Engineering topics

Wang, Yanxiang

Publications and source records attributed to Wang, Yanxiang.

12 records

DOE OSTI2023

Multi–Modular Design of Stable Pore–Space–Partitioned Metal–Organic Frameworks for Gas Separation Applications

Pore space partition (PSP) is an effective materials design method for developing high-performance small-pore materials for storage and separation of gas molecules. The continued success of PSP depends on broad availability and judicious choice of pore-partition ligands and better understanding of each structural module on stability and sorption properties. Here, by using substructural bioisosteric strategy (sub-BIS), a dramatic expansion of pore-partitioned materials is targeted by using ditopic dipyridyl ligands with non-aromatic cores or extenders, as well as by expanding heterometallic clusters to uncommon nickel–vanadium and nickel–indium clusters rarely known before in porous materials. The dual-module iterative refinement of pore-partition ligands and trimers leads to remarkable enhancement of chemical stability and porosity. Here a family of 23 pore-partitioned materials synthesized from five pore-partition ligands and seven types of trimeric clusters is reported. New materials with such compositionally and structurally diverse framework modules reveal key factors that dictate stability, porosity, and gas separation properties. Among these, materials based on heterometallic vanadium–nickel trimeric clusters give rise to the highest long-term hydrolytic stability and remarkable uptake capacity for CO 2 , C 2 H 2 /C 2 H 4 /C 2 H 6 , and C 3 H 6 /C 3 H 8 hydrocarbon gases. Here, the breakthrough experiment shows the potential application of new materials for separating gas mixtures such as C 2 H 2 /CO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Concurrent Enhancement of Acetylene Uptake Capacity and Selectivity by Progressive Core Expansion and Extra–Framework Anions in Pore–Space–Partitioned Metal–Organic Frameworks

A multi-stage core-expansion method is proposed here as one component of the integrative binding-site/extender/core-expansion (BEC) strategy. The conceptual deconstruction of the partitioning ligand into three editable parts draws our focus onto progressive core expansion and allows the optimization of both acetylene uptake and selectivity. Herein the effectiveness of this strategy is shown through a family of eight cationic pore-partitioned materials containing three different partitioning ligands and various counter anions. The optimized structure, Co 3 -cpt-tph-Cl (Hcpt=4-(p-carboxyphenyl)-1,2,4-triazole, H-tph=(2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene) with the largest surface area and highest C 2 H 2 uptake capacity (200 cm 3 /g at 298 K), also exhibits (desirably) the lowest CO 2 uptake and hence the highest C 2 H 2 /CO 2 selectivity. The successful boost in both C 2 H 2 capacity and IAST selectivity allows Co 3 -cpt-tph-Cl to rank among the best crystalline porous materials, ionic MOFs in particular, for C 2 H 2 uptake and C 2 H 2 /CO 2 experimental breakthrough separation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Developing Water–Stable Pore–Partitioned Metal–Organic Frameworks with Multi–Level Symmetry for High–Performance Sorption Applications

Here a new perspective is proposed in the design of pore-space-partitioned MOFs that is focused on ligand symmetry properties sub-divided here into three hierarchical levels: 1) overall ligand, 2) ligand substructure such as backbone or core, and 3) the substituent groups. Different combinations of the above symmetry properties exist. Given the close correlation between nature of chemical moiety and its symmetry, such a unique perspective into ligand symmetry and sub-symmetry in MOF design translates into the influences on MOF properties. Five new MOFs have been prepared that exhibit excellent hydrothermal stability and high-performance adsorption properties with potential applications such as C 3 H 6 /C 2 H 4 and C 2 H 2 /CO 2 selective adsorption. The combination of high stability with high benzene/cyclohexane selectivity of ≈13.7 is also of particular interest.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

In Situ Synthesized Homochiral Spiroborate Ester Metal–Organic Framework with Mono–, Di–, and Trivalent Cations

Here we report here a one–step method for synthesizing multi–component and in–situ–formed homochiral spiroborate–ester–based metal–organic framework CPM–B1. This unique material successfully integrates COF fragment spiroborate ester within the MOF and simultaneously incorporate homochirality and helicity. In addition, CPM–B1 is a rare example of framework materials that results from the cooperative assembly of three charge–complementary cations: +1 (lithium), +2 (cobalt), and +3 (boron). The sophistication of the co–assembly is further highlighted by the three structural roles of lithium ions. This unique structure contributes to its multi–functional properties such as ionic conductivity and catalytic activity for oxygen reduction reaction (by CPM–B1 carbonized material) and provides a new path to develop MOF materials with complex secondary building units and multi–functional applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Simultaneous Control of Pore‐Space Partition and Charge Distribution in Multi‐Modular Metal–Organic Frameworks

Abstract We report here a strategy for making anionic pacs type porous materials by combining pore space partition with charge reallocation. The method uses the first negatively charged pore partition ligand (2,5,8‐tri‐(4‐pyridyl)‐1,3,4,6,7,9‐hexaazaphenalene, H‐tph) that simultaneously enables pore partition and charge reallocation. Over two dozen anionic pacs materials have been made to demonstrate their excellent chemical stability and a high degree of tunability. Notably, Ni 3 ‐bdt‐tph (bdt=1,4‐benzeneditetrazolate) exhibits month‐long water stability, while CoV‐bdt‐tph sets a new benchmark for C 2 H 2 storage capacity under ambient conditions for ionic MOFs. In addition to tunable in‐framework modules, we show feasibility to tune the type and concentration of extra‐framework counter cations and their influence on both stability and capability to separate industrial C 3 H 8 /C 3 H 6 and C 6 H 6 /C 6 H 12 mixtures.

