Switching CO2 Electroreduction toward Ethanol by Delocalization State-Tuned Bond Cleavage.

The electrochemical CO2 reduction reaction by copper-based catalysts features a promising approach to generate value-added multicarbon (C2+) products. However, due to the unfavored formation of oxygenate intermediates on the catalyst surface, the selectivity of C2+ alcohols like ethanol remains unsatisfactory compared to that of ethylene. The bifurcation point (i.e., the CH2═CHO* intermediate adsorbed on Cu via a Cu-O-C linkage) is critical to the C2+ product selectivity, whereas the subsequent cleavage of the Cu-O or the O-C bond determines the ethanol or ethylene pathway. Inspired by the hard-soft acid-base theory, in this work, we demonstrate an electron delocalization tuning strategy of the Cu catalyst by a nitrene surface functionalization approach, which allows weakening and cleaving of the Cu-O bond of the adsorbed CH2═CHO*, as well as accelerating hydrogenation of the C═C bond along the ethanol pathway. As a result, the nitrene-functionalized Cu catalyst exhibited a much-enhanced ethanol Faradaic efficiency of 45% with a peak partial current density of 406 mA·cm-2, substantially exceeding that of unmodified Cu or amide-functionalized Cu. When assembled in a membrane electrode assembly electrolyzer, the catalyst presented a stable CO2-to-ethanol conversion for >300 h at an industrial current density of 400 mA·cm-2.

Electrocatalytic Glycerol Upgrading into Glyceric Acid on Ni3Sn Intermetallic Compound.

Electrochemical glycerol oxidation features an attractive approach of converting bulk chemicals into high-value products such as glyceric acid. Nonetheless, to date, the major product selectivity has mostly been limited as low-value C1 products such as formate, CO, and CO2, due to the fast cleavage of carbon-carbon (C-C) bonds during electro-oxidation. Herein, the study develops an atomically ordered Ni3Sn intermetallic compound catalyst, in which Sn atoms with low carbon-binding and high oxygen-binding capability allow to tune the adsorption of glycerol oxidation intermediates from multi-valent carbon binding to mono-valent carbon binding, as well as enhance *OH binding and subsequent nucleophilic attack. The Ni3Sn electrocatalyst exhibits one of the highest glycerol-to-glyceric acid performances, including a high glycerol conversion rate (1199 µmol h-1) and glyceric acid selectivity (62 ± 3%), a long electrochemical stability of > 150 h, and the capability of direct conversion of crude glycerol (85% purity) into glyceric acid. The work features the rational design of highly ordered catalytic sites for tailoring intermediate binding and reaction pathways, thereby facilitating the efficient production of high-value chemical products.

Weak-Field Electro-Flash Induced Asymmetric Catalytic Sites toward Efficient Solar Hydrogen Peroxide Production.

Borocarbonitride (BCN), in a mesoscopic asymmetric state, is regarded as a promising photocatalyst for artificial photosynthesis. However, BCN materials reported in the literature primarily consist of symmetric N-[B]3 units, which generate highly spatial coupled electron-hole pairs upon irradiation, thus kinetically suppressing the solar-to-chemical conversion efficiency. Here, we propose a facile and fast weak-field electro-flash strategy, with which structural symmetry breaking is introduced on key nitrogen sites. As-obtained double-substituted BCN (ds-BCN) possesses high-concentration asymmetric [B]2-N-C coordination, which displays a highly separated electron-hole state and broad visible-light harvesting, as well as provides electron-rich N sites for O2 affinity. Thereby, ds-BCN delivers an apparent quantum yield of 7.6% at 400 nm and a solar-to-chemical conversion efficiency of 0.3% for selective 2e-reduction of O2 to H2O2, over 4-fold higher than that of the traditional calcined BCN analogue and superior to the metal-free C3N4-based photocatalysts reported so far. The weak-field electro-flash method and as-induced catalytic site symmetry-breaking methodologically provide a new method for the fast and low-cost fabrication of efficient nonmetallic catalysts toward solar-to-chemical conversions.

(111) Facet-oriented Cu2Mg Intermetallic Compound with Cu3-Mg Sites for CO2 Electroreduction to Ethanol with Industrial Current Density.

