Hydrous Metal Research Articles

Generation-fusion strategy in metal-earth ionosome investigation using single-entity electrochemistry at the micro-water/trifluorotoluene interface

Ionosomes are water clusters/droplets formed in an organic phase via the spontaneous assembly of ionic bilayers by hydrated cations or anions. The ionosomes formed by monovalent ions, i.e., Li+, Na+, K+, Cl−, etc., have been thoroughly investigated. Herein, single nanowater clusters (viz. ionosomes) in organic solutions, which are formed by the transfer of metal earth cations (i.e., Mg2+, Ca2+, Ba2+) into organic lipophilic electrolytes, were discovered using single-entity electrochemistry (SEE). The generation-fusion strategy involving two-step potentiostatic chronoamperometry was applied to investigate single Mg2+-ionosomes at the water/α,α,α-trifluorotoluene (w/TFT) interface. After an exciting potential forced the hydrophilic ion into the organic phase, a train of current spikes with information on the integrated charges, frequency, and duration were recorded to gain insight into the ionosomes. Variates were thoroughly investigated, including the exciting potential, exciting time, recording potential, size of the applied w/TFT interface, ion species, and concentration. These results suggest that: (1) the size of a single Mg2+-ionosome was revealed; (2) the fleshly formed ionosomes are mainly located on the organic side of the w/TFT interfacial surface instead of diffusing into the organic bulk; (3) when the interface decreases, fewer ionosomes form, and the size of the ionosomes decreases; (4) the mean charge carried by a single ionosome is positively related to the charge density of a single cation; (5) by alternating the recording potential, the negative zeta potential of Mg2+-ionosomes was revealed; (6) Mg2+-ionosomes can form when the aqueous solution contains only 2 μmol·L−1 Mg2+. This work thoroughly investigated hydrated metal earth ion clusters in the organic phase via SEE and provides insights into the interface electric double layer from the electrochemistry perspective. In addition to promoting the understanding of ionosomes, this strategy can provide potential applications to identify high-purity water.

Construction of a Three-Phase MnS2/Co4S3/Ni3S2 Heterostructure for Boosting Oxygen Evolution.

The rational construction of highly efficient electrocatalysts for the oxygen evolution reaction (OER) plays a critical role in energy conversion systems. Designing heterostructures is a common and effective strategy to improve the performance of electrocatalysts. In this paper, an MnS2/Co4S3/Ni3S2 heterostructure was synthesized on Ni foam using a one-step vulcanization method. It provides a modified electronic structure and plentiful three-phase heterogeneous interfaces that can effectively enrich the active sites and accelerate electron transfer, thereby improving the OER activity. Thanks to the heterostructure, the MnS2/Co4S3/Ni3S2 exhibits a low overpotential of 265 and 304 mV for the OER to reach current densities of 50 and 100 mA/cm2, respectively. Furthermore, the surface reconstruction of MnS2/Co4S3/Ni3S2 has been investigated, which revealed the formation of metal hydr(oxy)oxides evolved during the OER process. This work provides a facile strategy for constructing three-phase heterostructures, shedding light on the development of high-performance, nonprecious metal-based OER electrocatalysts.

Study on hydration and heavy metal leaching of washed MSWI FA as a green cementitious material

Despite municipal solid waste incineration fly ash (MSWI FA) being classified as hazardous waste, there is a consensus on its significant potential for resource utilization. The high content of soluble chlorides in MSWI FA not only limits its co-disposal in cement kilns but also hinders its application in the field of construction materials. The research aimed to investigate the viability of MSWI FA as a binding material in the construction engineering field. Through examining the impact of liquid/solid ratio and pH levels on the chemical composition of MSWI FA during the washing procedure, the study delved into the mechanisms affecting hydration and the characteristics of heavy metal contamination before and after washing pretreatment. The results indicate the feasibility of developing MSWI FA into construction engineering materials. The liquid/solid ratio is a significant factor affecting the removal of chlorides, with an optimal ratio of 30. pH plays a crucial role in the mineral composition during the water-washing process of MSWI FA. An acidic environment can remove a higher proportion of chlorides, while an alkaline environment can form more calcium salts. The compressive strength of pure MSWI FA at 28 days is 3.92 MPa, which can be increased by 0.99 MPa after washing. The washed MSWI FA not only exhibits heightened reactivity but also demonstrates reduced leaching concentrations of heavy metals, and its leaching toxicity was much lower than the safe landfill threshold. Therefore, MSWI FA, after washing, is a very promising alternative material for construction engineering.

