Porous Materials Research Articles

Hierarchical porous carbon materials for lithium storage: Preparation, modification, and applications.

Secondary battery as an efficient energy conversion device have been highly attractive for alleviating the energy crisis and environmental pollution. Hierarchical porous carbon materials with multiple sizes pore channels are considered as promising materials for energy conversion and storage applications, due to their high specific surface area and excellent electrical conductivity. Although many reviews have reported on carbon materials for different fields, systematic summaries about hierarchical porous carbon materials for lithium storage are still rare. In this review, we fist summarize the main preparation methods of hierarchical porous carbon materials, including hard template method, soft template method, and template-free method. The modification methods including porosity and morphology tuning, heteroatom doping, and multiphase composites are introduced systematically. Then, the recent advances in hierarchical porous carbon materials on lithium storage are summarized. Finally, we outline the challenges and future perspectives for the application of hierarchical porous carbon materials in lithium storage.

Catalytic activity of Ni–Cr–Fe–Mo porous materials for hydrogen evolution reaction in alkaline media

The hydrogen evolution reaction (HER) based on water electrolysis represents an ideal approach for hydrogen production. The advancement of highly active non-precious metal catalysts holds paramount importance. This research employed powder metallurgy sintering to prepare Ni–Cr–Fe and Ni–Cr–Fe–Mo porous materials. It investigated the impact of Mo doping and sintering temperature on the catalytic activity and microstructural influence of hydrogen evolution materials. Furthermore, the materials' electrochemical performance and long-term stability in 6 mol/L KOH were examined. In complicated systems, the current work provides a feasible method for producing hydrogen from Ni–Cr–Fe–Mo porous materials in a strong alkali environment. The results exhibited that when Mo content is 5% and the sintering temperature is 800 °C, the porosity of Ni–Cr–Fe–Mo porous materials is up to 39.9% and the catalytic activity is up to 97%. At the same time, the current density decays to 7.1% after 1000 cycles of electrolysis and shows good HER stability after 48 h. The enhanced catalytic activity for hydrogen evolution emanated from the positive synergy among the transition metal elements.

Effects of porous structure and oxygen functionalities on electrochemical synthesis of hydrogen peroxide on ordered mesoporous carbon

Two-electron oxygen reduction reaction (2e− ORR) is a promising alternative to energy-intensive anthraquinone process for hydrogen peroxide (H2O2) production. Metal-free nanocarbon materials have garnered intensive attention as highly prospective electrocatalysts for H2O2 production, and an in-depth understanding of their porous structure and active sites have become a critical scientific challenge. The present research investigates a range of porous carbon catalysts, including non-porous, microporous, and mesoporous structures, to elucidate the impacts of porous structures on 2e− ORR activity. The results highlighted the superiority of mesoporous carbon over other porous materials, demonstrating remarkable H2O2 selectivity. Furthermore, integration of X-ray photoelectron spectroscopy (XPS) data analysis with electrochemical assessment results unravels the moderate surface oxygen content is the key to increase 2e− ORR activity. These results not only highlight the intricate interplay between pore structure and oxygen content in determining catalytic selectivity, but also enable the design of carbon catalysts for specific electrochemical reactions.

Deciphering Mechanisms of CO2-Selective Recognition over Acetylene within Porous Materials

Deciphering Mechanisms of CO₂-Selective Recognition over Acetylene within Porous Materials

An Alkyne-bridged Covalent Organic Framework Featuring Interactive Pockets for Bromine Capture.

The high degree of corrosivity and reactivity of bromine, which is released from various sources poses a serious threat to the environment. Moreover, its coexistence with iodine forming an equilibrium compound, iodine monobromide (IBr) necessitates the selective capture of bromine from halogen mixtures. The electrophilicity of halogens to π-electron rich structures enabled us to strategically design a covalent organic framework for halogen capture, featuring a defined pore environment with localized sorption sites. The higher capture capacity of bromine (4.6gg-1) over iodine by ~41% shows its potential in selective capture. Spectroscopic results uncovering the preferential interaction sites are supported by theoretical investigations. The alkyne bridge is a core functionality promoting the selectivity in capture by synergistic physisorption, rationalized by the higher orbital overlap of bromine due to its smaller atomic size as well as reversible chemical interactions. The slip stacking in the structure has further promoted this phenomenon by creating clusters of molecular interaction sites with bromine intercalated between the layers. The inclusion of unsaturated moieties, i.e. triple bonds and the complementary pore geometry offer a promising design strategy for the construction of porous materials for halogen capture.