The efficient ethanol electrosynthesis from CO2 is challenging with low selectivity at high CO2 electrolysis rates, due to the competition with H2 and other reduction products. Copper-based bimetallic electrocatalysts are potential candidates for the CO2-to-ethanol conversion, but the secondary metal has mainly been focused on active components (such as Ag, Sn) for CO2 electroreduction, which also promote selectivity of ethylene or other reduction products rather than ethanol. Limited attention has been given to alkali-earth metals due to their inherently active chemical property. Herein, we rationally synthesized a (111) facet-oriented nano Cu2Mg (designated as Cu2Mg(111)) intermetallic compound with high-density ordered Cu3-Mg sites. The in situ Raman spectroscopy and density function theory calculations revealed that the Cu3 - δ $_{^{\rm{{\rm \delta} }} }$ --Mg- δ $_{^{\rm{{\rm \delta} }} }$ + active sites allowed to increase *CO surface coverage, decrease reaction energy for *CO-CO coupling, and stabilize *CHCHOH intermediates, thus promoting the ethanol formation pathway. The Cu2Mg(111) catalyst exhibited a high FEC2H5OH of 76.2±4.8 % at 600 mA⋅cm-2, and a peak value of |jC2H5OH| of 720±34 mA⋅cm-2, almost 4 times of that using conventional Cu2Mg with (311) facets, comparable to the best reported values for the CO2-to-ethanol electroreduction.

Bipolaronic Motifs Induced Spatially Separated Catalytic Sites for Tunable Syngas Photosynthesis From CO2.

Photocatalytic reduction of CO2 into syngas is a promising way to tackle the energy and environmental challenges; however, it remains a challenge to achieve reaction decoupling of CO2 reduction and water splitting. Therefore, efficient production of syngas with a suitable CO/H2 ratio for Fischer-Tropsch synthesis can hardly be achieved. Herein, bipolaronic motifs including Co(II)-pyridine N motifs and Co(II)-imine N motifs are rationally designed into a crystalline imine-linked 1,10-phenanthroline-5,6-dione-based covalent organic framework (bp-Co-COF) with a triazine core. These featured structures with spatially separated active sites exhibit efficient photocatalytic performance toward CO2-to-syngas conversion with a suitable CO/H2 ratio (1:1-1:3). The bipolaronic motifs enable a highly separated electron-hole state, whereby the Co(II)-pyridine N motifs tend to be the active sites for CO2 activation and accelerate the hydrogenation to form *COOH intermediates; whilst, the Co(II)-imine N motifs increase surface hydrophilicity for H2 evolution. The photocatalytic reductions of CO2 and H2O thus decouple and proceed via a concerted way on the bipolaronic motifs of bp-Co-COF. The optimal bp-Co-COF photocatalyst achieves a high syngas evolution rate of 15.8 mmol g-1 h-1 with CO/H2 ratio of 1:2, outperforming previously reported COF-based photocatalysts.

Enhanced Carbon-Carbon Coupling at Interfaces with Abrupt Coordination Number Changes.

Cu-catalyzed electrochemical CO2 reduction reaction (CO2RR) produces multi-carbon (C2+) chemicals with considerable selectivities and activities, yet required high overpotentials impede its practical application. Here, we design interfaces with abrupt coordination number (CN) changes that greatly reduce the applied potential for achieving high C2+ Faradaic efficiency (FE). Encouraged by the mechanistic finding that the coupling between *CO and *CO(H) is the most probable C-C bond formation path, we use Cu2O- and Cu-phthalocyanine-derived Cu (OD-Cu and PD-Cu) to build the interface. Using operando X-ray absorption spectroscopy (XAS), we find that the Cu CN of OD-Cu is ~11, favoring CO* adsorption, while the PD-Cu has a COH*-favorable CN of ~4. Operando Raman spectroscopy revealed that the interfaces with abrupt CN changes promote *OCCOH formation. As a result, the designed catalyst achieves a C2+ FE of 85±2 % at 220 mA cm-2 in a zero-gap CO2 electrolyzer. An improvement of C2+ FE by 3 times is confirmed at the low potential regime where the current density is 60-140 mA cm-2, compared to bare OD-Cu. We report a 45-h stable CO2RR operation at 220 mA cm-2, producing a C2+ product FE of ~80 %.

Anthraquinone-Induced asymmetric antimony coordination center for selective O2 photoreduction to H2O2.