A complementary eco-friendly approach to heavy metal removal from wastewater/produced water streams through mineralization

With the world's ever-increasing population, portable water needs have significantly increased. This has put enormous pressure on the limited supply of freshwater around the globe and has necessitated the development of water treatment technologies that would convert saline waters into potable water for domestic and industrial uses. As saline water is treated for usage, so is wastewater generated from domestic and industrial processes. More prominently, another wastewater source is produced water consequent to oil production. Wastewater and produced water are similar in that they are both high in pollutants (heavy metals), which in discharge streams need to be kept within a threshold. The fact that heavy and rare earth metals linked to the produced water cannot be completely removed by state-of-the-art technologies is even more concerning. Thus, a complementary technology must be developed for this reason. This study investigates the mineralization of water-polluting heavy metals. The approach adopted involves the exposure of contaminated water to atmospheric or captured CO2 and the use of additives to achieve the removal. To gain a deeper understanding of how these innovative efforts function, the study also looked into the mechanism used to eliminate the heavy metals. The findings show that heavy metals in produced water and industrial effluent can be precipitated and immobilized to remove them. More so, this is made possible by the infusion of heavy metals into the crystal structures of precipitates like aragonite, calcite, and halite. Furthermore, the mechanism of the heavy metal removal involves their dehydration, immobilization and precipitation. Additionally, DFT calculations were utilized to support the experimental results by shedding light on the heavy metal hydration's ground-state structures and how EDTA chelates the heavy metals and enhances the process kinetics. The study's findings show how this strategy complements the most advanced wastewater treatment method in terms of increasing its efficiency and water security and safety. More so, as this is a pioneering effort, the optimum concentration of chelating agent and route (atmospheric or captured CO2) must be determined on a case-to-case basis for field implementation. Furthermore, the limitation of this study is that the efficiency of heavy metal removal may differ based on the starting brine composition, thus, optimization must be conducted beforehand.

Exploring the catalytic mechanism of the 10-23 DNAzyme: insights from pH-rate profiles.

The 10-23 DNAzyme, a catalytic DNA molecule with RNA-cleaving activity, has garnered significant interest for its potential therapeutic applications as a gene-silencing agent. However, the lack of a detailed understanding about its mechanism has hampered progress. A recent structural analysis has revealed a highly organized conformation thanks to the stabilization of specific interactions within the catalytic core of the 10-23 DNAzyme, which facilitate the cleavage of RNA. In this configuration, it has been shown that G14 is in good proximity to the cleavage site which suggests its role as a general base, by activating the 2'-OH nucleophile, in the catalysis of the 10-23 DNAzyme. Also, the possibility of a hydrated metal acting as a general acid has been proposed. In this study, through activity assays, we offer evidence of the involvement of general acid-base catalysis in the mechanism of the 10-23 DNAzyme by analyzing its pH-rate profiles and the role of G14, and metal cofactors like Mg2+ and Pb2+. By substituting G14 with its analogue 2-aminopurine and examining the resultant pH-rate profiles, we propose the participation of G14 in a catalytically relevant proton transfer event, acting as a general base. Further analysis, using Pb2+ as a cofactor, suggests the capability of the hydrated metal ion to act as a general acid. These functional results provide critical insights into the catalytic strategies of RNA-cleaving DNAzymes, revealing common mechanisms among nucleic acid enzymes that cleave RNA.

Latent heat absorption of alkali metal hydrates enables delayed ignition and improved flame retardancy of epoxy resin

In this work, alkali metal hydrates, barium hydroxide octahydrate (BHO) and sodium acetate trihydrate (SAT) were added into epoxy resin (EP) to prepare a series of flame-retardant EP composites. It showed that EP samples can pass the V-0 rating of UL-94 when the amount of hydrated salt exceeds 45 wt%. When the additional amount of SAT is 50 wt%, the LOI of the EP sample increases to as high as 39% compared to 19% of pure EP. In addition, the time to ignition (TTI) of EP with 50 wt% SAT was prolonged to 157 s from 63 s of pure EP, which can provide valuable time for fire escape. The peak heat release rate (PHRR) was reduced by 63.9% compared with that of pure EP (from 1392.4 kW/m2 to 502.18 kW/m2), which indicated that phase change heat absorption plays a crucial role in reducing fire hazards of EP.

