Interfacial Coordination Research Articles

Ambient γ-Rays-Mediated Noble-Metal Deposition on Defect-Rich Manganese Oxide for Glycerol-Assisted H2 Evolution at Industrial-Level Current Density.

Developing novel synthesis technologies is crucial to expanding bifunctional electrocatalysts for energy-saving hydrogen production. Herein, we report an ambient and controllable γ-ray radiation reduction to synthesize a series of noble metal nanoparticles anchored on defect-rich manganese oxides (M@MnO2-x , M=Ru, Pt, Pd, Ir) for glycerol-assisted H2 evolution. Benefiting from the strong penetrability of γ-rays, nanoparticles and defect supports are formed simultaneously and bridged by metal-oxygen bonds, guaranteeing structural stability and active site exposure. The special Ru-O-Mn bonds activate the Ru and Mn sites in Ru@MnO2-x through strong interfacial coordination, driving glycerol electrolysis at low overpotential. Furthermore, only a low cell voltage of 1.68 V is required to achieve 0.5 A cm-2 in a continuous-flow electrolyzer system along with excellent stability. In situ spectroscopic analysis reveals that the strong interfacial coordination in Ru@MnO2-x balances the competitive adsorption of glycerol and OH* on the catalyst surface. Theoretical calculations further demonstrate that the defect-rich MnO2 support promotes the dissociation of H2 O, while the defect-regulated Ru sites promote deprotonation and hydrogen desorption, synergistically enhancing glycerol-assisted hydrogen production.

Ambient γ‐Rays‐Mediated Noble‐Metal Deposition on Defect‐Rich Manganese Oxide for Glycerol‐Assisted H2 Evolution at Industrial‐Level Current Density

AbstractDeveloping novel synthesis technologies is crucial to expanding bifunctional electrocatalysts for energy‐saving hydrogen production. Herein, we report an ambient and controllable γ‐ray radiation reduction to synthesize a series of noble metal nanoparticles anchored on defect‐rich manganese oxides (M@MnO2‐x, M=Ru, Pt, Pd, Ir) for glycerol‐assisted H2 evolution. Benefiting from the strong penetrability of γ‐rays, nanoparticles and defect supports are formed simultaneously and bridged by metal‐oxygen bonds, guaranteeing structural stability and active site exposure. The special Ru−O−Mn bonds activate the Ru and Mn sites in Ru@MnO2‐x through strong interfacial coordination, driving glycerol electrolysis at low overpotential. Furthermore, only a low cell voltage of 1.68 V is required to achieve 0.5 A cm−2 in a continuous‐flow electrolyzer system along with excellent stability. In situ spectroscopic analysis reveals that the strong interfacial coordination in Ru@MnO2‐x balances the competitive adsorption of glycerol and OH* on the catalyst surface. Theoretical calculations further demonstrate that the defect‐rich MnO2 support promotes the dissociation of H2O, while the defect‐regulated Ru sites promote deprotonation and hydrogen desorption, synergistically enhancing glycerol‐assisted hydrogen production.

Design of thin-film nanocomposite membranes via synchronizing interfacial coordination and polymerization reactions for organic solvent nanofiltration

Thin-film nanocomposite (TFN) membranes have received immense research interest due to their high permeability and high selectivity in organic solvent nanofiltration (OSN). Herein, TFN membranes were fabricated by synchronizing interfacial coordination and polymerization reactions occurring at an ionic liquid/water interface. The one-pot interfacial reactions led to the simultaneous formation of Fe-MeIm nanofillers and polyamide thin layers with uniform dispersion and good compatibility. The resultant ternary membranes were denoted as Fe-MeIm/PA/PMIA, wherein the Fe-MeIm nanofillers were well-encapsulated in the ultrathin PA selective layer and both of them were located on top of the solvent-resistant PMIA substrate. The morphologies, microstructure, physicochemical properties, and OSN performance of the resultant TFN and traditional TFC membranes were systematically studied and compared. Moreover, the effects of the concentrations and ratios of reagents during the one-pot interfacial reactions were also elucidated. The optimal TFN membrane showed 5 times higher permeance than the TFC membrane without nanofillers while maintaining a high rejection for Congo red/ethanol separation. Moreover, it also showed good stability in various solvents and long-term stability and remarkably improved mechanical properties. This work provides a novel and time-saving fabrication strategy for TFN membranes for OSN application.

Surface Engineering over Metal-Organic Framework Nanoarray to Realize Boosted and Sustained Urea Oxidation.