Isomeric Porous Cu(I) Triazolate Frameworks Showing Periodic and Aperiodic Flexibility for Efficient CO Separation.

Guest-induced (crystal-to-crystal) transformation, i.e., periodic flexibility, is a typical feature of molecule-based crystalline porous materials, but its role for adsorptive separation is controversial. On the other hand, aperiodic flexibility is rarely studied. This work reports a pair of isomeric Cu(I) triazolate frameworks, namely, α-[Cu(fetz)] (MAF-2Fa) and β-[Cu(fetz)] (MAF-2Fb), which show typical periodic and aperiodic flexibility for CO chemical adsorption, respectively. Quantitative mixture breakthrough experiments show that, while MAF-2Fa exhibits high adsorption capacity at high pressures but negligible adsorption below the threshold pressure and with leakage concentrations of 3-8%, MAF-2Fb exhibits relatively low adsorption capacity at high pressures but no leakage (residual CO concentration <1 ppb). Tandem connection of MAF-2Fa and MAF-2Fb can combine their advantages of high CO adsorption capacities at high and low pressures, respectively. MAF-2Fa and MAF-2Fb can both keep the separation performances unchanged at high relative humidities, but only MAF-2Fb shows a unique coadsorption behavior at a relative humidity of 82%, which can be used to improve purification performances.

An Alkyne‐bridged Covalent Organic Framework Featuring Interactive Pockets for Bromine Capture

The high degree of corrosivity and reactivity of bromine, which is released from various sources poses a serious threat to the environment. Moreover, its coexistence with iodine forming an equilibrium compound, iodine monobromide (IBr) necessitates the selective capture of bromine from halogen mixtures. The electrophilicity of halogens to π‐electron rich structures enabled us to strategically design a covalent organic framework for halogen capture, featuring a defined pore environment with localized sorption sites. The higher capture capacity of bromine (4.6 g g‐1) over iodine by ~41 % shows its potential in selective capture. Spectroscopic results uncovering the preferential interaction sites are supported by theoretical investigations. The alkyne bridge is a core functionality promoting the selectivity in capture by synergistic physisorption, rationalized by the higher orbital overlap of bromine due to its smaller atomic size as well as reversible chemical interactions. The slip stacking in the structure has further promoted this phenomenon by creating clusters of molecular interaction sites with bromine intercalated between the layers. The inclusion of unsaturated moieties, i.e. triple bonds and the complementary pore geometry offer a promising design strategy for the construction of porous materials for halogen capture.

Photocatalytic Degradation of Quinolones by Magnetic MOFs Materials and Mechanism Study

With the rising incidence of various diseases in China and the constant development of the pharmaceutical industry, there is a growing demand for floxacin-type antibiotics. Due to the large-scale production and high cost of waste treatment, the parent drug and its metabolites constantly enter the water environment through domestic sewage, production wastewater, and other pathways. In recent years, the pollution of the aquatic environment by floxacin has become increasingly serious, making the technology to degrade floxacin in the aquatic environment a research hotspot in the field of environmental science. Metal–organic frameworks (MOFs), as a new type of porous material, have attracted much attention in recent years. In this paper, four photocatalytic materials, MIL-53(Fe), NH2-MIL-53(Fe), MIL-100(Fe), and g-C3N4, were synthesised and applied to the study of the removal of ofloxacin and enrofloxacin. Among them, the MIL-100(Fe) material exhibited the best photocatalytic effect. The degradation efficiency of ofloxacin reached 95.1% after 3 h under visible light, while enrofloxacin was basically completely degraded. The effects of different materials on the visible photocatalytic degradation of the floxacin were investigated. Furthermore, the photocatalytic mechanism of enrofloxacin and ofloxacin was revealed by the use of three trappers (®O2−, h+, and ®OH), demonstrating that the role of ®O2− promoted the degradation effect of the materials under photocatalysis.

In Situ Laser-Induced 3D Porous Graphene within Transparent Polymers for Encapsulation-Free and Tunable Ultrabroadband Terahertz Absorption.

