Metal-organic Framework Precursor Research Articles

Hydrothermally synthesized Ti/Zr bimetallic MOFs derived N self-doped TiO2/ZrO2 composite catalysts with enhanced photocatalytic degradation of methylene blue

The nitrogen-rich Ti/Zr bimetallic metal organic framework (MOF) precursors were synthesized by a facile one-step hydrothermal method. By pyrolyzing the MOF precursors at 600 °C, the N self-doped TiO2/ZrO2 composites were obtained, and the morphology of the MOF precursor was well preserved. The powder X-ray diffraction (XRD) patterns and transmission electron microscopy (TEM) indicated the highly crystalline polycrystallization of mix-phase TiO2 and tetragonal ZrO2 in the composites. The X-ray photoelectron spectroscopy (XPS) and elemental mapping image demonstrated the successful uniform doping of N. The scanning electron microscopy (SEM) proved that the bimetal oxides retained the thin disk morphology of the MOF precursor. The photoluminescence (PL) spectroscopic analysis proved that the N-doped TiO2/ZrO2 composites have a lower photogenerated electron and hole pair recombination rate than single metal oxides. Mott-Schottky analysis confirmed that the N-doped TiO2/ZrO2 composites belonged to the n-n heterojunction. The N doped TiO2/ZrO2 composites exhibited the outstanding performance of methylene blue (MB) photodegradation under UV light illumination with an efficiency of 93.2% after 80 min. In addition, the degradation rate of N-doped TiO2/ZrO2 for tetracycline and phenol and was 86.3% and 72.4% after 120 min, respectively. The quenching test demonstrated that the •OH was the main active radicals, and the electron spin resonance (ESR) confirmed the existence of •OH radicals. The stability and reusability of the composites were confirmed by cyclic experiments, and the possible photocatalytic mechanism was discussed. Overall, N-doped TiO2/ZrO2 composites have the considerable application prospect for photocatalysis of organic pollutants in the polluted water.

General Synthesis of Hierarchically Macro/Mesoporous Fe,Ni-Doped CoSe/N-Doped Carbon Nanoshells for Enhanced Electrocatalytic Oxygen Evolution.

Constructing hierarchical porosity and designing rational hybrid composition are effective strategies for enhancing the electrocatalytic performance of hybrid catalysts for electrochemical energy conversion. Here, we develop a multistep "molecule/ion-exchange" strategy toward the synthesis of hierarchically macro/mesoporous Fe,Ni-doped CoSe/N-doped carbon nanoshells with tunable pore structures and compositions. Polystyrene (PS)@Co-based amorphous coordination polymer (Co-CP) core-shell particles with hierarchically macro/mesoporous nanoshells are first prepared by ligand-molecule-exchange etching of the outer layers in PS@Co-based metal-organic framework precursors. Afterward, a liquid-solid dual-ion-exchange reaction of PS@Co-CP particles with [Fe(CN)6]3- and [Ni(CN)4]2- ions leads to the formation of PS@Co-CP/Co-Fe Prussian blue analogue (PBA)/Co-Ni PBA particles, which are further transformed into hierarchically macro/mesoporous Fe,Ni-doped CoSe/N-doped carbon particles via a vapor-solid selenization reaction. Moreover, this approach could be extended to synthesize different hierarchically porous core-shell composites with various morphologies and tailored compositions. Because of their unique hierarchically porous nanoarchitecture, these Fe,Ni-doped CoSe/N-doped carbon particles with optimized composition show enhanced performance for electrocatalytic oxygen evolution.

Heterogeneous Growth of UiO-66-NH2 on Oxidized Single-Walled Carbon Nanotubes to Form "Beads-on-a-String" Composites.

In this work, we demonstrate a facile synthesis of UiO-66-NH2 metal-organic framework (MOF)/oxidized single-walled carbon nanotubes (ox-SWCNTs) composite at room temperature. Acetic acid (HAc) was used as a modulator to manipulate the morphology of the MOF in these composites. With a zirconium oxide cluster (Zr) to 2-aminoteraphthalate linker (ATA) 1:1.42 ratio and acetic acid modulator, we achieved predominately heterogeneous MOF growth on the sidewalls of CNTs. Understanding the growth mechanism of these composites was facilitated by conducting DFT calculations to investigate the interactions between ox-SWCNTs and the MOF precursors. The synthesized composites combine both microporosity of the MOF and electrical conductivity of the SWCNTs. Gas sensing tests demonstrated higher response for UiO-66-NH2/ox-SWCNT hybrid toward dry air saturated with dimethyl methylphosphonate (DMMP) vapor compared to oxidized single-walled carbon nanotubes (ox-SWCNTs) alone.