Hong, Anh N.↗

DOE OSTI2022

Simultaneous Control of Pore-Space Partition and Charge Distribution in Multi-Modular Metal–Organic Frameworks

Here we report here a strategy for making anionic pacs type porous materials by combining pore space partition with charge reallocation. The method uses the first negatively charged pore partition ligand (2,5,8-tri-(4-pyridyl)-1,3,4,6,7,9-hexaazaphenalene, H-tph) that simultaneously enables pore partition and charge reallocation. Over two dozen anionic pacs materials have been made to demonstrate their excellent chemical stability and a high degree of tunability. Notably, Ni 3 -bdt-tph (bdt=1,4-benzeneditetrazolate) exhibits month-long water stability, while CoV-bdt-tph sets a new benchmark for C 2 H 2 storage capacity under ambient conditions for ionic MOFs. In addition to tunable in-framework modules, we show feasibility to tune the type and concentration of extra-framework counter cations and their influence on both stability and capability to separate industrial C 3 H 8 /C 3 H 6 and C 6 H 6 /C 6 H 12 mixtures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2021

Pore-Space Partition and Optimization for Propane-Selective High-Performance Propane/Propylene Separation

The development of effective propane (C 3 H 8 )-selective adsorbents for the purification of propylene (C 3 H 6 ) from C 3 H 8 /C 3 H 6 mixture is a promising alternative to replace the energy-intensive cryogenic distillation. However, few materials possess the dual desirable features of propane selectivity and high uptake capacity. Here, we report a family of pore-space-partitioned crystalline porous materials (CPM) with remarkable C 3 H 8 uptake capacity (up to 10.9 mmol/g) and the highly desirable, yet uncommon C 3 H 8 selectivity (up to 1.54 at 0.1 bar and 1.44 at 1bar). The selectivity-capacity synergy endows them with record-performing C 3 H 8 /C 3 H 6 separation potential (i.e., C 3 H 6 recovered from the mixture). Moreover, these CPMs exhibit outstanding properties including high stability, low regeneration energy, and multi-modular chemical and geometrical tunability within the same isoreticular framework. Furthermore, the high C 3 H 8 /C 3 H 6 separation performance was further confirmed by the breakthrough experiments.

36 MATERIALS SCIENCE↗

DOE OSTI2020

A Strategy for Constructing Pore‐Space‐Partitioned MOFs with High Uptake Capacity for C 2 Hydrocarbons and CO 2

Abstract Introduction of pore partition agents into hexagonal channels of MIL‐88 type (acs topology) endows materials with high tunability in gas sorption. Here, we report a strategy to partition acs framework into pacs (partitioned acs) crystalline porous materials (CPM). This strategy is based on insertion of in situ synthesized 4,4′‐dipyridylsulfide (dps) ligands. One third of open metal sites in the acs net are retained in pacs MOFs; two thirds are used for pore‐space partition. The Co 2 V‐pacs MOFs exhibit near or at record high uptake capacities for C 2 H 2 , C 2 H 4 , C 2 H 6 , and CO 2 among MOFs. The storage capacity of C 2 H 2 is 234 cm 3 g −1 (298 K) and 330 cm 3 g −1 (273 K) at 1 atm for CPM‐733‐dps (the Co 2 V‐BDC form, BDC=1,4‐benzenedicarboxylate). These high uptake capacities are accomplished with low heat of adsorption, a feature desirable for low‐energy‐cost adsorbent regeneration. CPM‐733‐dps is stable and shows no loss of C 2 H 2 adsorption capacity following multiple adsorption–desorption cycles.