Facilitating C─N bond cleavage and promoting *COO desorption are essential yet challenging in urea oxidation reactions (UORs). Herein a novel interfacial coordination assembly protocol is established to modify the Co-phytate coordination complex on the Ni-based metal-organic framework (MOF) nanosheet array (CC/Ni-BDC@Co-PA) toward boosted and sustained UOR electrocatalysis. Comprehensive experimental and theoretical investigations unveil that surface Co-PA modification over Ni-BDC can manipulate the electronic state of Ni sites, and in situ evolved charge-redistributed surface can promote urea adsorption and the subsequent C─N bond cleavage. Impressively, Co-PA functionalization can impart a negatively charged catalyst surface with improved aerophobicity, not only weakening *COO adsorption and promoting CO2 departure, but also repelling CO3 2- approaching to deactivate Ni species, eventually alleviating CO2 poisoning and enhancing operational durability. Beyond that, improved hydrophilic and aerophobic characteristics would also contribute to better mass transfer kinetics. Consequently, CC/Ni-BDC@Co-PA exhibits prominent UOR performance with an ultralow potential of 1.300V versus RHE to attain 10mA cm-2 , a small Tafel slope of 45mV dec-1 , and strong durability, comparable to the best Ni-based electrocatalysts documented thus far. This work affords a novel paradigm to construct MOF-based materials for promoted and sustained UOR catalysis through elegant surface engineering based on a metal-PA complex.

Strain-activated porous helical-spiny-like PtCu with exposed high-index facets for efficient alkaline hydrogen evolution

Integrating various control factors, including strain regulation, high-index crystal facets, and interfacial unsaturated coordination atoms, to improve the intrinsic performance of Pt-based catalysts is a very promising synthetic engineering approach for obtaining catalysts with ultra-high hydrogen evolution reaction (HER) activity. However, residual stress control and morphological regulation are inherently difficult to construct and, incidentally, keep the geometry. Herein, the phase engineering regulation method was used to synthesize porous helical-spiny-like PtCu (phs-PtCu) architecture with increased compressive strain. The porous pores in phs-PtCu further expose high-index facets and unsaturated atoms. Simultaneously, phs-PtCu exhibited an overpotential of only 434.7 mV under a high current density of 400 mA/cm2, much better than hs-PtCu and commercial Pt/C under alkaline conditions. Density functional theory (DFT) calculation indicated that the Gibbs free energy (ΔGH∗) of H–OH splitting and H∗ adsorption on the surface of phs-PtCu NWs (311) with the 3% compress strain exhibited the smallest value compared to phs-PtCu NWs and hs-PtCu NWs samples, revealing the adopted facile strategies play significant guidance to construct catalysts with high-index facets and strains.

Constructing epoxy and imidazole dual-functionalized polyurethane@Zinc oxide core-shell crosslinker based on coordination interactions for the preparation of strong, tough, and water-resistant soybean flour adhesives

Nanofilling has been regarded as an effective strategy to enhance adhesion performances of soybean flour (SF) adhesives, while it still exists huge challenges to regulate the interfacial properties of nanocomposites toward strong, tough, and water-resistant system. Here, we report on engineering interfacial crosslinking of nanohybrid and SF matrix via core–shell structure design. The reactive core–shell nanohybrid is prepared by epoxy and imidazole dual-functionalized polyurethane shell and zinc oxide (ZnO) nanofiller core under deposition effect of interfacial coordination interactions. Combining reactive epoxy groups and dynamic imidazole/ZnO bonds, a high-performance crosslinking structure with energy dissipation mechanism has been constructed at the interface of ZnO and SF matrix. The structure not only improves the stability of SF adhesive network to resist the external destruction of stress and moisture but also provides dynamic imidazole/metal cation coordination bonds as sacrificial units to facilitate energy dissipation during loading. Results show that the adhesives modified by 5 wt% core–shell nanohybrid present the best performances, in which an 142.0%, 162.3%, and 283.6% increment are observed in dry adhesion strength, wet adhesion strength, and adhesion toughness compared to pristine SF adhesives. Overall, such a high-performance biomass-derived adhesive has great potential for the practical use in wood industry.