Recent Advances in High‐Performance Direct Seawater Electrolysis for “Green” Hydrogen

Electrocatalytic water splitting through the electrolyzer is the most promising strategy for hydrogen production. Recently, water electrolysis is mainly based on high‐purity freshwater, which not only consumes a large number of freshwater resources but also improves the overall cost due to the extra water purification system. Hence, direct electrolysis of seawater is more desirable for large‐scale hydrogen generation. As is known, the dominant rate‐determining step of overall water splitting is the anodic oxygen evolution reaction (OER), which involves four‐electron transfer and owns a much larger overpotential than cathodic hydrogen evolution reaction. The large challenge for the design of OER catalysts in the seawater media is the competition reaction between OER and chloride oxidation reaction, which greatly influences energy efficiency. Hence, except for the activity and stability, selectivity is another key point for seawater splitting. Herein, after a brief introduction of two half reactions for water splitting, the latest metal hydr(oxide) electrocatalysts with different crystalline structures are summarized according to the previous reports. Moreover, the advantages and disadvantages of three common water electrolyzers are compared. Finally, the perspectives of seawater electrolysis for hydrogen production are outlined for practical applications.

Study of magnetic, thermoelectric, and mechanical properties of double perovskites Be2XH6 (X = Cr and Mn) for spintronic and hydrogen-storage applications

Metal hydrides are highly significant for hydrogen storage because of high gravimetric and kinetic factors. Therefore, the double perovskites hydrides Be2XH6 (X = Cr and Mn) have outstanding hydrogen storage capability with gravimetric hydrogen densities of 7.9 wt% and 7.6 wt%, respectively. Moreover, the DFT-based PBE-GGA and TB-mBJ potential have been implemented to systematically analyze the electronic, Curie temperature, and magnetic characteristics of Be2XH6 (X = Cr and Mn). The tolerance factor and formation energy analysis indicate the structural and thermodynamic stabilities. The band structures, density of states and Curie Weiss law ensure the above room temperature half metallic ferromagnetism with complete spin polarization. The ultralow lattice thermal conductivity and high thermoelectric performance also significantly increase their importance. Finally, the mechanical and thermodynamic behavior have also been addressed in detail. These conclusions are significant for future hydrogen storage growth increases in metal hydrates.

The hydration and heavy metal immobilization performance of the CO2-active incineration fly ash-calcined clay-cement (CFC3) composite low-carbon cementitious system

CO2-active enhances the performance of municipal solid waste incineration fly ash as a supplementary cementitious material, increasing its utilization in cementitious systems. CFC3, a low-carbon cementitious material, effectively utilizes CO2-active incineration fly ash (CIFA). To minimize cement usage, the component effects on hydration need to be studied. In this study, hydration, mechanical and environmental properties of CFC3 were evaluated based on cement dosage and calcined clay/CIFA values. The maximum compressive strength of the samples reached 18.0 MPa at 3d and 47.6 MPa at 56d. The introduction of CIFA delayed the reactions of C3S and aluminates. Calcined clay contributes to improved gel polymerization, optimizes the Si/AlCASH ratio, and refines pore structure. A decrease in cement content increased in the aluminate phases, making monocarbonate the primary hydration product. The results of leaching tests indicated that Cd and Pb in R2C50 were transformed into non-leachable, inactive substances. Demonstrating the environmental friendliness of CFC3.

Circumventing the Theoretical Scaling Relation Limit for the Oxygen Evolution Reaction.

Transition metal hydr(oxy)oxides (TMHs) are considered efficient electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions. Toward identification of potential descriptors to circumvent the scaling relation limit for the OER, first-principles calculations were used to quantify the effects on the overpotential of different s (Mg), p (Al), and d (Ti, V, Cr, Fe, Co, Sc, and Zn) electron dopants in Ni-based TMHs. Both the adsorbate evolution mechanism (AEM) and the lattice oxygen-mediated mechanism (LOM) were examined. The results demonstrate that the formation energy of oxygen vacancies (EVO) is strongly affected by the chemical nature of the dopants. A linear relationship is identified between EVO and the free energy difference for the oxygen-oxygen coupling. A descriptor could be employed to discriminate whether the LOM is energetically favored over the AEM. These findings fill existing gaps in appropriate yet computationally light descriptors for direct identification between the AEM and LOM.

Hydration numbers of biologically relevant divalent metal cations from abinitio molecular dynamics and continuum solvation methods.