Three-dimensional (3D) porous carbon materials have great potential for fabricating flexible tunable broadband absorbers owing to their high electrical conductivity, strong dielectric loss, and unique microstructure. Herein, we introduce an innovative method for synthesizing 3D porous graphene that incorporates advanced tuning and encapsulation processes to augment its functional efficacy. Through the modulation of both thermal and nonthermal interactions between a femtosecond (fs) laser and a polydimethylsiloxane (PDMS) film, we have synergistically fine-tuned the surface morphology and lattice properties of 3D porous graphene. This approach enabled us to create a flexible terahertz (THz) absorber with customizable characteristics, boasting an impressive absorbance range of 80%-99% in the 0.4-1.0 THz spectrum, alongside a peak reflection loss (RL) of up to 35.6 dB. Furthermore, we have successfully demonstrated the production of photoinduced 3D porous graphene within a PDMS film, which serves as both a carbon precursor and protective layer. This simplifies the conventional packaging process. These devices exhibit a RL of up to 41.6 dB and an absorption bandwidth of 2.5 THz (0.6-3.1 THz). Our study presents a production methodology for high-performance, flexible THz absorbers, offering a straightforward and innovative solution for the rapid development of sophisticated, flexible THz absorbing materials.

Preparation and Investigation of High Surface Area Aerogels from Crosslinked Polypropylenes

Polypropylene-based aerogels with high surface area have been developed for the first time. By chemical crosslinking of polypropylene with oligomeric capped-end amino compounds, followed by dissolution, thermally induced phase separation, and the supercritical CO2 drying process or freeze-drying method, the aerogels exhibit high specific surface areas up to 200 m2/g. Moreover, the silica-cage multi-amino compound was utilized in a similar vein for forming hybrid polypropylene aerogels. According to the SEM, the developed polypropylene-based aerogels exhibit highly porous morphology with micro-nanoscale structural features that can be controlled by processing conditions. Our simple and inexpensive synthetic strategy results in a low-cost, chemically resistant, and highly porous material that can be tailored according to end-use applications.

Diffusion in Porous Rock Is Anomalous.

Molecular diffusion of chemical species in subsurface environments─rock formations, soil sediments, marine, river, and lake sediments─plays a critical role in a variety of dynamic processes, many of which affect water chemistry. We investigate and demonstrate the occurrence of anomalous (non-Fickian) diffusion behavior, distinct from classically assumed Fickian diffusion. We measured molecular diffusion through a series of five chalk and dolomite rock samples over a period of about two months. We demonstrate that in all cases, diffusion behavior is significantly different than Fickian. We then analyze the results using a continuous time random walk framework that can describe anomalous diffusion in heterogeneous porous materials such as rock. This methodology shows extreme long-time tailing of tracer advance as compared to conventional Fickian diffusion processes. The finding that distinct anomalous diffusion occurs ubiquitously implies that diffusion-driven processes in subsurface zones should be analyzed using tools that account for non-Fickian diffusion.

Utilizing banana peel in conjunction with TiO2 photocatalyst for the efficient decolorization of malachite green

Porous materials are frequently integrated into TiO2 photocatalysts due to their enhanced surface area and reaction efficiency. This study aimed to enhance the efficiency of wastewater treatment by developing a TiO2 combined with banana peel (BP) through the sol-gel method. The TiO2/BP composite was extensively analyzed using a range of methods, such as X-ray diffraction (XRD), field emission transmission electron microscopy (FESEM), energy dispersive X-ray (EDX) analysis, diffuse reflectance spectroscopy (DRS UV–vis), photoluminescence spectra (PL), and Brunauer–Emmett–Teller (BET) analysis. Subsequent evaluation of the photoactivity of the TiO2/BP composite compared to bare TiO2 particles revealed a noteworthy enhancement in decolorizing malachite green (MG) dye under visible light. Furthermore, recyclability testing further demonstrated consistent performance for up to four cycles, highlighting the potential application of this porous material-based photocatalytic composite in wastewater treatment.

Mathematical modelling of impurity deposition during evaporation of dirty liquid in a porous material

When a contaminated liquid evaporates from within a porous material, the impurities or dirt accumulate and deposit within the pore space. This occurs during the cleaning of filters and fouling of textiles, and is related to the ‘coffee-ring’ problem. To investigate how and where dirt is deposited in the pore space, we present a model for the motion of an evaporation front through a porous material, and the related accumulation, transport, and deposition of dirt, assuming that the liquid remains stationary. For physically relevant parameters, vapour transport out of the porous material is quasi-steady and we derive a single ordinary differential equation describing the motion of the evaporation front in time. Model solutions exhibit spatially non-uniform profiles of the deposited dirt-layer thickness through the porous material. The dirt accumulation and evaporation problems are coupled: deposited dirt hinders vapour transport through the porous material, slowing the evaporation. We identify two scenarios in which the porous material becomes clogged with dirt. Accumulation of suspended dirt at the evaporating interface along with slow dirt diffusion results in the deposited dirt layers clogging the pores at the evaporating interface, halting the drying and trapping liquid in the porous material. Alternatively, slow dirt deposition results in the suspended dirt being pushed far into the porous material by the evaporation, eventually leaving only dirt (with no liquid) in the pore space. We investigate the dynamics of both clogging scenarios, characterising the parameter regimes for which each occurs. Both clogging scenarios must be avoided in practice since they may be detrimental to future filter efficacy or textile breathability.