Wang, Yong↗

DOE OSTI2020

A Strategy for Constructing Pore-Space-Partitioned MOFs with High Uptake Capacity for C 2 Hydrocarbons and CO 2

Introduction of pore partition agents into hexagonal channels of MIL-88 type (acs topology) endows materials with high tunability in gas sorption. Here, we report a strategy to partition acs framework into pacs (partitioned acs) crystalline porous materials (CPM). This strategy is based on insertion of in situ synthesized 4, 4'-dipyridylsulfide (dps) ligands. As a result, one third of open metal sites in the parent acs net are retained in pacs MOFs, while two thirds are used for pore space partition. The newly synthesized Co 2 V-pacs MOFs, with optimized pore space and open metal sites, exhibit near or at record high uptake capacities for C 2 H 2 , C 2 H 4 , C 2 H 6 , and CO 2 among MOFs. For example, the storage capacity of C 2 H 2 is 234 cm 3 /g -1 (298 K) and 330 cm 3 /g -1 (273K) at 1 atm for CPM-733-dps (the Co 2 V-BDC form, BDC=1,4-benzenedicarboxylate), higher than benchmark MOFs such as MOF-74 and all other pacs members. These high uptake capacities are accomplished with low heat of adsorption, a feature desirable for low-energy-cost adsorbent regeneration. CPM-733-dps is stable and shows no loss of C 2 H 2 adsorption capacity following multiple adsorption–desorption cycles.

25 ENERGY STORAGE↗

DOE OSTI2020

Tunable Metal–Organic Frameworks Based on 8-Connected Metal Trimers for High Ethane Uptake

Metal trimers [M 3 (O/OH)](OOCR) 6 are among the most important structural building blocks. From these trimers, a great success has been achieved in the design of 6- or 9-connected framework materials with various topological features and outstanding gas-sorption properties. In comparison, 8-connected trimer-based MOFs are rare. Given multiple competitive pathways for the formation of 6- or 9-connected frameworks, it remains challenging to identify synthetic or structural parameters that can be used to direct self-assembly process towards trimer-based 8-connected materials. Here, we reveal a viable strategy called angle bending modulation for creating a prototypical MOF type based on 8-connected M 3 (OH)(OOCR) 5 (Py-R) 3 trimers, M = Zn, Co, Fe). As a proof of concept, we synthesized six members in this family using three types of ligands (CPM-80, -81, and -82). These materials do not possess open-metal sites and show excellent uptake capacity for various hydrocarbon gas molecules and inverse C 2 H 6 /C 2 H 4 selectivity. CPM-81-Co, made from 2,5-furandicarboxylate and isonicotinate, features selectivity of 1.80 with high uptake capacity for ethane (123 cm 3 /g -1 ) and ethylene (113 cm 3 /g -1 ) at 298 K and 1 bar.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Bifunctional Heterometallic Metal-Organic Frameworks for Solvent-Free Heterogeneous Cascade Catalysis

A family of heterometallic metal-organic frameworks (MOFs) (CPM200s) harmoniously coexisting as Lewis acids and base (azo) sites were prepared. Seven CPM200s were employed as multifunctional heterogeneous cascade catalysts for the one-pot deacetalization-Knoevenagel reaction in a solvent-free system. Benefiting from the cooperation between Lewis acids from the open metal sites and base sites from the ligands, the CPM200s showed high activity and selectivity for the tandem reaction. The heterometallic 3D porous framework reported here not only offers a combination of two opposite active sites in the same framework of materials but also increases mass transfer of the substrate, thus maximizing the efficiency and substrate selectivity of the bifunctional catalysts. The CPM200s showed the highest turnover frequency (TOF), outperforming that of the reported MOFs in tandem with the deacetalization-Knoevenagel reaction. A strong correlation between the TOF and charge-to-radius ratio (z/r) of metal ions in the CPM200s was observed for the first time. The bifunctional CPM200s catalysts can be reused five times without significant loss of activity.

36 MATERIALS SCIENCE↗

DOE OSTI2020

Pore-Space-Partition-Enabled Exceptional Ethane Uptake and Ethane-Selective Ethane–Ethylene Separation

A modell material for C 2 H 6 /C 2 H 4 separation would simultaneously have the highest C 2 H 6 uptake capacity and the highest C 2 H 6 /C 2 H 4 selectivity. But such material is elusive. A benchmark material for ethane-selective C 2 H 6 /C 2 H 4 separation is peroxo-functionalized MOF-74-Fe that exhibits the best known separation performance due to its high C 2 H 6 /C 2 H 4 selectivity (4.4), although its C 2 H 6 uptake capacity is moderate (74.3 cm 3 /g). Here, we report a family of pore-space-partitioned crystalline porous materials (CPMs) with exceptional C 2 H 6 uptake capacity and C 2 H 6 /C 2 H 4 separation potential (i.e., C 2 H 4 recovered from the mixture) despite their moderate C 2 H 6 /C 2 H 4 selectivity (up to 1.75). The ethane uptake capacity as high as 166.8 cm 3 /g at 1 atm and 298 K, more than twice that of peroxo-MOF-74-Fe, was previously achieved even though the isosteric heat of adsorption (21.9–30.4 kJ/mol) for these CPMs is as low as about one-third of that for peroxo-MOF-74-Fe (66.8 kJ/mol). While the overall C 2 H 6 /C 2 H 4 separation potentials have not yet surpassed peroxo-MOF-74-Fe, these robust CPMs exhibit outstanding properties including high thermal stability (up to 450 °C) and aqueous stability, low regeneration energy, and a high degree of chemical and geometrical tunability within the same isoreticular framework.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