Interfacial Engineering of Magnesiophilic Coordination Layer Stabilizes Mg Metal Anode

AbstractRechargeable magnesium batteries (RMBs) are seriously plagued by the direct exposure of the Mg anode to the electrolyte components, leading to spontaneous and electrochemical side reactions and interfacial passivation. Herein, a benign coordination layer is constructed at the Mg/electrolyte interface where aniline with a strong magnesiophilic amine group and high stability to Mg is chosen as representative, which has higher adsorption energy than DME (1,2‐dimethoxyethane) and trace water. This Mg coordination environment mitigates side reactions, forming a non‐passivating interface consisting of aniline and much fewer by‐products after several cycles. Therefore, the Mg symmetrical cell operates with a low overpotential and uniform Mg0 deposition. This interfacial coordination can also be adopted for Mg anode protection in various electrolyte cases of Mg(TFSI)2 electrolyte systems.

Interfacial Engineering of Magnesiophilic Coordination Layer Stabilizes Mg Metal Anode.

Rechargeable magnesium batteries (RMBs) are seriously plagued by the direct exposure of the Mg anode to the electrolyte components, leading to spontaneous and electrochemical side reactions and interfacial passivation. Herein, a benign coordination layer is constructed at the Mg/electrolyte interface where aniline with a strong magnesiophilic amine group and high stability to Mg is chosen as representative, which has higher adsorption energy than DME (1,2-dimethoxyethane) and trace water. This Mg coordination environment mitigates side reactions, forming a non-passivating interface consisting of aniline and much fewer by-products after several cycles. Therefore, the Mg symmetrical cell operates with a low overpotential and uniform Mg0 deposition. This interfacial coordination can also be adopted for Mg anode protection in various electrolyte cases of Mg(TFSI)2 electrolyte systems.

Investigation of coordinated behavior of deformation at the interface of Cu–Al laminated composite

To understand the differences between the microstructure and stress states owing to uncoordinated deformation in different regions of a Cu–Al contact interface, the normal stress distribution at the contact interface of the Cu–Al composites and the Al metal adhesion on the peeling surface of the Cu layer are investigated by performing numerical simulations and experimental studies. The results show that the percentage of Al metal adhered to the Cu side gradually increased from the edge to the central region. This is mainly because the central area of the contact interface bore a larger normal stress than the edge position, and when the interface normal stress exceeded 470 MPa, the pressure threshold value required for the extrusion of virgin metal from the surface-hardened layer on the Al side was satisfied. The effect of the initial Cu:Al thickness ratio on the degree of interfacial coordination is investigated, and the degree of coordination of the contact interface was observed to improve and then worsen with the increase in the initial Cu:Al thickness ratio (from 3:9 to 8:4). For composites with a Cu:Al thickness ratio of 4:8, the interface was well coordinated, and the bond strength reached 6.13 MPa, corresponding to a 173.7% improvement compared with the Cu–Al composite with more severe stress concentration (8:4).

Crosslinking two-dimensional metalloporphyrin (Me-TCPP) nanosheet with poly(ethylene) glycol semi-interpenetrating polymer network for ultrahigh CO2/N2 separation selectivity via “rubber-band” straightening effect

To efficient separate carbon dioxide from power plant flue gas, three two-dimensional (2D) metalloporphyrin (Me-TCPP) nanosheets, Zn-TCPP, Cu-TCPP, and Ni-TCPP are crosslinked with poly(ethylene) glycol (PEO) semi-interpenetrating polymer via “rubber-band” straightening effect. Dispersion-corrected periodic density functional (DFT-D2) calculation reveals that the lowest N4-Metalδ+···Oδ− distance (2.81 Å) and the highest binding energy (19.9 kJ mol−1) are obtained between CO2 molecule and metalloporphyrin center (Zn–N4), as well as the lowest O4-Metalδ+···Oδ− distance (4.68 Å) and the highest binding energy (18.8 kJ mol−1) on metal cluster (Zn–O4). The 2D Zn-TCPP nanosheet with the strongest affinity toward CO2 molecule generates Zn2+-CO2 complex to remarkably boost CO2 solubility in mixed matrix membrane (MMMs). Thus, 2.5 wt% Zn-TCPP nanosheet incorporated PEO-based MMMs dramatically promotes CO2 permeability to 198 Barrers and ultrahigh CO2/N2 selectivity to 81. A novel “rubber-band” straightening effect is found and verified, which is induced by abundant interfacial coordination bonds between metal ions in nanosheets and ester groups (O–CO) in PEO polymer chains, the strong Me–O–CO interaction sites hold polymer chains and lead to their regular rearrangement. Owing to the abundant PEG groups in PEGMEA macromolecule chains, incorporating 1 wt% Zn-TCPP nanosheet into crosslinked XLPEGDAcoPEGMEA polymer achieves the highest CO2 permeability of 398 Barrers.