Porous Organic Framework Materials (MOF, COF, and HOF) as the Multifunctional Separator for Rechargeable Lithium Metal Batteries.

The separator is an important component in batteries, with the primary function of separating the positive and negative electrodes and allowing the free passage of ions. Porous organic framework materials have a stable connection structure, large specific surface area, and ordered pores, which are natural places to store electrolytes. And these materials with specific functions can be designed according to the needs of researchers. The performance of porous organic framework-based separators used in rechargeable lithium metal batteries is much better than that of polyethylene/propylene separators. In this paper, thethree most classic organic framework materials (MOF, COF, and HOF) are analyzed and summarized. The applications of MOF, COF, and HOF separators in lithium-sulfur batteries, lithium metal anode, and solid electrolytes are reviewed. Meanwhile, the research progress of these three materials in different fields is discussed based on time. Finally, in the conclusion, the problems encountered by MOF, COF, and HOF in different fields as well as their future research priorities are presented. This review will provide theoretical guidance for the design of porous framework materials with specific functions and further stimulate researchers to conduct research on porous framework materials.

Analysis of COF-300 synthesis: probing degradation processes and 3D electron diffraction structure.

Although COF-300 is often used as an example to study the synthesis and structure of (3D) covalent organic frameworks (COFs), knowledge of the underlying synthetic processes is still fragmented. Here, an optimized synthetic procedure based on a combination of linker protection and modulation was applied. Using this approach, the influence of time and temperature on the synthesis of COF-300 was studied. Synthesis times that were too short produced materials with limited crystallinity and porosity, lacking the typical pore flexibility associated with COF-300. On the other hand, synthesis times that weretoo long could be characterized by loss of crystallinity and pore order by degradation of the tetrakis(4-aminophenyl)methane (TAM) linker used. The presence of the degradation product was confirmed by visual inspection, Raman spectroscopy and X-ray photoelectron spectroscopy (XPS). As TAM is by far the most popular linker for the synthesis of 3D COFs, this degradation process might be one of the reasons why the development of 3D COFs is still lagging compared with 2D COFs. However, COF crystals obtained via an optimized procedure could be structurally probed using 3D electron diffraction (3DED). The 3DED analysis resulted in a full structure determination of COF-300 at atomic resolution with satisfying data parameters. Comparison of our 3DED-derived structural model with previously reported single-crystal X-ray diffraction data for this material, as well as parameters derived from the Cambridge Structural Database, demonstrates the high accuracy of the 3DED method for structure determination. This validation might accelerate the exploitation of 3DED as a structure determination technique for COFs and other porous materials.

Unifying O(3) Equivariant Neural Networks Design with Tensor-Network Formalism

Abstract Many learning tasks, including learning potential energy surfaces from ab initio calculations, involve global spatial symmetries and permutational symmetry between atoms or general particles. Equivariant graph neural networks are a standard approach to such problems, with one of the most successful methods employing tensor products between various tensors that transform under the spatial group. However, as the number of different tensors and the complexity of relationships between them increase, maintaining parsimony and equivariance becomes increasingly challenging. In this paper, we propose using fusion diagrams, a technique widely employed in simulating SU($2$)-symmetric quantum many-body problems, to design new equivariant components for equivariant neural networks. This results in a diagrammatic approach to constructing novel neural network architectures. When applied to particles within a given local neighborhood, the resulting components, which we term "fusion blocks," serve as universal approximators of any continuous equivariant function defined on the neighborhood. We incorporate a fusion block into pre-existing equivariant architectures (Cormorant and MACE), leading to improved performance with fewer parameters on a range of challenging chemical problems. Furthermore, we apply group-equivariant neural networks to study non-adiabatic molecular dynamics of stilbene cis-trans isomerization and water adsorption cycles in porous materials, such as metal-organic frameworks. Our approach, which combines tensor networks with equivariant neural networks, suggests a potentially fruitful direction for designing more expressive equivariant neural networks.

