nanoparticles was proposed based on comprehensive characterizations and analyses, which indicated that the dissolved CO2 in methanol was able to perturb the pre-equilibrium states of crystallization intermediates and led to a comparatively fast nucleation rate due to a low number of overcoordinated species between the metal ion and the ligand. Both methanol and the base were critically important to the dissolution-recrystallization of ZIF-8, wherein the methyl carbonate linker might be reversibly produced by CO2 insertion into the methoxide group (Zn-OCH3). Also, the CO2-mediated synthesis led to the small particle size, high crystallinity, good thermal stability, and high purity of ZIF-8, as compared to the conventional ZIF-8 prepared without CO2 gas bubbling. As proof of workability, the prepared monodispersed ZIF-8 nanoparticles showed a much higher photocatalytic activity toward various organic dyes' decomposition than the conventional ZIF-8. Also, the CO2 bubbling-mediated method could be further extended to prepare other ZIFs (e.g., ZIF-67).

Effective Recovery of Vanadium from Oil Refinery Waste into Vanadium-Based Metal-Organic Frameworks.

Carbon black waste, an oil refinery waste, contains a high concentration of vanadium(V) leftover from the processing of crude oil. For the sake of environmental sustainability, it is therefore of interest to recover the vanadium as useful products instead of disposing of it. In this work, V was recovered in the form of vanadium-based metal-organic frameworks (V-MOFs) via a novel pathway by using the leaching solution of carbon black waste instead of commercially available vanadium chemicals. Two different types of V-MOFs with high levels of crystallinity and phase purity were fabricated in very high yields (>98%) based on a coordination modulation method. The V-MOFs exhibited well-defined and controlled shapes such as nanofibers (length: > 10 µm) and nanorods (length: ∼270 nm). Furthermore, the V-MOFs showed high catalytic activities for the oxidation of benzyl alcohol to benzaldehyde, indicating the strong potential of the waste-derived V-MOFs in catalysis applications. Overall, our work offers a green synthesis pathway for the preparation of V-MOFs by using heavy metals of industrial waste as the metal source.

Mesoporous bubble-like manganese silicate as a versatile platform for design and synthesis of nanostructured catalysts.

Manganese silicate in bubble-like morphology was used as a versatile platform to prepare a new class of yolk-shell hybrids. The mesoporosity of the shell was generated from the interbubble space and the bubble structure of manganese silica was used to hold and support nanoparticles (e.g., Au, Ag, Pt, Co, Ni, Au-Pd alloy, MoO2 , Fe3 O4 , carbon nanotubes and their combinations). We also used heterogeneous catalysis reactions to demonstrate the workability of these catalysts in both liquid and gas phases.

Biocompatible Copper-Based Nanocomposites for Combined Cancer Therapy.

Copper (Cu) and Cu-based nanomaterials have received tremendous attention in recent years because of their unique physicochemical properties and good biocompatibility in the treatment of various diseases, especially cancer. To date, researchers have designed and fabricated a variety of integrated Cu-based nanocomplexes with distinctive nanostructures and applied them in cancer therapy, mainly including chemotherapy, radiotherapy (RT), photothermal therapy (PTT), chemodynamic therapy (CDT), photodynamic therapy (PDT), cuproptosis-mediated therapy, etc. Due to the limited effect of a single treatment method, the development of composite diagnostic nanosystems that integrate chemotherapy, PTT, CDT, PDT, and other treatments is of great significance and offers great potential for the development of the next generation of anticancer nanomedicines. In view of the rapid development of Cu-based nanocomplexes in the field of cancer therapy, this review focuses on the current state of research on Cu-based nanomaterials, followed by a discussion of Cu-based nanocomplexes for combined cancer therapy. Moreover, the current challenges and future prospects of Cu-based nanocomplexes in clinical translation are proposed to provide some insights into the design of integrated Cu-based nanotherapeutic platforms.

Construction of Ni/In2O3 Integrated Nanocatalysts Based on MIL-68(In) Precursors for Efficient CO2 Hydrogenation to Methanol.