Sulfur-modified nickel selenide as an efficient electrocatalyst for the oxygen evolution reaction

The sluggish four-electron transfer of the oxygen evolution reaction (OER) limits the performance of water electrolyzers. Hence, OER electrocatalysts based on earth-abundant elements are urgently needed. Heteroatom doping has been an efficient approach to boost the intrinsic OER activity of the active sites by modifying the electronic structure. Here, a simple anion substitution strategy is reported that increases the OER activity of nickel selenides via a one-step hydrothermal treatment of a metal–organic framework precursor. The resulting S-substituted Ni3Se4 nanoparticles display distortion of their crystal lattice. As expected, the sulfur substitution modifies the electronic structure of Ni3Se4 and leads to outstanding electrocatalytic activity. All the S-substituted Ni3Se4 catalysts exhibit higher OER activities than the original Ni3Se4. The optimized catalyst achieves a current density of 10 mA cm−2 at an overpotential of 275 mV with a Tafel slope of 64 mV dec−1 in 1.0 M KOH. In addition to its electrochemical activity, the S-Ni3Se4-2 catalyst also exhibits good stability with only a 7.5% increase in overpotential at 50 mA cm−2 after 100 hours. This work demonstrates one strategy to modify the electronic structure of transition metal compounds by anion regulation.

Urea‐Assisted Synthesis and Tailoring Cobalt Cores for Synergetic Promotion of Hydrogen Evolution Reaction in Acid and Alkaline Media

Interconnected N‐doped carbon nanotubes enclosed with Co nanoparticles have been synthesized by a strategy of urea‐assisted pyrolysis of bimetallic metal–organic framework (MOF) precursor. The modulation of Co/Zn ratio in bimetallic MOF precursors can not only regulate spatial dispersion and local structural disorder of Co cores, but also lead to the alterable proportion of the component nitrogen types in catalysts, which impacts the charge distribution of the carbon sheath and further ameliorates the charge transfer. Moreover, urea, an assisted nitrogen/carbon source, plays an active role in the formation and growth of N‐doped carbon nanotubes. Such Co–N–C system results in more provided active sites (e.g., Co and Co–Nx moieties), noncorrosive metal cores protected by carbon materials as well as short diffusion pathway of ions due to the synergetic effect of core–sheath structure. Benefiting from these controllable strategies, C1Z1 (pyrolysis product of Co0.5Zn0.5‐ZIF and urea precursor) embraces the current density of 10 mA cm−2 at the overpotential of 251 and 279 mV for hydrogen evolution reaction (HER) in acid and alkaline media, respectively, which enables it to be an efficient electrocatalyst for HER under both extreme pH conditions.

Performance Fabrics Obtained by In Situ Growth of Metal-Organic Frameworks in Electrospun Fibers.

Metal–organic frameworks (MOFs) exhibit an exceptional surface area-to-volume ratio, variable pore sizes, and selective binding, and hence, there is an ongoing effort to advance their processability for broadening their utilization in different applications. In this work, we demonstrate a general scheme for fabricating freestanding MOF-embedded polymeric fibers, in which the fibers themselves act as microreactors for the in situ growth of the MOF crystals. The MOF-embedded fibers are obtained via a two-step process, in which, initially, polymer solutions containing the MOF precursors are electrospun to obtain microfibers, and then, the growth of MOF crystals is initiated and performed via antisolvent-induced crystallization. Using this approach, we demonstrate the fabrication of composite microfibers containing two types of MOFs: copper (II) benzene-1,3,5-tricarboxylic acid (HKUST-1) and zinc (II) 2-methylimidazole (ZIF-8). The MOF crystals grow from the fiber’s core toward its outer rims, leading to exposed MOF crystals that are well rooted within the polymer matrix. The MOF fibers obtained using this method can reach lengths of hundreds of meters and exhibit mechanical strength that allows arranging them into dense, flexible, and highly durable nonwoven meshes. We also examined the use of the MOF fiber meshes for the immobilization of the enzymes catalase and horse radish peroxidase (HRP), and the enzyme-MOF fabrics exhibit improved performance. The MOF-embedded fibers, demonstrated in this work, hold promise for different applications including separation of specific chemical species, selective catalysis, and sensing and pave the way to new MOF-containing performance fabrics and active membranes.

