Backbone Engineering of Polymeric Catalysts for High-Performance CO2 Reduction in Bipolar Membrane Zero-Gap Electrolyzer.

Bipolar membranes (BPMs) have emerged as a promising solution for mitigating CO2 losses, salt precipitation and high maintenance costs associated with the commonly used anion-exchange membrane electrode assembly for CO2 reduction reaction (CO2RR). However, the industrial implementation of BPM-based zero-gap electrolyzer is hampered by the poor CO2RR performance, largely attributed to the local acidic environment. Here, we report a backbone engineering strategy to improve the CO2RR performance of molecular catalysts in BPM-based zero-gap electrolyzers by covalently grafting cobalt tetraaminophthalocyanine onto a positively charged polyfluorene backbone (PF-CoTAPc). PF-CoTAPc shows a high acid tolerance in BPM electrode assembly (BPMEA), achieving a high FE of 82.6 % for CO at 100 mA/cm2 and a high CO2 utilization efficiency of 87.8 %. Notably, the CO2RR selectivity, carbon utilization efficiency and long-term stability of PF-CoTAPc in BPMEA outperform reported BPM systems. We attribute the enhancement to the stable cationic shield in the double layer and suppression of proton migration, ultimately inhibiting the undesired hydrogen evolution and improving the CO2RR selectivity. Techno-economic analysis shows the least energy consumption (957 kJ/mol) for the PF-CoTAPc catalyst in BPMEA. Our findings provide a viable strategy for designing efficient CO2RR catalysts in acidic environments.

Host-Guest Recognition Boosts Biomimetic Mono/Multivalent Cation Separation.

Biomimetic ion permselective membranes with ultrahigh ion permeability and selectivity represent a research frontier in ion separation, yet the successful fabrication of such membranes remains a formidable challenge. Here, we demonstrate a 4-sulfocalix[4]arene (4-SCA)-modified graphene oxide (GO) membrane that shows extraordinary performance in separating mono-from multivalent cations, as well as having reversible pH-responsiveness. The resulting 4-SCA-modified GO (SCA-GO) membrane preferentially transports potassium ions (K+) over radionuclide cations (Co2+, UO22+, La3+, Eu3+, and Th4+). The ion selectivities are an order of magnitude higher than that of the unmodified GO membrane. Theoretical calculations and experimental investigations demonstrate that the much-improved ion selectivity arises from the specific recognition between 4-SCA and radionuclide cations. The transport of multivalent radionuclides is impeded by a binding-obstructing mechanism from the host-guest interactions. Interestingly, the host-guest interactions are responsive to the protonation/deprotonation transformation of the 4-SCA. Therefore, the SCA-GO membrane mimics pH-regulated ion selective behavior found in biological ion channels. Our strategy of designing a biomimetic permselective GO membrane may allow efficient nuclear wastewater treatment and, more importantly, deepen our understanding of biomimetic ion transport mechanisms.

A π-Conjugated Anion-Exchange Membrane with an Ordered Ion-Conducting Channel via the McMurray Coupling Reaction.

The McMurry coupling is a facile, gentle and low-cost chemical reaction for synthesizing. Here, for the first time, we employed the McMurry coupling reaction to prepare π-conjugated anion exchange membranes (AEMs). The inter-chain π-π stacking between adjacent benzene rings induces directional self-assembly aggregation and enables highly ordered ion-conductive channels. The resulting structure was characterized through UV/VIS spectrum, X-ray diffraction (XRD) pattern, small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and density functional theory (DFT) calculations, leading to high OH- conductivity of 135.5 mS cm-1 at 80 °C. Furthermore, the double bonds in the π-conjugated system also trigger in situ self-crosslinking of the AEMs to enhance dimensional and alkaline stability. Benefiting from this advantage, the as-obtained Cr-QPPV-2.51 AEM exhibits superior alkaline stability (95 % conductivity retention after 3000 hrs in 1 M KOH at 80 °C) and high mechanical strength of 34.8 MPa. Moreover, the fuel cell using Cr-QPPV-2.51 shows a maximum peak power density of 1.27 W cm-2 at 80 °C.

Physically and Chemically Stable Anion Exchange Membranes with Hydrogen-Bond Induced Ion Conducting Channels.