In Situ Formation ZnIn2 S4 /Mo2 TiC2 Schottky Junction for Accelerating Photocatalytic Hydrogen Evolution Kinetics: Manipulation of Local Coordination and Electronic Structure.

Regulating electronic structures of the active site by manipulating the local coordination is one of the advantageous means to improve photocatalytic hydrogen evolution (PHE) kinetics. Herein, the ZnIn2 S4 /Mo2 TiC2 Schottky junctions are designed to be constructed through the interfacial local coordination of In3+ with the electronegative O terminal group on Mo2 TiC2 based on the different work functions. Kelvin probe force microscopy and charge density difference reveal that an electronic unidirectional transport channel across the Schottky interface from ZnIn2 S4 to Mo2 TiC2 is established by the formed local nucleophilic/electrophilic region. The increased local electron density of Mo2 TiC2 inhibits the backflow of electrons, boosts the charge transfer and separation, and optimizes the hydrogen adsorption energy. Therefore, the ZnIn2 S4 /Mo2 TiC2 photocatalyst exhibits a superior PHE rate of 3.12 mmol g-1 h-1 under visible light, reaching 3.03 times that of the pristine ZnIn2 S4 . This work provides some insights and inspiration for preparing MXene-based Schottky catalysts to accelerate PHE kinetics.

Metal nanoparticles capped with plant polyphenol for oxygen reduction electrocatalysis

The development of a convenient and universal strategy for the synthesis of inorganic–organic hybrid nanomaterials with phenolic coating on the surface is of special significance for the preparation of electrocatalysts. In this work, we report an environmentally friendly, practical, and convenient method for one-step reduction and generation of organically capped nanocatalysts using natural polyphenol tannic acid (TA) as reducing agents and coating agents. TA coated metal (Pd, Ag and Au) nanoparticles are prepared by this strategy, among which TA coated Pd nanoparticles (PdTA NPs) show excellent oxygen reduction reaction activity and stability under alkaline conditions. Interestingly, the TA in the outer layer makes PdTA NPs methanol resistant, and TA acts as molecular armor against CO poisoning. We propose an efficient interfacial coordination coating strategy, which opens up new way to regulate the interface engineering of electrocatalysts reasonably and has broad application prospects.

17O hyperfine spectroscopy in surface chemistry and catalysis

Oxide-based materials are of key technological importance in different areas including advanced functional materials, solid state chemistry and catalysis. Many of the key questions concerning these areas involve understanding the chemical bond between the metal and the oxygen ions in the first or subsequent coordinating shells. The spectroscopic study of oxygen is therefore of fundamental importance to elucidate the complex interfacial coordination chemistry that underlies the development of metal-oxide supported catalysts and other advanced materials. Oxygen atoms at solid surfaces or lining the pores of zeolite frameworks play a vital role in stabilizing and defining the electronic and geometric structure of single metal atoms or clusters that act as catalytically active sites. In the case of paramagnetic species, EPR and its related hyperfine techniques offer a unique opportunity to explore and understand the nature of the chemical bonding in metal-oxide systems through the detection of the 17O hyperfine interaction. In this perspective we offer an overview of experimental considerations and relevant examples specific to 17O hyperfine spectroscopy of transition metal ions in zeolites relevant to catalysis. 17O hyperfine coupling values are obtained, which allow discriminating σ- and π-bonding channels in metal-oxygen bonds involving first-row transition metal ions. An exhaustive collection of 17O hyperfine and nuclear quadrupole couplings in different systems including molecular and biomolecular chemistry is provided, emphasizing the connection between interfacial and molecular inorganic coordination chemistry.

Interfacial oxygen coordination environment regulation towards high-performance Li-rich layered oxide cathode

Lithium-rich layered oxides (LLO) have drawn increasing attention as one of the most promising cathodes for next-generation high-energy–density lithium-ion batteries (LIBs). However, they are plagued by low initial Coulombic efficiency (ICE) and terrible cyclic stability due to their intrinsic irreversible oxygen release. Herein, to enhance the comprehensive electrochemical performance of LLO, an effective strategy is brought up to regulate the interfacial oxygen coordination environment via lithium deficiencies, Na+ ion doping, as well as the induced Li+/Ni2+ antisite defects and in-situ epitaxial grown spinel phase. The density functional theory calculations (DFT) confirm that the existence of lithium deficiencies and Na+ ions doping can decrease the diffusion energy barrier of Li+ ions. Meanwhile, the regulated oxygen coordination environment results in an increase in the oxygen vacancy formation energy, which is beneficial for the improvement of the lattice oxygen stability in the deeply charged state. As a result, the modified sample exhibits high initial coulombic efficiency of 91.2% and good capacity retention of 95.3% after 400 cycles at 1C (1C = 250 mA g−1). This work offers a new idea for designing advanced LLO cathodes, which could promote their practical applications in high-energy–density LIBs.