Kirkendall effect induced bifunctional hybrid electrocatalyst (Co9S8@MoS2/N-doped hollow carbon) for high performance overall water splitting

Rational design of electrocatalysts with the tuneable structural and electrocatalytic properties are essential to accomplish bifunctional activity of hydrogen and oxygen evolution reaction (HER/OER), and thus efficient water splitting systems. Here, we present a bifunctional hybrid electrocatalyst consisting of Co9S8 (OER-active) and MoS2 (HER-active) with the structural merits of hierarchical morphology, huge electrochemically active sites, and greater charge transfer ability. The structural features of the hybrid electrocatalyst (Co9S8@MoS2/N-doped hollow carbon) that is derived from metal organic framework (MOF) precursor are elaborately controlled by the temperature dependent-Kirkendall diffusion effect. Specifically, the imbalanced diffusion rates between two ionic species (Co2+ and S2−), confined in the MOF-precursor geometry, induces the formation of internal voids and outward growth of Co9S8 while retaining MoS2 layers on the surface. As a result, the hybrid electrocatalyst exhibits greatly enhanced HER (126 mV@−10 mA cm−2) and OER (233 mV@10 mA cm−2) performance. Furthermore, the bifunctional electrode couple demonstrates efficient overall water splitting performance (1.56 V@10 mA cm−2) compared to the benchmark electrode couple of IrO2/C//Pt/C (1.63 V@10 mA cm−2) in 1 M KOH solution. The results highlight that inducing “Kirkendall effect” through temperature-tuning approach for structure-properties modulation can be extensively applied to design various bifunctional hybrid electrocatalysts.

Improved Electrochemical Performance of a Li1.2Ni0.2Mn0.6O2 Cathode by a Hydrothermal Method with a Metal–Organic Framework as a Precursor

Metal–organic frameworks (MOFs) have been successfully applied as precursors and adsorbents to synthesize a Li1.2Ni0.2Mn0.6O2 cathode material via a hydrothermal method. A MOF precursor is composed...

Metal-organic framework precursors derived Ni-doping porous carbon spheres for sensitive electrochemical detection of acetaminophen

The sensitive and selective determination of acetaminophen (AP) in the human body is highly desirable to ensure human health. In this work, nickel-doping nanoporous carbon (Ni/C) was fabricated by directly calcining Ni based metal-organic framework (Ni-MOF). The Ni/C based electrochemical sensor was developed for sensitive and selective determination of AP in human blood serum and urine samples. The prepared Ni/C composite possess plentiful catalytic active sites, ordered mesoporous structure and large specific surface area, which endow the constructed Ni/C sensor with a prominent performance for acetaminophen sensing. Under the optimal conditions, the developed method offered good linearity in the range of 0.20–53.75 μM with a low detection limit (S/N = 3) of 4.04 × 10−2 μM. The electrocatalytic performance of the sensor towards AP was further measured by differential pulse voltammetry and cyclic voltammetry. The results demonstrated that the Ni/C sensor can be feasibly employed for the determination of AP in human blood serum and urine samples with excellent anti-interference stability and good reproducibility. The research reveals a great promising of the Ni/C electrochemical sensor for clinical applications and paves a way for the construction of high-performance electrochemical sensors for AP determination.

Three-dimensional assembly and disassembly of Fe3O4-decorated porous carbon nanocomposite with enhanced transversal relaxation for magnetic resonance sensing of bisphenol A.