Highly Efficient Capture of Volatile Iodine by Conjugated Microporous Polymers Constructed Using Planar 3- and 4-Connected Organic Monomers

The effective capture and recovery of radioiodine species associated with nuclear fuel reprocessing is of significant importance in nuclear power plants. Porous materials have been proven to be one of the most effective adsorbents for the capture of radioiodine. In this work, we design and synthesize a series of conjugated microporous polymers (CMPs), namely, TPDA–TFPB CMP, TPDA–TATBA CMP, and TPDA–TECHO CMP, which are constructed based on a planar rectangular 4-connected organic monomer and three triangular 3-connected organic monomers, respectively. The resultant CMPs are characterized using various characterization techniques and used as effective adsorbents for iodine capture. Our experiments indicated that the CMPs exhibit excellent iodine adsorption capacities as high as 6.48, 6.25, and 6.37 g g−1 at 348 K and ambient pressure. The adsorption mechanism was further investigated and the strong chemical adsorption between the iodine and the imine/tertiary ammonia of the CMPs, 3D network structure with accessible hierarchical pores, uniform micromorphology, wide π-conjugated structure, and high-density Lewis-base sites synergistically contribute to their excellent iodine adsorption performance. Moreover, the CMPs demonstrated good recyclability. This work provides guidance for the construction of novel iodine adsorbent materials with high efficiency in the nuclear power field.

Thickness-Driven Synthesis and Applications of Covalent Organic Framework Nanosheets.

Covalent organic frameworks (COFs) are two-dimensional, crystalline porous framework materials with numerous scopes of tunability like porosity, functionality, stability and aspect ratio (thickness to length ratio). The manipulation of π-stacking in COFs results in truly 2D materials, namely covalent organic nanosheets (CONs) adds advantages in many applications. In this review, we have discussed both top-down (COFs→CONs) and bottom-up (molecules→CONs) with precise information on thickness and lateral growth. We have showcased the research progress of CONs in few selected applications like batteries, catalysis, sensing and biomedical applications. This review specifically highlights the reports where the authors compare the performance of CONs with COFs by demonstrating the impact of thickness and lateral growth of the nanosheets. Eventually, we have provided the possible scope of exploration of CONs research in terms of inter-dimensional conversion like graphene to carbon nanotube and future technologies..

Thickness‐Driven Synthesis and Applications of Covalent Organic Framework Nanosheets

Covalent organic frameworks (COFs) are two‐dimensional, crystalline porous framework materials with numerous scopes of tunability like porosity, functionality, stability and aspect ratio (thickness to length ratio). The manipulation of π‐stacking in COFs results in truly 2D materials, namely covalent organic nanosheets (CONs) adds advantages in many applications. In this review, we have discussed both top‐down (COFs→CONs) and bottom‐up (molecules→CONs) with precise information on thickness and lateral growth. We have showcased the research progress of CONs in few selected applications like batteries, catalysis, sensing and biomedical applications. This review specifically highlights the reports where the authors compare the performance of CONs with COFs by demonstrating the impact of thickness and lateral growth of the nanosheets. Eventually, we have provided the possible scope of exploration of CONs research in terms of inter‐dimensional conversion like graphene to carbon nanotube and future technologies..

Photo-Responsive Hydrogen-Bonded Molecular Networks Capable of Retaining Crystalline Periodicity after Isomerization.

The molecular conformation, crystalline morphology, and properties of photochromic organic crystals can be controlled through photoirradiation, making them promising candidates for functional organic materials. However, photochromic porous molecular crystals with a networked framework structure are rare due to the difficulty in maintaining space that allows for photo-induced molecular motion in the crystalline state. This study describes a photo-responsive single crystal based on hydrogen-bonded (H-bonded) network of dihydrodimethylbenzo[e]pyrene derivative 4BDHP. A crystal composed of H-bonded undulate layers, 4BDHP-2, underwent photo-isomerization in the crystalline state due to loose stacking of the layers. Particularly, enantio-pure crystal (S,S)-4BDHP-2 allowed to reveal the structure of the photoisomerized crystal, in which the closed form (4BDHP) and open form (4CPD) were arranged alternately with keeping crystalline periodicity, although side reactions were also implied. The present proof-of-concept system of a photochromic framework that retains crystalline periodicity after photo-isomerization may provide new light-driven porous functional materials.