The efficient and economic conversion of CO2 and renewable H2 into methanol has received intensive attention due to growing concern for anthropogenic CO2 emissions, particularly from fossil fuel combustion. Herein, we have developed a novel method for preparing Ni/In2O3 nanocatalysts by using porous MIL-68(In) and nickel(II) acetylacetonate (Ni(acac)2) as the dual precursors of In2O3 and Ni components, respectively. Combined with in-depth characterization analysis, it was revealed that the utilization of MIL-68(In) as precursors favored the good distribution of Ni nanoparticles (∼6.2 nm) on the porous In2O3 support and inhibited the metal sintering at high temperatures. The varied catalyst fabrication parameters were explored, indicating that the designed Ni/In2O3 catalyst (Ni content of 5 wt %) exhibited better catalytic performance than the compared catalyst prepared using In(OH)3 as a precursor of In2O3. The obtained Ni/In2O3 catalyst also showed excellent durability in long-term tests (120 h). However, a high Ni loading (31 wt %) would result in the formation of the Ni-In alloy phase during the CO2 hydrogenation which favored CO formation with selectivity as high as 69%. This phenomenon is more obvious if Ni and In2O3 had a strong interaction, depending on the catalyst fabrication methods. In addition, with the aid of in situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory (DFT) calculations, the Ni/In2O3 catalyst predominantly follows the formate pathway in the CO2 hydrogenation to methanol, with HCOO* and *H3CO as the major intermediates, while the small size of Ni particles is beneficial to the formation of formate species based on DFT calculation. This study suggests that the Ni/In2O3 nanocatalyst fabricated using metal-organic frameworks as precursors can effectively promote CO2 thermal hydrogenation to methanol.

Recent Advances of Indium Oxide-Based Catalysts for CO2 Hydrogenation to Methanol: Experimental and Theoretical.

Methanol synthesis from the hydrogenation of carbon dioxide (CO2) with green H2 has been proven as a promising method for CO2 utilization. Among the various catalysts, indium oxide (In2O3)-based catalysts received tremendous research interest due to the excellent methanol selectivity with appreciable CO2 conversion. Herein, the recent experimental and theoretical studies on In2O3-based catalysts for thermochemical CO2 hydrogenation to methanol were systematically reviewed. It can be found that a variety of steps, such as the synthesis method and pretreatment conditions, were taken to promote the formation of oxygen vacancies on the In2O3 surface, which can inhibit side reactions to ensure the highly selective conversion of CO2 into methanol. The catalytic mechanism involving the formate pathway or carboxyl pathway over In2O3 was comprehensively explored by kinetic studies, in situ and ex situ characterizations, and density functional theory calculations, mostly demonstrating that the formate pathway was extremely significant for methanol production. Additionally, based on the cognition of the In2O3 active site and the reaction path of CO2 hydrogenation over In2O3, strategies were adopted to improve the catalytic performance, including (i) metal doping to enhance the adsorption and dissociation of hydrogen, improve the ability of hydrogen spillover, and form a special metal-In2O3 interface, and (ii) hybrid with other metal oxides to improve the dispersion of In2O3, enhance CO2 adsorption capacity, and stabilize the key intermediates. Lastly, some suggestions in future research were proposed to enhance the catalytic activity of In2O3-based catalysts for methanol production. The present review is helpful for researchers to have an explicit version of the research status of In2O3-based catalysts for CO2 hydrogenation to methanol and the design direction of next-generation catalysts.

Design of Ti-Pt Co-doped α-Fe2O3 photoanodes for enhanced performance of photoelectrochemical water splitting.

This study demonstrates Ti and Pt co-doping can synergistically improve the PEC performance of the α-Fe2O3 photoanode. By varying the doping methods, the sample with in-situ Ti ex-situ Pt doping (Tii-Pte) exhibits the best performance. It demonstrates that Ti doping in bulk facilities charge separation and Pt doping on the surface further accelerates charge transfer. In contrast, Ti doping on the surface inhibits charge separation, and Pt doping in bulk hinders charge separation and transfer. HCl treatment is used to minimize the onset potential further, while it is favorable for the ex-situ doped α-Fe2O3, which is more efficient on Tie than the Pte-doped ones. On the ex-situ Ti-doped α-Fe2O3 after HCl treatment, anatase TiO2 is probed, suggesting that Ti-O bonds accumulate when Fe-O bonds are partly removed, which enhances the charge transfer in surface states. Unfortunately, HCl treatment also induces lattice defects that are adverse to charge transport, inhibiting the performance of in-situ doped α-Fe2O3 and excessively treated ex-situ doped ones. Coupled with methanol solvothermal treatment and NiOOH/FeOOH cocatalysts loading, the optimized Ti-Pt/Fe2O3 photoanode exhibits an impressive photocurrent density of 2.81 mA cm-2 at 1.23 V vs. RHE and a low onset potential of 0.60 V vs. RHE.