Hydration and, in particular, the coordination number of a metal ion is of paramount importance as it defines many of its (bio)physicochemical properties. It is not only essential for understanding its behavior in aqueous solutions but also determines the metal ion reference state and its binding energy to (bio)molecules. In this paper, for divalent metal cations Ca2+, Cd2+, Cu2+, Fe2+, Hg2+, Mg2+, Ni2+, Pb2+, and Zn2+, we compare two approaches for predicting hydration numbers: (1) a mixed explicit/continuum DFT-D3//COSMO-RS solvation model and (2) density functional theory based abinitio molecular dynamics. The former approach is employed to calculate the Gibbs free energy change for the sequential hydration reactions, starting from [M(H2O)2]2+ aqua complexes to [M(H2O)9]2+, allowing explicit water molecules to bind in the first or second coordination sphere and determining the most stable [M(H2O)n]2+ structure. In the latter approach, the hydration number is obtained by integrating the ion-water radial distribution function. With a couple of exceptions, the metal ion hydration numbers predicted by the two approaches are in mutual agreement, as well as in agreement with the experimental data.

PH-dependent interactions of biologically important metal ions with hen egg white lysozyme based on its hydration properties: Thermodynamic and mechanistic insights

Importance of metal ion selectivity in biomolecules and their key role in proteins are widely explored. However, understanding the thermodynamics of how hydrated metal ions alter the protein hydration and their conformation is also important. In this study, the interaction of some biologically important Ca2+, Mn2+, Co2+, Cu2+, and Zn2+ ions with hen egg white lysozyme at pH 2.1, 3.0, 4.5 and 7.4 has been investigated. Intrinsic fluorescence studies have been employed for metal ion-induced protein conformational changes analysis. Thermostability based on protein hydration has been investigated using differential scanning calorimetry (DSC). Thermodynamic parameters emphasizing on metal ion-protein binding mechanistic insights have been well discussed using isothermal titration calorimetry (ITC). Overall, these experiments have reported that their interactions are pH-dependent and entropically driven. This research also reports the strongly hydrated metal ions as water structure breaker unlike osmolytes based on DSC studies. These experimental results have highlighted higher concentrations of different metal ions effect on the protein hydration and thermostability which might be helpful in understanding their interactions in aqueous solutions.

Trapping waste metal ions in a hydrogel/coal powder composite for boosting sewage purification via solar-driven interfacial water evaporation with long-term durability

The improper disposal of effluents contaminated with waste metal ions poses significant threats to clean water resources. Recently, solar-driven interfacial water evaporation has gained increasing interests for sustainable water purification, nevertheless, the presence of various hydrated metal ions from industrial effluents makes it challenging for conventional distillers to achieve efficient purification performances. Herein, a waste metal ion trapping strategy based on a novel solar vapor generator (SVG) toward highly efficient solar-driven sewage purification with prolonged durability is reported. This SVG is constructed based on a polyion complex (PIC) hydrogel/coal powder composite (PCC), where the PIC skeleton provides metal ion entrapment capabilities, and the low-cost coal powders act as solar absorbents. PCC enables improved solar-driven sewage purification from two aspects: first, the entrapped multivalent ions help to activate the water molecules inside PCC and lower water evaporation enthalpy, leading to enlarged evaporation rate; second, the strong interactions between the multivalent metal ions and polyelectrolyte chains aid in stabilizing their porous structure and maintaining continuous water transport capabilities. The resultant PCC-based SVG demonstrated high evaporation rate up to 3.6 kg · m−2· h−1 in simulated industrial sewage under one sun illumination, as well as stable and efficient clean water generation in actual coal washery wastewater even for three weeks. We envision that the rational design of SVG with ions trapping capabilities and cost-effective solar absorbers should broaden the practical applications of SVG for harsh wastewater treatment.

Structure and size of complete hydration shells of metal ions and inorganic anions in aqueous solution.