Interfacial Coordination Bonding-Assisted Redox Mechanism-Driven Highly Selective Precious Metal Recovery on Covalent-Functionalized Ultrathin 1T-MoS2.

Rational design of functional material interfaces with well-defined physico-chemical-driven forces is crucial for achieving highly efficient interfacial chemical reaction dynamics for resource recovery. Herein, via an interfacial structure engineering strategy, precious metal (PM) coordination-active pyridine groups have been successfully covalently integrated into ultrathin 1T-MoS2 (Py-MoS2). The constructed Py-MoS2 shows highly selective interfacial coordination bonding-assisted redox (ICBAR) functionality toward PM recycling. Py-MoS2 shows state-of-the-art high recovery selectivity toward Au3+ and Pd4+ within 13 metal cation mixture solutions. The related recycling capacity reaches up to 3343.00 and 2330.74 mg/g for Au3+ and Pd4+, respectively. More importantly, above 90% recovery efficiencies have been achieved in representative PMs containing electronic solid waste leachate, such as computer processing units (CPU) and spent catalysts. The ICBAR mechanism developed here paves the way for interface engineering of the well-documented functional materials toward highly efficient PM recovery.

Strong spin-lattice entanglement in cobaltites

Strongly correlated electronic system contains strong coupling among multi-order parameters and is easy to efficiently tune by external field. Cobaltite (LaCoO<sub>3</sub>) is a typical multiferroic (ferroelastic and ferromagnetic) material, which has been extensively investigated over decades. Conventional research on cobaltites has focused on the ferroelastic phase transition and structure modulation under stress. Recently, researchers have discovered that cobaltite thin films undergo a paramagnetic-to-ferromagnetic phase transition under tensile strain, however, its origin has been controversial over decades. Some experimental evidence shows that stress leads the valence state of cobalt ions to decrease, and thus producing spin state transition. Other researchers believe that the stress-induced nano-domain structure will present a long-range ordered arrangement of high spin states, which is the main reason for producing the ferromagnetism of cobalt oxide films. In this paper, we review a series of recent researches of the strong correlation between spin and lattice degrees of freedom in cobalt oxide thin films and heterojunctions. The reversible spin state transition in cobalt oxide film is induced by structural factors such as thin-film thickness, lattice mismatch stress, crystal symmetry, surface morphology, interfacial oxygen ion coordination, and oxygen octahedral tilting while the valence state of cobalt ions is kept unchanged, and thus forming highly adjustable macroscopic magnetism. Furthermore, the atomic-level precision controllable film growth technology is utilized to construct single cell layer cobaltite superlattices, thereby achieving ultra-thin two-dimensional magnetic oxide materials through efficient structure regulation. These advances not only clarified the strong coupling between lattice and spin order parameters in the strongly correlated electronic system, but also provided excellent candidate for the realization of ultra-thin room temperature ferromagnets that are required by oxide spintronic devices.

Adaptable thermal conductive, high toughness and compliant Poly(dimethylsiloxane) elastomer composites based on interfacial coordination bonds

Compliant elastomers have been widely used in industry and daily life benefited from their large reversible deformability. But poor thermal conductivity and toughness of unfilled elastomers usually limit their use in thermal management. The most common method to increase these properties is to incorporate thermally conductive fillers to polymeric materials. However, thermally conductive network formed by the large of fillers not only decreases the elastomeric compliance, but may also damages the toughness. Herein, to study the effect of polymer/filler interfacial interaction on thermal and mechanical properties, we choose shorter poly(dimethylsiloxane) without entanglement to construct elastomer composites by non-covalent interfacial carboxyl/aluminum and carboxyl/zinc oxide coordination bonds. Time-domain thermoreflectance technique demonstrates that the strong interfacial interaction leads to reduced interfacial thermal resistance between polymeric materials and fillers, resulting in enhanced thermal conductivity of the elastomer composites. Otherwise, two independent dynamic coordination bonds have been investigated on temperature- and frequency-sweep rheometer. The results reveal that the elastomer composites can counteract the negative effect of high filler content on toughness and compliance according to energy-dissipation of dissociation and generation of dynamic coordination bonds. Thanks to the enhanced interfacial interaction, our material shows high toughness (1073 J/m2), thermally conductive (2.37 W/(m·K)), compliant (stress is 0.11 MPa and elongation break is 910%) and fully reprocess. For the application as thermal interface materials, we demonstrate effective heat dissipation on chip and LED. Our present work suggests that the design principles based on interfacial coordination interaction can be applied to the development of new classes of elastomer composites.