Achieving O2 photoreduction to H2O2 with high selectivity control and durability while using easily accessible catalyst requires new synthesis strategies. Herein, we propose an asymmteric Sb coordination active center strategy of introducing anthraquinone (AQ) and heptazine to form local N3 - Sb - O coordination by a rapid and simple explosive crystallization approach, resulting in a mesoporous conjugated heptazine-amide-AQ polymer coordinated Sb (HAAQ-Sb). It is demonstrated that the N3 - Sb - O coordination effectively suppresses the charge recombination and acts as the highly active site for O2 adsorption. Moreover, as-introduced AQ units initiate low-barrier hydrogen transfer through a reversible redox process that triggers highly-efficient H2O2 production. A superior apparent quantum yield of 20.2 % at 400 nm and a remarkable solar-to-chemical conversion efficiency of 0.71 % are achieved on the optimal HAAQ-Sb, which is the highest among C3N4-based photocatalysts at present. This asymmetric coordination concept and material design method provide new perspectives for the research of novel catalysts toward artificial photosynthesis.

Custom-Design of Strong Electron/Proton Extractor on COFs for Efficient Photocatalytic H2O2 Production.

The development of photocatalysts with continuous electron extraction and rapid proton transfer could kinetically accelerate the artificial photosynthesis, but remains a challenge. Herein, we report the topology-guided synthesis of a high-crystalline triazine covalent organic framework (COF) decorated by uniformly distributed polar oxygen functional groups (sulfonic group or carboxyl) as the strong electron/proton extractor for efficient photocatalytic H2O2 production. It was found that the polarity-based proton transfer as well as electron enrichment in as-obtained COFs played a crucial role in improving the H2O2 photosynthesis efficiency (i.e., with an activity order of sulfonic acid- (SO3H-COF)>carboxyl- (COOH-COF)>hydrogen- (H-COF) functionalized COFs). The strong polar sulfonic acid group in the high-crystalline SO3H-COF triggered a well-oriented built-in electric field and more hydrophilic surface, which serves as an efficient carrier extractor enabling a continuous transportation of the photogenerated electrons and interfacial proton to the active sites (i.e., C atoms linked to -SO3H group). As-accelerated proton-coupled electron transfer (PCET), together with the stabilized O2 adsorption finally leads to the highest H2O2 production rate of 4971 µmol g-1 h-1 under visible light irradiation. Meanwhile, a quantum yield of 15 % at 400 nm is obtained, superior to most reported COF-based photocatalysts.

Tailoring the *CO and *H Coverage for Selective CO2 Electroreduction to CH4 or C2H4.

In the electrochemical CO2 reduction reaction (CO2RR), the coverages of *CO and *H intermediates on a catalyst surface are critical for the selective generation of C1 or C2 products. In this work, we have synthesized several CuxZnyMnz ternary alloy electrocatalysts, including Cu8ZnMn, Cu8Zn6Mn, and Cu8ZnMn2, by varying the doping compositions of Zn and Mn, which are efficient in binding *CO and *H adsorbates in the CO2 electroreduction process, respectively. The increase of *H coverage allows to promotion of the CH4 and H2 formation, while the increase of the *CO coverage facilitates the production of C2H4 and CO. As a result, the Cu8ZnMn catalyst presented a high CO2-to-CH4 partial current density (-418 ± 22 mA cm-2) with a Faradaic efficiency of 55 ± 2.8%, while the Cu8Zn6Mn catalyst exhibited a CO2-to-C2H4 partial current density (-440 ± 41 mA cm-2) with a Faradaic efficiency of 58 ± 4.5%. The study suggests a useful strategy for rational design and fabrication of Cu electrocatalysts with different doping for tailoring the reduction products.

1D Insertion Chains Induced Small-Polaron Collapse in MoS2 2D Layers Toward Fast-Charging Sodium-Ion Batteries.