Thedesign and construction of a novel magnetic resonance sensor (MRS) is presentedfor bisphenol A (BPA) detection. The MRS has been built based on the core component of magnetic Fe3O4 nanoparticles (~ 40nm), which were uniformly distributed in nanoporous carbon (abbreviated as Fe3O4@NPC). The synthesis was derived from the calcination of the metal organic framework (MOF) precursor of Fe-MIL-101 at high temperature. Fe3O4@NPC was confirmed with enhanced transversal relaxation with r2 value of 118.2mM-1s-1, which was around 1.7 times higher than that of the naked Fe3O4 nanoparticle. This enhancement is attributed to the excellent proton transverse relaxation rate of Fe3O4@NPC caused by the reduced self-diffusion coefficient of water molecules in the vicinityof Fe3O4 nanoparticles in the nanoporous carbon. BPA antibody (Ab) and antigen (Ag)-ovalbumin (OVA) were immobilized onto the Fe3O4@NPC to form Ab-Fe3O4@NPC and Ag-Fe3O4@NPC, respectively. These two composites can cause the three-dimensional assembly of Fe3O4@NPC via immunological recognition. The presence of BPA can compete with antigen-OVA to combine with Ab-Fe3O4@NPC, thereby breaking the assembly process (disassembly). The difference in the change of the T2 value before and after adding BPA can thus be used to monitor BPA. The proposed MRS not only revealed a wide linear range of BPA concentration from 0.05 to 50ngmL-1 with an extremely low detection limit of 0.012ngmL-1 (S/N = 3), but also displayed high selectivity towards matrix interferences. The recoveries of BPA ranged from 95.6 to 108.4% for spiked tea π, and 93.4 to 104.7% for spiked canned oranges samples, respectively, and the RSD (n = 3) was less than 4.4% for 3 successive assays. The versatility of Fe3O4@NPC with customized relaxation responses provides the possibility for the adaptation of magnetic resonance platforms for food safety development. The magnetic Fe3O4 nanoparticles are uniformly dispersed in the nanoporous carbon (Fe3O4@NPC), which derived from the calcinating of the metal organic framework (MOF) precursor of Fe-MIL-101. And the magnetic Fe3O4@NPCs are adopted for the construction of magnetic resonance sensor (MRS) for bisphenol A (BPA) detection.

Porous array with CoP nanoparticle modification derived from MOF grown on carbon cloth for effective alkaline hydrogen evolution

Abstract Metal organic framework (MOF) as a template strategy to get dispersed metal particle with high catalytic activity is widely used in the design of electrodes for hydrogen production. Herein, we report using carbon nanotube (CNT) as a multifunctional active binder that would promote the growth of MOF arrays on carbon fiber cloth (CFC) substrate and the release of hydrogen. By modified CFC with this new active binder: (1) the active material was more firmly anchored to the carbon fiber; (2) the overall electron transport efficiency was improved; and (3) the MOF precursor grew more uniformly on the carbon fiber, and greatly increased the number of active sites. Benefited from the CNT modification, the obtained porous array with CoP nanoparticle modification (CFC-CNT-CoOx/CoP) catalyst displayed superior alkaline hydrogen evolution reaction (HER) performance and excellent stability with an overpotential of 108 mV at the current density of 10 mA cm−2 and a small Tafel slope of 60 mV dec−1. The excellent HER performance mainly derived from the structure optimization and enhanced electron transfer brought by the active binders. In addition, Co(OH)2 appeared in the long-time HER process and the synergistic interaction of CoOx, CoP, Co(OH)2 and CNT maintained the good stability.

Electrochemical characteristics of Cu/Cu2O/C composite electrode for supercapacitor application

Metal-organic frameworks (MOF) have attracted much attention from researchers in various fields due to their controllable morphology, high porosity and multifunctionalities. MOF is a new class of porous materials that are made by metal ions and organic ligands which can be applied in a wide variety of applications including energy conversion and storage devices. In this work, a simple and cost-effective method was introduced in synthesizing MOF using copper ions and 2-methylimidazole. Cu/Cu2O/C composite was then being derived from the MOF precursor, at various temperatures of 700, 800 and 900 °C as electrode materials for supercapacitor application. MOF precursor (CM-RT) contributed only 16 Cg−1 at the current density of 0.25 Ag−1 in 1 M potassium hydroxide (KOH) electrolyte. However, MOF that has been heated at temperature 900 °C (CM-900) has achieved a maximum capacity value of 249 Cg−1 at a current density of 0.25 Ag−1 in a standard three electrode system. The asymmetrical supercapacitors which were assembled using commercial activated carbon and heated MOF, AC//CM-900 cell delivered an energy density of 30 Wh kg−1 and power density of 107 W kg−1. The developed electrode materials of Cu/Cu2O/C composite showed excellent electrochemical properties and new insights of copper-based MOF as electrode materials for energy storage applications.