Anion exchange membranes (AEMs) with desirable properties are the crucial components for numerous energy devices such as AEM fuel cells (AEMFCs), AEM water electrolyzers (AEMWEs), etc. However, the lack of suitable AEMs severely limits the performance of devices. Here, a series of physically and chemically stable AEMs have been prepared by the reaction between the alkyl bromine terminal ether-bond-free aryl backbone and the urea group-containing crosslinker. Morphology analyses confirm that the hydrogen bonding interaction between urea groups is capable of driving the ammonium cations to aggregate and further form continuous ion-conducting channels. Therefore, the resultant AEM demonstrates remarkable OH− conductivity (59.1 mS cm−1 at 30 °C and 122.9 mS cm−1 at 90 °C) despite a moderate IEC (1.77 mmol g−1). Simultaneously, due to the adoption of ether-bond-free aryl backbone and alkylene chain-modified trimethylammonium cation, the AEM possesses excellent alkaline stability (87.3% IEC retention after soaking in 1 M NaOH for 1080 h). Moreover, the prepared AEM shows desirable mechanical properties (tensile stress > 25 MPa) and dimensional stability (SR = 20.3% at 90 °C) contributed by the covalent-bond and hydrogen-bond crosslinking network structures. Moreover, the resulting AEM reaches a peak power density of 555 mW cm−2 in an alkaline H2/O2 single fuel cell at 70 °C without back pressure. This rational structural design presented here provides inspiration for the development of high-performance AEMs, which are crucial for membrane technologies.

3D-Zipped Interface: In Situ Covalent-Locking for High Performance of Anion Exchange Membrane Fuel Cells.

Polymer electrolyte membrane fuel cells can generate high power using a potentially green fuel (H2 ) and zero emissions of greenhouse gas (CO2 ). However, significant mass transport resistances in the interface region of the membrane electrode assemblies (MEAs), between the membrane and the catalyst layers remains a barrier to achieving MEAs with high power densities and long-term stabilities. Here, a 3D-interfacial zipping concept is presented to overcome this challenge. Vinylbenzyl-terminated bi-cationic quaternary-ammonium-based polyelectrolyte is employed as both the anionomer in the anion-exchange membrane (AEM) and catalyst layers. A quaternary-ammonium-containing covalently locked interface is formed by thermally induced inter-crosslinking of the terminal vinyl groups. Ex situ evaluation of interfacial bonding strength and in situ durability tests demonstrate that this 3D-zipped interface strategy prevents interfacial delamination without any sacrifice of fuel cell performance. A H2 /O2 AEMFC test demonstration shows promisingly high power densities (1.5 W cm-2 at 70 °C with 100% RH and 0.2 MPa backpressure gas feeds), which can retain performances for at least 120 h at a usefully high current density of 0.6 A cm-2 .

Fast Bulky Anion Conduction Enabled by Free Shuttling Phosphonium Cations.

Highly conductive anion-exchange membranes (AEMs) are desirable for applications in various energy storage and conversion technologies. However, conventional AEMs with bulky HCO3 - or Br- as counterion generally exhibit low conductivity because the covalent bonding restrains the tethered cationic group's mobility and rotation. Here, we report an alternative polyrotaxane AEM with nontethered and free-shuttling phosphonium cation. As proved by temperature-dependent NMR, solid-state NMR, and molecular dynamics simulation, the phosphonium cation possesses a thermally trigged shuttling behavior, broader extension range, and greater mobility, thus accelerating the diffusion conduction of bulky anions. Owing to this striking feature, high HCO3 - conductivity of 105 mS cm-1 at 90°C was obtained at a relatively lower ion-exchange capacity of 1.17 mmol g-1. This study provides a new concept for developing highly conductive anion-exchange membranes and will catalyze the exploration of new applications for polyrotaxanes in ion conduction processes.

Self-assembly of platinum(ii) 6-phenyl-2,2'-bipyridine complexes with solvato- and iono-chromic phenomena.

Mono- and di-nuclear organoplatinum(ii) monomers with cyclometalated 6-phenyl-2,2'-bipyridine ligands have been successfully constructed. These systems are capable of displaying intriguing solvato- and iono-chromic phenomena by elaborately manipulating non-covalent PtPt metal-metal and π-π stacking interactions for their self-assembly processes.