Molybdenum disulfide (MoS2 ) with high theoretical capacity is viewed as a promising anode for sodium-ion batteries but suffers from inferior rate capability owing to the polaron-induced slow charge transfer. Herein, a polaron collapse strategy induced by electron-rich insertions is proposed to effectively solve the above issue. Specifically, 1D [MoS] chains are inserted into MoS2 to break the symmetry states of 2D layers and induce small-polaron collapse to gain fast charge transfer so that the as-obtained thermodynamically stable Mo2 S3 shows metallic behavior with 107 times larger electrical conductivity than that of MoS2 . Theoretical calculations demonstrate that Mo2 S3 owns highly delocalized anions, which substantially reduce the interactions of Na-S to efficiently accelerate Na+ diffusion, endowing Mo2 S3 lower energy barrier (0.38 vs 0.65 eV of MoS2 ). The novel Mo2 S3 anode exhibits a high capacity of 510 mAh g-1 at 0.5 C and a superior high-rate stability of 217 mAh g-1 at 40 C over 15 000 cycles. Further in situ and ex situ characterizations reveal the in-depth reversible redox chemistry in Mo2 S3 . The proposed polaron collapse strategy for intrinsically facilitating charge transfer can be conducive to electrode design for fast-charging batteries.

High-Power CO2-to-C2 Electroreduction on Ga-Spaced, Square-like Cu Sites.

The electrochemical conversion of CO2 into multicarbon (C2) products on Cu-based catalysts is strongly affected by the surface coverage of adsorbed CO (*CO) intermediates and the subsequent C-C coupling. However, the increased *CO coverage inevitably leads to strong *CO repulsion and a reduced C-C coupling efficiency, thus resulting in suboptimal CO2-to-C2 activity and selectivity, especially at ampere-level electrolysis current densities. Herein, we developed an atomically ordered Cu9Ga4 intermetallic compound consisting of Cu square-like binding sites interspaced by catalytically inert Ga atoms. Compared to Cu(100) previously known with a high C2 selectivity, the Ga-spaced, square-like Cu sites presented an elongated Cu-Cu distance that allowed to reduce *CO repulsion and increased *CO coverage simultaneously, thus endowing more efficient C-C coupling to C2 products than Cu(100) and Cu(111). The Cu9Ga4 catalyst exhibited an outstanding CO2-to-C2 electroreduction, with a peak C2 partial current density of 1207 mA cm-2 and a corresponding Faradaic efficiency of 71%. Moreover, the Cu9Ga4 catalyst demonstrated a high-power (∼200 W) electrolysis capability with excellent electrochemical stability.

Assessment of visual function in blind mice and monkeys with subretinally implanted nanowire arrays as artificial photoreceptors.

Retinal prostheses could restore image-forming vision in conditions of photoreceptor degeneration. However, contrast sensitivity and visual acuity are often insufficient. Here we report the performance, in mice and monkeys with induced photoreceptor degeneration, of subretinally implanted gold-nanoparticle-coated titania nanowire arrays providing a spatial resolution of 77.5 µm and a temporal resolution of 3.92 Hz in ex vivo retinas (as determined by patch-clamp recording of retinal ganglion cells). In blind mice, the arrays allowed for the detection of drifting gratings and flashing objects at light-intensity thresholds of 15.70-18.09 µW mm-2, and offered visual acuities of 0.3-0.4 cycles per degree, as determined by recordings of visually evoked potentials and optomotor-response tests. In monkeys, the arrays were stable for 54 weeks, allowed for the detection of a 10-µW mm-2 beam of light (0.5° in beam angle) in visually guided saccade experiments, and induced plastic changes in the primary visual cortex, as indicated by long-term in vivo calcium imaging. Nanomaterials as artificial photoreceptors may ameliorate visual deficits in patients with photoreceptor degeneration.

Photo-Driven Quasi-Topological Transformation Exposing Highly Active Nitrogen Cation Sites for Enhanced Photocatalytic H2 O2 Production.

Herein, the exposure of highly-active nitrogen cation sites has been accomplished by photo-driven quasi-topological transformation of a 1,10-phenanthroline-5,6-dione-based covalent organic framework (COF), which contributes to hydrogen peroxide (H2 O2 ) synthesis during the 2-electron O2 photoreduction. The exposed nitrogen cation sites with photo-enhanced Lewis acidity not only act as the electron-transfer motor to adjust the inherent charge distribution, powering continuous and stable charge separation, and broadening visible-light adsorption, but also providing a large number of active sites for O2 adsorption. The optimal catalyst shows a high H2 O2 production rate of 11965 µmol g-1 h-1 under visible light irradiation and a remarkable apparent quantum yield of 12.9 % at 400 nm, better than most of the previously reported COF photocatalysts. This work provides new insights for designing photo-switchable nitrogen cation sites as catalytic centers toward efficient solar to chemical energy conversion.