A novel metal-organic framework precursor strategy to fabricate sub-micron CuO microspheres for catalytic thermal decomposition of ammonium perchlorate

A novel metal-organic framework (MOF) precursor strategy to fabricate CuO microspheres via air-flow impacting (AFI) synthetic method was reprted in the work. The MOF precursor HKUST-1 and its derived CuO microspheres were characterized by means of X-ray diffraction (XRD) and scanning electron microscopy (SEM). In addition, the catalytic activity of CuO microspheres on the thermal decomposition of ammonium perchlorate (AP) was investigated by differential thermal analysis (DTA). The results of DTA indicated that the addition of CuO microspheres to AP observably reduces the decomposition temperature due to its high contact area and much catalytic active sites. The HKUST-1 derived CuO microspheres are expected to remarkably improve the catalytic performance in AP-based composite solid rocket propellants.

An in situ investigation of the thermal decomposition of metal-organic framework NH2-MIL-125 (Ti)

Abstract Titanium based metal-organic frameworks (MOFs) are interesting self-sacrificial precursors to derive semiconducting porous nanocomposites for highly efficient heterogeneous catalysis. However, there is a lack of systematic and in-depth mechanistic understanding of the pyrolytic conversion of MOF precursors into the desired functional composite materials. In this work, TGA-MS and in situ STEM/EDX combined with other characterization techniques were employed to investigate the evolution of the structural, physicochemical, textural and morphological properties of NH2-MIL-125(Ti) pyrolysis at different temperatures in an inert gaseous atmosphere. In situ thermal analysis of NH2-MIL-125(Ti) reveals the presence of 3 rather defined stages of thermal transformation in the following order: phase-pure, highly porous and crystalline MOF → intermediate amorphous phase without accessible porosity → recrystallized porous phase. The three stages occur from room temperature till 300 °C, between 350 and 550 °C and above ~550 °C respectively. It is found that the framework of NH2-MIL-125(Ti) starts to collapse around 350 °C, accompanied with the cleavage of coordination and covalent bonds between organic linkers [O2C–C6H3(NH2)–CO2]6 and the Ti oxo-cluster Ti8O8(OH)4. The organic linker continues fragmentation at 450 °C causing the shrinkage of particle sizes. The dominant pore size of 0.7 nm for NH2-MIL-125(Ti) gradually expands to 1.4 nm at 800 °C along with the formation of mesopores. The derived disc-like particles exhibit an approximately 35% volume shrinkage compared to the pristine MOF precursor. Highly crystalline N and/or C self-doped TiO2 nanoparticles are homogeneously distributed in the porous carbon matrix. The original 3D tetragonal disc-like morphology of the NH2-MIL-125(Ti) remains preserved in derived N and/or C doped TiO2/C composites. This study will provide an in-depth understanding of the thermal conversion behavior of MOFs to rationally select and design the derived composites for the relevant applications.

Facile synthesis of nickel/carbon nanotubes hybrid derived from metal organic framework as a lightweight, strong and efficient microwave absorber

Transition metal carbon composites derived from metal organic frameworks (MOFs) attract increasing attention in microwave absorption field. However, finding a relatively facile and green method to prepare MOFs precursor is still a challenge. Besides, it is also difficult to obtain carbon nanotubes based compounds by only using MOF as sacrificed template. Herein, nickel (Ni) MOF is fabricated at room temperature with water as solvent. Afterwards, nickel/carbon nanotubes composite (Ni/CN) is prepared via only in-situ pyrolysis of Ni MOF. The pyrolysis temperature greatly affects nitrogen (N) dopant state for Ni/CN composites. The Ni/CN composite prepared at 700 °C (Ni/CN-700) exhibits the maximum reflection loss (RL) of −65 dB with the effective absorbing bandwidth (EAB) about 4.6 GHz at 1.9 mm, when the filling loading is only 10 wt% in the matrix. Remarkably, the Ni/CN composite is excellent microwave absorber with lightweight and strong absorption. The magnetic metal/carbon nanotubes derived from MOF prepared in green solvent offers a facile, environmentally friendly and designable strategy for exploring excellent microwave absorber.

Effects of Superparamagnetic Iron Nanoparticles on Electrocatalysts for the Reduction of Oxygen.