Construction of Immobilized Enzymes with Yeast and Metal-Organic Frameworks for Enhanced Biocatalytic Activities.

Metal-organic frameworks (MOFs) have become promising host materials for enzyme immobilization and protection. Herein, ZIF-8 nanocubes were successfully self-assembled onto yeast as a biological template to obtain hybrid Y@ZIF-8. The size, morphology, and loading efficiency of ZIF-8 nanoparticles assembled on yeast templates can be well-regulated by adjusting the various synthetic parameters. Particularly, the amount of water significantly affected the particle size of ZIF-8 assembled on yeast. Through using a cross-linking agent, the relative enzyme activity of Y@ZIF-8@t-CAT could be greatly enhanced and remained the highest even after seven consecutive cycles, with improved cycling stability, as compared to that of Y@ZIF-8@CAT. In addition to the effect of the physicochemical properties of Y@ZIF-8 on the loading efficiency, the temperature tolerance, pH tolerance, and storage stability of Y@ZIF-8@t-CAT were also systematically investigated. Importantly, the catalytic activity of free catalase was decreased to 72% by 45 days, while the activity of the immobilized catalase remained above 99%, suggesting good storage stability. The present work demonstrates that yeast-templated ZIF-8 nanoparticles have a high potential to be used as biocompatible immobilization materials and are promising candidates for the preparation of effective biocatalysts in biomedicine applications.

Fabrication of supported Pt/CeO2 nanocatalysts doped with different elements for CO oxidation: theoretical and experimental studies.

Supported Pt/CeO2 catalysts have been widely used in carbon monoxide (CO) oxidation; however, the high oxygen vacancy formation energy (Evac) in the process leads to the poor performance of these catalysts. Herein, we explored different element (Pr, Cu, or N) doped CeO2 supports using Ce-based metal-organic frameworks (MOFs) as precursors via calcination treatment. The obtained CeO2 supports were used to load Pt nanoparticles. These catalysts were systematically characterized by various techniques, and they showed superior catalytic activity for CO oxidation compared to undoped catalysts which could be attributed to the formation of Ce3+, and high amounts of Oads/(Oads + Olat) and Ptδ+/Pttotal. Moreover, density functional theory calculations with on-site Coulomb interaction correction (DFT+U) were performed to provide atomic-scale insights into the reaction process by the Mars-van Krevelen (M-vK) mechanism, which revealed that the element-doped catalysts could simultaneously reduce the adsorption energies of CO and lower reaction energy barriers in the *OOCO associative pathway.

Enhancement in the photoelectrochemical performance of BiVO4 photoanode with high (040) facet exposure.

Morphology and geometrical dimensions play crucial roles in the photoelectrochemical (PEC) performance of bismuth vanadate (BiVO4) for water splitting. Decahedral BiVO4 was synthesized through a facile hydrothermal process, which exhibited superior charge injection efficiency to the nanoporous counterpart prepared by the traditional method. More importantly, the crystal size and facet proportion of BiVO4 decahedrons were facilely controlled. The charge separation efficiency can be significantly improved with a reduction in the crystal size and an increase in (040) facet exposure. A new method was developed for rate law analysis: illumination intensity-modulated oxygen evolution reaction rate versus open circuit potential difference, which suggested that the surface reaction kinetics was not affected by facet regulation. Furthermore, after decorating the FeOOH and NiOOH as dual oxygen evolution cocatalysts, an enhanced photocurrent density of 3.2 mA cm-2 at 1.23 V versus reversible hydrogen electrode and interfacial charge injection efficiency of 97.0% can be reached. Our work inspires the development of facet-regulated BiVO4 photoanodes with high charge injection efficiency in the PEC field and provides a feasible route to enhance its charge separation efficiency.

Biocompatible 2D Cu-TCPP Nanosheets Derived from Cu2O Nanocubes as Multifunctional Nanoplatforms for Combined Anticancer Therapy.