Promoting CO2 Electroreduction to Acetate by an Amine-Terminal, Dendrimer-Functionalized Cu Catalyst.

Acetate derived from electrocatalytic CO2 reduction represents a potential low-carbon synthesis approach. However, the CO2-to-acetate activity and selectivity are largely inhibited by the low surface coverage of in situ generated *CO, as well as the inefficient ethenone intermediate formation due to the side reaction between CO2 and alkaline electrolytes. Tuning catalyst microenvironments by chemical modification of the catalyst surface is a potential strategy to enhance CO2 capture and increase local *CO concentrations, while it also increases the selectivity of side reduction products, such as methane or ethylene. To solve this challenge, herein, we developed a hydrophilic amine-tailed, dendrimer network with enhanced *CO intermediate coverage on Cu catalytic sites while at the same time retaining the in situ generated OH- as a high local pH environment that favors the ethenone intermediate toward acetate. The optimized amine-network coordinated Cu catalyst (G3-NH2/Cu) exhibits one of the highest CO2-to-acetate Faradaic efficiencies of 47.0% with a partial current density of 202 mA cm-2 at -0.97 V versus the reversible hydrogen electrode.

Interfacial Water Tuning by Intermolecular Spacing for Stable CO2 Electroreduction to C2+ Products.

Electroreduction of CO2 to multi-carbon (C2+ ) products is a promising approach for utilization of renewable energy, in which the interfacial water quantity is critical for both the C2+ product selectivity and the stability of Cu-based electrocatalytic sites. Functionalization of long-chain alkyl molecules on a catalyst surface can help to increase its stability, while it also tends to block the transport of water, thus inhibiting the C2+ product formation. Herein, we demonstrate the fine tuning of interfacial water by surface assembly of toluene on Cu nanosheets, allowing for sustained and enriched CO2 supply but retarded water transfer to catalytic surface. Compared to bare Cu with fast cathodic corrosion and long-chain alkyl-modified Cu with main CO product, the toluene assembly on Cu nanosheet surface enabled a high Faradaic efficiency of 78 % for C2+ and a partial current density of 1.81 A cm-2 . The toluene-modified Cu catalyst further exhibited highly stable CO2 -to-C2 H4 conversion of 400 h in a membrane-electrode-assembly electrolyzer, suggesting the attractive feature for both efficient C2+ selectivity and excellent stability.

Promoting CO2 Electroreduction to Multi-Carbon Products by Hydrophobicity-Induced Electro-Kinetic Retardation.

Advancing the performance of the Cu-catalyzed electrochemical CO2 reduction reaction (CO2 RR) is crucial for its practical applications. Still, the wettable pristine Cu surface often suffers from low exposure to CO2 , reducing the Faradaic efficiencies (FEs) and current densities for multi-carbon (C2+ ) products. Recent studies have proposed that increasing surface availability for CO2 by cation-exchange ionomers can enhance the C2+ product formation rates. However, due to the rapid formation and consumption of *CO, such promotion in reaction kinetics can shorten the residence of *CO whose adsorption determines C2+ selectivity, and thus the resulting C2+ FEs remain low. Herein, we discover that the electro-kinetic retardation caused by the strong hydrophobicity of quaternary ammonium group-functionalized polynorbornene ionomers can greatly prolong the *CO residence on Cu. This unconventional electro-kinetic effect is demonstrated by the increased Tafel slopes and the decreased sensitivity of *CO coverage change to potentials. As a result, the strongly hydrophobic Cu electrodes exhibit C2+ Faradaic efficiencies of ≈90 % at a partial current density of 223 mA cm-2 , more than twice of bare or hydrophilic Cu surfaces.

Efficient photosynthesis of hydrogen peroxide by triazole-modified covalent triazine framework nanosheets.