In-situ formation of cobalt phosphide nanoparticles confined in three-dimensional porous carbon for high-performing zinc-air battery and water splitting

AbstractThe rational design of efficient and stable carbon-based electrocatalysts for oxygen reduction and oxygen evolution reactions is crucial for improving energy density and long-term stability of rechargeable zinc-air batteries (ZABs). Herein, a general and controllable synthesis method was developed to prepare three-dimensional (3D) porous carbon composites embedded with diverse metal phosphide nanocrystallites by interfacial coordination of transition metal ions with phytic acid-doped polyaniline networks and subsequent pyrolysis. Phytic acid as the dopant of polyaniline provides favorable anchoring sites for metal ions owing to the coordination interaction. Specifically, adjusting the concentration of adsorbed cobalt ions can achieve the phase regulation of transition metal phosphides. Thus, with abundant cobalt phosphide nanoparticles and nitrogen- and phosphorus-doping sites, the obtained carbon-based electrocatalysts exhibited efficient electrocatalytic activities toward oxygen reduction and evolution reactions. Consequently, the fabricated ZABs exhibited a high energy density, high power density of 368 mW cm−2, and good cycling/mechanical stability, which could power water splitting for integrated device fabrication with high gas yields.

Multiple chemical valences induced interface regulation in perovskite nickelate/carbon nitride for boosting photocatalytic hydrogen evolution

Recent developments in transition metal-based photocatalysts have heightened the need for superior solar utilization. Evidence suggests that properly adjusting the chemical valence of the transition metal elements could simultaneously achieve broad-spectrum absorption and efficient charge separation for the photocatalysts. However, the understanding and application of this strategy remain a significant challenge. Herein, a series of La0.9Ni0.8Co0.2O3-α/g-C3N4 (LNCO/CN) composites were synthesized employing a mild reduction procedure in the H2/Ar atmosphere. Experimental studies reveal that the composites regulated by interfacial coordination unsaturation Ni2+ and metal Ni0 possess accelerated Z-scheme charge transfer through the interfacial bond between Ni2+ and N. Besides, the localized-surface-plasmon-resonance-induced “hot electrons” injection process of in situ grown Ni0 nanoparticle is confirmed, which can efficiently quench the photoinduced holes and create hole vacancies around the interface. Due to the synergistic effect between Ni2+ and Ni0, the lifetime of the photo-excited electrons is prolonged with inhibited recombination behavior. After modulation, optimal LNCO/CN Z-scheme hybrid exhibits 9-fold promotion of photocatalytic hydrogen evolution rate compared to pristine LNCO/CN. This study gives valuable insight into the purposeful utilization of the chemical valence modulating strategy, which alters the chemical valence of transition metal elements to enhance the performance of perovskite-based photocatalysts dramatically.

Metal Ion‐Directed Coordination Programming of Biomolecules to Bioinspired Nanoflowers

AbstractBioinspired molecular and macromolecular systems could be a driver for new generation semiconductor‐synthetic biology (Semi‐Syn‐Bio) technologies, shifting the materials design paradigm by utilizing bioinspired and biological structures to design molecular and supramolecular architectures as bionanomaterials in the fabrication of devices and components. Herein, a simple and rapid self‐assembly approach of interfacial coordination programming of a biological amphiphile, a fatty acid, using a transition metal ion, copper cation (Cu2+) to direct the formation of nanoflowers of Cu2+‐conjugated supramolecular structures is demonstrated. The fatty acid molecules form complexes with the copper ions and then self‐assemble into microstructures with flower‐like petals, which are highly nanoporous thin sheets. The growth of microstructures is found to be independent from the precursors’ stoichiometric ratios, demonstrating a versatile interfacial coordination programming approach to make crystalline, uniquely shaped‐double peony flower‐like microstructures. It is anticipated that design principles and directed self‐assembly approaches for the interfacial coordination programming of biomolecules may advance the state‐of‐the‐art of biomaterials research, providing deeper understanding in the paradigm of design, synthesis, self‐assembly, and fabrication of Semi‐Syn‐Bio superstructure systems.