It is of great research interest to understand the nanostructures contributing to the activity observed in the reduction of oxygen by non-platinum group metal (PGM) electrocatalysts in acidic media. Iron- and nitrogen-containing carbon networks are often the most studied structures, among which single-atom iron-coordinated nitrogen (FeNx) moieties have often been proposed to be the structures leading to the high activity in these non-PGM electrocatalysts. Iron nanoparticles embedded within a carbon support are also formed under certain conditions as a result of the synthetic processes in making non-PGM electrocatalysts. In this study, we present a study to understand the oxygen reduction reaction (ORR) activity of prepared iron- and nitrogen-containing non-PGM electrocatalysts obtained through the pyrolysis of metal-organic framework (MOF) precursors. We studied the structure-property relationship among nanostructures made from the MOF precursor ZIF-8 under different pyrolysis conditions. Density functional theory calculations were used to explain the effect of structural moieties on the ORR activity. Our results suggest that iron-coordinated C-N structures and iron nanoparticles act synergistically to catalyze the ORR.

Highly dispersed secondary building unit-stabilized binary metal center on a hierarchical porous carbon matrix for enhanced oxygen evolution reaction.

Restricting the aggregation and rationally adjusting the electronic structure of binary metal centers in metal-organic framework (MOF) precursors are important for optimizing their performance as electrocatalysts for the oxygen evolution reaction (OER) and achieving low overpotential and high stability in such applications. Herein, we demonstrate the possibility of enhancing the electrochemical activity of MOF-derived binary metal center catalysts by controlling the form of the Fe species. The introduction of Fe-SBU (iron 2,5-dihydroxyterephthalic acid) into ZIF-67 is found to induce a distinct confinement effect and this can be exploited to improve the electroconductivity of binary metal center catalysts, and therefore, to reduce the OER reaction barrier (OOH* → O*). When applied as an OER catalyst in 1 M KOH solution, the Fe-SBU@Co-Matrix catalyst exhibits a low overpotential of 249 mV to reach a current density of 10 mA cm-2 and high stability for over 40 h. This work describes the secondary growth treatment of MOF-derived porous carbons to promote their application as catalysts in energy conversion reactions.

Metal–organic framework (MOF) derived flower-shaped CoSe2 nanoplates as a superior bifunctional electrocatalyst for both oxygen and hydrogen evolution reactions

A jasmine-flower like CoSe2 nanoplates termed as MOF-D CoSe2 has been successfully derived from a cobalt MOF precursor, namely, ([Co3(tiron-bpy)2(bpy)(H2O)8]·(H2O)2) and tested as a bifunctional electrocatalyst in both acidic and alkaline media.

Ultrathin Metal–Organic Framework Nanosheets-Derived Yolk–Shell Ni 0.85 Se@NC with Rich Se-Vacancies for Enhanced Water Electrolysis

We present a controlled fabrication of selective ultrathin metal–organic framework (MOF) nanosheets as preassembling platforms, yolk–shell structured with a few-layered N-doped carbon (NC) shell-en...

Morphology-controlled synthesis of metal-organic frameworks derived lattice plane-altered iron oxide for efficient trifunctional electrocatalysts

Developing efficient trifunctional electrocatalysts with high activity and long durability is extraordinarily desirable. Metal-organic frameworks (MOFs) are ideal self-sacrificial templates, and their derived electrocatalysts are promising for the oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Herein, Fe-based MOFs with well-aligned morphologies have been synthesized by elaborately tuning the competitive coordinated cations from diverse metal sources and solvent systems through a one-step solvothermal method. In this process, the competitive coordination with the metal sites between the ligands and the solvent molecules allows the feasibility to regulate the morphologies of these MOF precursors. After pyrolysis, the resulting Fe2O3 compounds not only inherit the morphologies of the precursors, but also expose different active lattice planes, producing disparate intrinsic active sites. Particularly, the concave octahedral (CO)-Fe2O3 with higher active facets and more accessible surface-active sites exhibits a superior electrocatalytic activity and stability for ORR, OER and HER compared with other morphologies and structures. This competitive coordination strategy paves an innovative and feasible pathway for morphology- and structure-controlled MOFs derivatives with tailored catalytic centers toward electrochemical energy storage and convention.