Two-dimensional (2D) polymeric semiconductors, especially covalent triazine framework (CTF) nanosheets with aromatic triazine linkages are emerging as attractive metal-free photocatalysts owing to their predictable structures, good semiconducting properties, and high stability. However, the quantum size effect and ineffective electron screening of 2D CTF nanosheets cause an enlargement of electronic band gap and high excited electron-hole binding energies, which lead to low-level enhancements in photocatalytic performance. Herein, we present a novel triazole groups functionalized CTF nanosheet (CTF-LTZ) synthesized by facile combination of ionothermal polymerization and freeze-drying strategy from the unique letrozole precursor. The incorporation of the high-nitrogen-containing triazole group effectively modulates the optical and electronic properties, resulting in narrowed bandgap from 2.92 eV for unfunctionalized CTF to 2.22 eV for CTF-LTZ and dramatically improved charge separation, as well as highly-active sites for O2 adsorption. As a result, CTF-LTZ photocatalyst exhibits excellent performance and superior stability in H2O2 photosynthesis, with a high H2O2 production rate of 4068 µmol h-1 g-1 and a remarkable apparent quantum efficiency of 4.5 % at 400 nm. This work provides a simple and effective approach for rational design highly-efficient polymeric photocatalysts for H2O2 production.

A Surfactant-Free and General Strategy for the Synthesis of Bimetallic Core-Shell Nanocrystals on Reduced Graphene Oxide through Targeted Photodeposition.

Tunable physicochemical properties of bimetallic core-shell heterostructured nanocrystals (HNCs) have shown enormous potential in electrocatalytic reactions. In many cases, HNCs are required to load on supports to inhibit catalyst aggregation. However, the introduction of supports during the process of growing core-shell HNCs makes the synthesis much more complicated and difficult to control precisely. Herein, we reported a universal photochemical synthetic strategy for the controlled synthesis of well-defined surfactant-free core-shell metal HNCs on a reduced graphene oxide (rGO) support, which was assisted by the fine control of photogenerated electrons directly transferring to the targeted metal seeds via rGO and the precisely tuned adsorption capacity of the added second metal precursors. The surface photovoltage microscopy (SPVM) platform proved that photogenerated electrons flowed through rGO to Pd particles under illumination. We have successfully synthesized 24 different core-shell metal HNCs, i.,e., MA@MB (MA = Pd, Au, and Pt; MB = Au, Ag, Pt, Pd, Ir, Ru, Rh, Ni and Cu), on the rGO supports. The as-prepared Pd@Cu core-shell HNCs showed outstanding performance in the electrocatalytic reduction of CO2 to CH4. This work could shed light on the controlled synthesis of more functional bimetallic nanostructured materials on diverse supports for various applications.

Over 2 A cm-2 CO2 -to-Ethanol Conversion by Alkali-Metal Cation Induced Copper With Dominant (200) Facets.

The high-rate ethanol electrosynthesis from CO2 is challenging due to the low selectivity and poor activity, which requires the competition with other reduction products and H2 . Here, the electrochemical reconstruction of Cs3 Cu2 Cl5 perovskite to form surface Cl-bonded, low-coordinated Cs modified Cu(200) nanocubes (CuClCs), is demonstrated. Density functional theory calculations reveal that the CuClCs structure possesses low Bader charges and a large coordination capacity; and thus, can promote the CO2 -to-ethanol pathway via stabilizing C-O bond in oxygenate intermediates. The CuClCs catalyst exhibits outstanding partial current densities for producing ethanol (up to 2124 ± 54 mA cm-2 ) as one of the highest reported values in the electrochemical CO2 or CO reduction. This work suggests an attractive strategy with surface alkali-metal cations for ampere-level CO2 -to-ethanol electrosynthesis.

Promoting Electrocatalytic CO2 Reduction to CH4 by Copper Porphyrin with Donor-Acceptor Structures.

Molecular catalysts have been receiving increasingly attention in the electrochemical CO2 reduction reaction (CO2 RR) with attractive features such as precise catalytic sites and tunable ligands. However, the insufficient activity and low selectivity of deep reduction products restrain the utilization of molecular catalysts in CO2 RR. Herein, a donor-acceptor modified Cu porphyrin (CuTAPP) is developed, in which amino groups are linked to donate electrons toward the central CuN4 site to enhance the CO2 RR activity. The CuTAPP catalyst exhibited an excellent CO2 -to-CH4 electroreduction performance, including a high CH4 partial current density of 290.5 mA cm-2 and a corresponding Faradaic efficiency of 54.8% at -1.63 V versus reversible hydrogen electrode in flow cells. Density functional theory calculations indicated that CuTAPP presented a much lower energy gap in the pathway of producing *CHO than Cu porphyrin without amino group modification. This work suggests a useful strategy of introducing designed donor-acceptor structures into molecular catalysts for enhancing electrochemical CO2 conversion toward deep reduction products.