Two-dimensional (2D) metal-organic frameworks (MOFs) could serve as multifunctional nanoplatforms to load small-molecule drugs and enzyme-mimicking nanoparticles (NPs) with a high efficiency for combined cancer therapy. Herein, we have prepared novel 2D Cu-tetrakis (4-carboxyphenyl) porphyrin (TCPP) nanosheets with an average thickness of 1.2 ± 0.1 nm using Cu2O nanocubes (50 nm) as a template and solid copper ion supplier. Cu2O nanocubes can be consumed and hybridized with the obtained Cu-TCPP, depending on the molar ratio of Cu2O and TCPP linker. The resultant Cu2O/Cu-TCPP could serve as nanoplatforms for co-loading of Pt and Au NPs to construct multifunctional Cu2O/Cu-TCPP/(Pt-Au) nanomedicines, which showed a superior anticancer effect via multiple therapeutic modes. For instance, Cu(II)-TCPP can produce 1O2 in the presence of acidic H2O2 by the Russell mechanism and the intrinsic Cu(I) ions (derived from the residual Cu2O) could mediate a Fenton-like reaction in tumorous tissues to generate toxic hydroxyl radicals (•OH). Moreover, the loaded Pt NPs with catalase (CAT)-mimic activity could decompose hydrogen peroxide (H2O2) into O2 within the tumor cells, increasing the local O2 concentration, modulating the tumorous hypoxia atmosphere, and promoting the O2-dependent glucose oxidation reaction. Furthermore, Au NPs with glucose oxidase (GOx)-mimic activity could accelerate the consumption of glucose and cut nutrient supply to induce starvation therapy. Consequently, our designed 2D MOF-based therapeutic nanomedicines would be a promising candidate for future smart and combined cancer therapy.

Cobalt Phthalocyanine Supported on Mesoporous CeO2 as an Active Molecular Catalyst for CO Oxidation.

Heterogenization of biomolecules by immobilizing on a metal oxide support could greatly enhance their catalytic activity and stability, but their interactions are generally weak. Herein, cobalt phthalocyanine (CoPc) molecules were firmly anchored on a Ce-based metal-organic framework (Ce-BTC) due to π-π stacking interaction between CoPc and aromatic frameworks of the BTC linker, which was followed by a calcination treatment to convert Ce-BTC to mesoporous CeO2 and realize a molecular-level dispersion of CoPc on the surface of CeO2. Various characterization results confirm the successful fabrication of molecular-based CoPc/CeO2 catalysts which exhibited good CO oxidation performance. Importantly, we found that the mixing manner of Ce-BTC and CoPc remarkably affects the physicochemical properties which then determined the catalytic performance of the resultant CoPc/CeO2 catalysts. In contrast, the direct physical mixing of CoPc and CeO2 led to poor performance toward CO oxidation, manifesting that the Ce-BTC-mediated CoPc loading strategy is promising for the heterogenization of catalytic biomolecules.

3D printing of recombinant Escherichia coli/Au nanocomposites as agitating paddles towards robust catalytic reduction of 4-nitrophenol.

Three-dimensional (3D) printing technology has received remarkable attention in manufacturing catalysts with tailored shapes and high precision, particularly facilitating catalyst recovery, maximizing heat/mass transfer, as well as enhancing catalytic performance. Herein, an engineered recombinant Escherichia coli strain (denoted as e-E. coli) with overexpressing metallothionein (a metal-binding protein) was explored to synthesize Au nanoparticles serving as both reducing and stabilizing agents. Then, the mixed inks containing e-E. coli/Au composite and biocompatible polymers (sodium alginate and gelatin) were extruded based on a direct ink writing method followed by chemical crosslinking to form robust 3D grids with square symmetry. To boost the mass transfer and minimize pressure drop, the monolith catalysts were assembled into agitating paddles and used for liquid-phase batch reactions (volume: 1 L). As such, the reaction solutions were mixed internally via the powered "catalytic paddles" with high mechanical strength, excellent reactivity, and easy recyclability, which could be reused at least 7 cycles without performance loss. Our work provides a novel strategy for the fabrication of supported Au catalysts, and the proof-of-concept "catalytic paddles" by 3D printing technology can be applied to other industrial solution-based reactions.

Structure engineering of alveoli-like ZSM-5 with encapsulated Pt nanoparticles for the enhanced benzene oxidation.