The structures of nine hydrated metal ions in aqueous solution have been redetermined by large angle X-ray scattering to obtain experimental data of better quality than those reported 40-50 years ago. Accurate M-OI and M-(OI-H)⋯OII distances and M-OI(H)⋯OII bond angles are reported for the hydrated magnesium(II), aluminium(III), manganese(II), iron(II), iron(III), cobalt(II), nickel(II), copper(II) and zinc(II) ions; the subscripts I and II denote oxygen atoms in the first and second hydration sphere, respectively. Reported structures of hydrated metal ions in aqueous solution are summarized and evaluated with emphasis on a possible relationship between M-OI-OII bond angles and bonding character. Metal ions with high charge density have M-OI-OII bond angles close to 120°, indicative of a mainly electrostatic interaction with the oxygen atom in the water molecule in the first hydration shell. Metal ions forming bonds with a significant covalent contribution, as e.g. mercury(II) and tin(II), have M-OI-OII bond angles close to 109.5°. This implies that they bind to one of the free electron pairs in the water molecule. Comparison of M-O bond distances of hydrated metal ions in the solid state with one hydration shell, and in aqueous solution with in most cases at least two hydration shells, shows no significant differences. On the other hand, the X-O bond distance in hydrated oxoanions increases by ca. 0.02 Å in aqueous solution in comparison with the corresponding X-O distance in the solid state. A linear correlation is observed between volume, calculated from the van der Waals radius of the hydrated ion, and the ionic diffusion coefficient in aqueous solution. This correlation strongly indicates that monovalent metal ions, except lithium and silver(I), and singly-charged monovalent oxoanions have a single hydration shell. Divalent metal ions, bismuth(III) and the lanthanoid(III) and actinoid(III) ions have two hydration shells. Trivalent transition and tetravalent metal ions have two full hydration shells and portion of a third one. Doubly charged oxoanions have one well-defined hydration shell and an ill-defined second one.

A comprehensive assessment of green concrete incorporated with municipal solid waste incineration bottom: Experiments and life cycle assessment (LCA)

To reduce the high carbon emissions in the concrete field and facilitate the sustainable development of concrete, in this study, we repurposed high-volume municipal solid waste incineration bottom ash (MSWIBA) as a supplementary cementitious materials (SCMs) for the production of concrete at different percentages (0%, 10%, 20%, 30%, 40%, 50% and 60%). The influence of MSWIBA on the compressive strength, hydration, microstructure and heavy metal leaching behaviour of concrete was investigated. The results showed that a high volume of MSWIBA will reduce the compressive strength (from 56.81 MPa to 12.65 MPa) because aluminium produces hydrogen in an alkaline environment and excessive incorporation of MSWIBA leads to insufficient active substances. The content of ettringites and calcium silicate hydrate (C-S-H) initially increases (from 0.286 ％ to 0.405 ％ and from 0.635 ％ to 0.893 ％) and subsequently decreases (from 0.405 ％ to 0.275 ％ and from 0.893 ％ to 0.500 ％) as the proportion of MSWIBA in the mixture gradually increases due to the aluminium salt content reacting with the sulfate and pozzolanic reactivity of MSWIBA. In addition, compared with those in MSWIBA, the amounts of leachable hazardous ions (Cu, Pb, Cr, As and Hg) in concrete were effectively reduced by 87.1%, 83.3%, 70.0%, 90.3%, and 89.3%, respectively. Additionally, the measured heavy metal leaching met Chinese specification requirements. Life cycle assessment (LCA) was employed to evaluate environmental impacts (EIs), and it was found that using MSWIBA as a SCM can reduce the EI by 7.5 ％− 44.1 ％ (from 2.58E-11 to 1.56E-11) when the replacement cement ratio of MSWIBA is from 10 ％ to 60 ％. By normalizing the EI indices, it was found that the global warming potential (GWP) and eutrophication potential (EP) were the main contributors to the EI. Finally, a model was established to assess the comprehensive performance, including the environmental impact, compressive strength, porosity, apparent density, and ecology-strength efficiency, of the different MSWIBA formulations, and the comprehensive performance improved when the MSWIBA percentage was 30%.

Metal ion attachment in cavities of metal organic polyhedra to enhance framework robustness and catalytic performance

By adjusting the auxiliary ligands, the selective attachment of hydrated copper ions to the cage of metal organic polyhedra (MOP) was achieved. The introduction of hydrated metal ions improved the robustness and catalytic performance of MOPs.

Strong and Tough Antifreezing Hydrogel Sensor via the Synergy of Coordination and Hydrogen Bonds.