Inspired by the alveolar configuration, an alveoli-like ZSM-5 and the corresponding platinum encapsulated nanocomposite (Pt@PZ5) were fabricated via a dual-template method and a controlled selective desilication-recrystallization strategy. The dimensions of the central cavity, interconnected zeolitic vesicles, and mesoporous shell could be tuned by adjusting the synthesis parameters, as verified by scanning electron microscopy, transmission electron microscopy, nitrogen physisorption investigations, X-ray photoelectron spectroscopy, and X-ray diffraction techniques. Thanks to these properties and merits, the alveoli-like Pt@PZ5 showed the highest catalytic performance with excellent stability, obtaining 100% benzene conversion at 180 °C. Adsorption experiments combined with a finite-element simulation study uncovered that the alveolar architecture could expedite the accumulation of reactants and boost mass transfer; the conversion of intermediates in the voids could be further facilitated, giving optimal catalytic performance. Additionally, the alveolar architecture is resistant to metal sintering (5-20 nm) and leaching, even after calcination at 850 °C for 360 min. This work provides an alveolar concept into the rational design of efficient catalysts for fundamental catalytic action.

Semi-hydrogenation of α,ß-unsaturated aldehydes over sandwich-structured nanocatalysts prepared by phase transformation of thin-film Al2O3 to Al-TCPP.

The semi-hydrogenation of α,ß-unsaturated aldehydes to the desired unsaturated alcohols with both high conversion and high selectivity remains a big challenge. Herein, we designed a sandwich-structured nanocatalyst for the highly selective hydrogenation of various α,ß-unsaturated aldehydes (e.g., cinnamaldehyde, furfural, crotonaldehyde, and 3-methyl-2-butenal) to the targeted unsaturated alcohols. Highly accessible platinum nanoparticles were sandwiched between a metal-organic framework (MOF) core (i.e., MIL-88B(Fe)) and a MOF shell (i.e., Al-TCPP). In particular, the growth of the Al-TCPP shell was achieved by atomic layer deposition (ALD) of thin-film Al2O3 followed by phase transformation with a tetrakis(4-carboxyphenyl)porphyrin (H4TCPP) linker. The thickness of the Al-TCPP shell can be finely controlled by adjusting the cycle number of alumina ALD and the concentration of the H4TCPP linker during the phase transformation of Al2O3 to Al-TCPP. It was proven that the permeable MOF shells could serve as selectivity regulators for the activation of the CO bonds in α,ß-unsaturated aldehydes (in preference to the CC bonds), leading to higher selectivity towards unsaturated alcohols as compared to the conventional surface supported Pt catalysts. Mechanistic insights showed that the enhanced catalytic performance was attributed to (i) the modified electronic state of sandwiched Pt nanoparticles by the two MOF layers and (ii) the steric hindrance effect on substrate diffusion through the sandwich-structured catalysts.

Fabrication of Versatile Hollow Metal-Organic Framework Nanoplatforms for Folate-Targeted and Combined Cancer Imaging and Therapy.

Metal-organic frameworks (MOFs) have received extensive attention in the field of biomedicine, particularly serving as multifunctional theranostic nanoplatforms by integrating chemodrugs, imaging agents, and targeting agents. Herein, we report a facile strategy for the fabrication of a hollow and monodisperse MOF (denoted hMIL-88B(Fe)@ZIF-8) consisting of ZIF-8 nanoparticles loaded on the external shell of hollow MIL-88B(Fe). In particular, the hybrid hollow MOF was constructed by partially etching spindlelike MIL-88B(Fe) nanoparticles with 2-methylimidazole in the presence of zinc ions. The obtained hMIL-88B(Fe)@ZIF-8 was then used as a drug/cargo delivery vehicle for loading doxorubicin (DOX), manganese oxide (MnOx) nanoparticles, and folic acid (FA), forming a multifunctional nanoplatform (denoted hM@ZMDF). Importantly, the resulting hM@ZMDF exhibited a specific targeting property for the FA receptor-overexpressed cancer cells (MCF-7 and HepG-2 cells) and then it unloaded DOX and Fe3+ in the tumor microenvironment. Consequently, DOX played dual roles as a chemotherapeutic drug and a fluorescent imaging agent. Also, the released Fe3+ could mediate the Fenton reaction and intracellularly generate toxic hydroxyl radicals in the presence of high glutathione in cancer cells. In addition, MnOx nanoparticles could participate in magnetic resonance imaging. Therefore, the versatile hM@ZMDF nanoplatforms have great potential for smart cancer therapy.

Metal oxide/CeO2 nanocomposites derived from Ce-benzene tricarboxylate (Ce-BTC) adsorbing with metal acetylacetonate complexes for catalytic oxidation of carbon monoxide.

Herein, a series of metal oxide/CeO2 (M/CeO2) nanocomposites derived from Ce-benzene tricarboxylate (Ce-BTC) adsorbing with different metal acetylacetonate complexes were prepared for CO oxidation under four different CO gas atmospheres. It was demonstrated that Cu/CeO2 exhibited the highest catalytic activity and stability in CO oxidation. Remarkably, both O2 selectivity and CO selectivity to CO2 are 100% in most of the investigated conditions. Several analytical tools such as N2 adsorption-desorption and powder X-ray diffraction, were employed to characterize the prepared catalysts. In addition, the excellent catalytic performance of Cu/CeO2 in CO oxidation was revealed by H2 temperature-program reduction experiment, X-ray photoelectron spectroscopy, and in situ diffuse reflectance infrared Fourier transform spectroscopy. The result showed that high oxygen vacancy and high CO adsorption capacity (Cu+-CO) caused by the electron exchanges of Cu2+/Cu+ and Ce3+/Ce4+ pairs (Ce4+ + Cu+ ⇆ Ce3+ + Cu2+) are two key factors contributing to the high oxidation performance of Cu/CeO2 catalyst.

Improving light absorption and photoelectrochemical performance of thin-film photoelectrode with a reflective substrate.

The charge separation/transport efficiency is relatively high in thin-film hematite photoanodes in which the distance for charge transport is short, but simultaneously the high loss of light absorption due to transmission is confronted. To increase light absorption in thin-film Fe2O3:Ti, commercial substrates such as Cu foil, Ag foil, and a mirror are adopted acting as back-reflectors and individually integrated with the Fe2O3:Ti electrode. The promotion effect of the commercial back-reflectors on the light absorption efficiency and photoelectrochemical (PEC) performance of the hydrothermally prepared Fe2O3:Ti electrodes with a variety of film thicknesses is investigated. As a result, Ag foil and the mirror show favorable and equal efficacy while the promoting effect of Cu foil is limited. In addition, the photocurrent increment achieved by the Ag back-reflector decreases linearly along with the logarithmic of the film thickness and the optimized film thickness of the Fe2O3:Ti electrode is decreased from 520 to 290 nm. The high durability of Ag foil in the alkaline electrolyte during solar light irradiation is demonstrated. Furthermore, the reflective substrate also shows a promotion effect on the BiVO4 photoanode and CuBi2O4 photocathode, as well as the unbiased photocurrent from a tandem cell constituted by TiO2 and CuBi2O4.

Intercalation of laminar Cu-Al LDHs with molecular TCPP(M) (M = Zn, Co, Ni, and Fe) towards high-performance CO2 hydrogenation catalysts.

A confined space is broadly applied to enhance the dispersion and limit the aggregation of catalytically active sites, especially at high temperatures. In this work, we provided an efficient approach to immobilize transition metal ions (e.g., Zn2+, Co2+, Ni2+, and Fe2+) into the confined space of laminar Cu-Al layered double hydroxides (LDHs) using a range of molecular metalloporphyrins (viz., TCPP(M)) as shuttles. The deprotonated TCPP(M) not only provides nitrogen-based coordination sites to anchor a series of transition metal ions, but also intercalates and diffuses facilely into the interlayer gallery of LDHs by ion exchange. The obtained TCPP(M)@Cu-Al LDHs were then used as solid precursors for the fabrication of a series of heterogeneous catalysts for CO2 hydrogenation via high-temperature calcination. Two restriction forces contributed to the enhanced dispersion of the active species over the catalyst surface structures. Remarkably, the transition metals positioned within the confined space of LDHs significantly affected the catalytic performance of CO2 hydrogenation. Mainly CO, methanol, and methane were found as the C1 products, and their selectivities are highly dependent on the reaction intermediates, as suggested by the in situ DRIFTS study. Moreover, the designed catalysts fabricated via molecular TCPP(M) intercalation exhibited much better performance than the conventional catalysts derived from surface-supported CA-LDHs, due to their better metal dispersion and smaller particle size.