Hydrogel sensors are fascinating as flexible sensors and electronic skin due to their excellent biocompatibility and structure controllability. However, developing conductive hydrogels possessing both excellent mechanical and antifreezing properties for environmental-adaptive sensors remains a challenge. Herein, a strategy of combining betaine and metal ions to construct poly(acrylic acid) (PAA)-based high-conductive hydrogels has been reported. PAA-Al3+/betaine hydrogels with high toughness and antifreezing property were prepared by a one-step UV curing method. Their high toughness is attributed to the coordination of metal ions with the carboxylic groups in PAA, the interaction of betaine with PAA, and the formation of hydrogen bonds between them and water molecules. Moreover, the significant antifreezing property is due to the reduction of free water in the hydrogel. This, in turn, is attributed to the hydration of metal ions and the synergistic hydrogen bonding between betaine and water. The experiments demonstrate that the hydrogel has excellent mechanical property, high conductivity, superior transparency, antiswelling property, antipuncture as well as shape memory properties, and especially, low cytotoxicity. It can be used as a sensor for motion detection and information recognition. This work provides new insights into the application of flexible sensors and human-machine interfaces in multienvironmental conditions.

Radiation damage by extensive local water ionization from two-step electron-transfer-mediated decay of solvated ions

Biomolecular radiation damage is largely mediated by radicals and low-energy electrons formed by water ionization rather than by direct ionization of biomolecules. It was speculated that such an extensive, localized water ionization can be caused by ultrafast processes following excitation by core-level ionization of hydrated metal ions. In this model, ions relax via a cascade of local Auger–Meitner and, importantly, non-local charge- and energy-transfer processes involving the water environment. Here, we experimentally and theoretically show that, for solvated paradigmatic intermediate-mass Al3+ ions, electronic relaxation involves two sequential solute–solvent electron transfer-mediated decay processes. The electron transfer-mediated decay steps correspond to sequential relaxation from Al5+ to Al3+ accompanied by formation of four ionized water molecules and two low-energy electrons. Such charge multiplication and the generated highly reactive species are expected to initiate cascades of radical reactions.

Self-assembled layered lithium manganese oxide shows ultra-large adsorption capacity and high selectivity for lithium

Lithium manganese oxides (LMOs) are competitive materials for lithium extraction from aqueous resources. However, traditional LMOs are yet to be industrialized based on their existing lithium adsorption capacities. In this work, Li1.90Mn1.52O4, a self-assembled layered LMO, is innovatively synthesized with an accurately measured structure using multiple high-precision characterization technologies, and its adsorbent has an ultra-large lithium adsorption capacity of 66 mg/g. Synthesis experiments and related density functional theory (DFT) calculations show that the self-assembled synthesis of Li1.90Mn1.52O4 occurs during the hydrothermal process and is abstracted into three steps: first, manganese oxide dissolves into manganese oxide octahedron [MnO6] groups; second, the [MnO6] groups form metastable and thin-layer δ-type manganese oxide (δ-MnO2) by self-assembly; third, the pre-product of Li1.90Mn1.52O4 is formed by the reaction between the δ-MnO2 and the hydroxide ions with lithium ions embedded between layers. The selectivity experiments and corresponding DFT calculations show that the selective adsorption process of H1.90Mn1.52O4 follows the selectivity order “Li+ ≫ Na+ > K+ > Ca2+ > Mg2+” and is divided into two steps: first, the hydrated metal ions from the liquid resources leave the water molecules and transfer to the surface of H1.90Mn1.52O4; second, the metal ions migrate into the adsorption sites via the ultra-narrow ion transfer channels.

Surface Polarity Induced Simultaneous Enhancement of Nanopore Accessibility and Metal Utilization in Metal and Nitrogen Co-Doped Carbon Electrocatalysts for CO2 Reduction

The efficient utilization of active centers for the emerging class of metal (M) and nitrogen (N) co-doped carbon (M–N–C) catalysts remains a research hotspot for electrochemical synthesis such as the reduction reactions of CO2, O2, N2, or functional groups in organic molecules. However, keeping sufficient accessibility to these active centers upon thermal treatment at high temperatures can be challenging due to possible nanopore blocking issues. To tackle this limitation, this work presents a precise surface modulation approach based on a kind of porous carbon support with an ultrapolar surface, over which the unusual enhancement of nanopore accessibility and metal utilization is achieved. The strategy is well applicable to transition metals, precious metals, and rare earth metals. Experimental evidence revealed that the ultrapolar pore walls can be spontaneously wetted by hydrated metal ions. The unprecedented wettability ensured a unique metal-support interaction, which not only warrants the anchoring metal species in a dispersed manner but also induces the development of transport nanopores by dynamical etching of the polar carbon walls during thermal treatment. By this way, this strategy addresses the trade-off issue between metal utilization efficiency and accessibility to the active centers for the M–N–C type catalysts.