Activating inert non-defect sites in Bi catalysts using tensile strain engineering for highly active CO electroreduction.

Bi-defect sites are highly effective for CO reduction (CORR) to formic acid, yet most catalytic surfaces predominantly feature inert, non-defective Bi sites. To overcome this limitation, herein, tensile strain is introduced on wholescale non-defective Bi sites. Under rapid thermal shock, the Bi-based metal-organic framework (Bi-MOF-TS) shows weakened Bi-O bonds and produced tiny Bi clusters.

Planar chlorination engineering induced symmetry-broken single-atom site catalyst for enhanced CO electroreduction.

Breaking the geometric symmetry of traditional metal-N sites and further boosting catalytic activity are significant but challenging. Herein, planar chlorination engineering is proposed for successfully converting the traditional Zn-N site with low activity and selectivity for CO reduction reaction (CORR) into highly active Zn-N site with broken symmetry. The optimal catalyst Zn-SA/CNCl-1000 displays a highest faradaic efficiency for CO (FE) around 97 ± 3% and good stability during 50 h test at high current density of 200 mA/cm in zero-gap membrane electrode assembly (MEA) electrolyzer, with promising application in industrial catalysis.

Switching CO Electroreduction toward C Products and CH by Regulating the Dimerization and Protonation in Platinum/Copper Catalysts.

Copper (Cu)-based catalysts exhibit distinctive performance in the electrochemical CO reduction reaction (CORR) with complex mechanism and sophisticated types of products. The management of key intermediates *CO and *H is a necessary factor for achieving high product selectivity, but lack of efficient and versatile strategies. Herein, we designed Pt modified Cu catalysts to effectively modulate the competitive coverage of those intermediates.

Topological transformation of microbial proteins into iron single-atom sites for selective hydrogen peroxide electrosynthesis.

The emergence of single-atom catalysts offers exciting prospects for the green production of hydrogen peroxide; however, their optimal local structure and the underlying structure-activity relationships remain unclear. Here we show trace Fe, up to 278 mg/kg and derived from microbial protein, serve as precursors to synthesize a variety of Fe single-atom catalysts containing FeNO (1 ≤ x ≤ 4) moieties through controlled pyrolysis. These moieties resemble the structural features of nonheme Fe-dependent enzymes while being effectively confined on a microbe-derived, electrically conductive carbon support, enabling high-current density electrolysis.

Organic Molecule Functionalization Enables Selective Electrochemical Reduction of Dilute CO Feedstock.

The electrochemical conversion of low-concentration CO feedstock to value-added chemicals and fuels is a promising pathway for achieving direct valorization of waste gas streams. However, this is challenging due to significant competition from the hydrogen evolution reaction (HER) and lowered CO reduction (COR) kinetics as compared to systems that employ pure CO. Here we show that terephthalic acid (TPA) functionalization can boost selectivity towards COR and suppress HER over a range of catalysts including Bi, Cu and Zn.

Copper Atom Pairs Stabilize *OCCO Dipole Toward Highly Selective CO Electroreduction to CH.

Deeply electrolytic reduction of carbon dioxide (CO) to high-value ethylene (CH) is very attractive. However, the sluggish kinetics of C-C coupling seriously results in the low selectivity of CO electroreduction to CH. Herein, we report a copper-based polyhedron (Cu2) that features uniformly distributed and atomically precise bi-Cu units, which can stabilize *OCCO dipole to facilitate the C-C coupling for high selective CH production.

Dynamical Janus Interface Design for Reversible and Fast-Charging Zinc-Iodine Battery under Extreme Operating Conditions.

Aqueous zinc (Zn) iodine (I) batteries have emerged as viable alternatives to conventional metal-ion batteries. However, undesirable Zn deposition and irreversible iodine conversion during cycling have impeded their progress. To overcome these concerns, we report a dynamical interface design by cation chemistry that improves the reversibility of Zn deposition and four-electron iodine conversion.

Regulating Reconstruction-Engineered Active Sites for Accelerated Electrocatalytic Conversion of Urea.

Reconstruction-engineered electrocatalysts with enriched high active Ni species for urea oxidation reaction (UOR) have recently become promising candidates for energy conversion. However, to inhibit the over-oxidation of urea brought by the high valence state of Ni, tremendous efforts are devoted to obtaining low-value products of nitrogen gas to avoid toxic nitrite formation, undesirably causing inefficient utilization of the nitrogen cycle. Herein, we proposed a mediation engineering strategy to significantly boost high-value nitrite formation to help close a loop for the employment of a nitrogen economy.

Ultra-High Proportion of Grain Boundaries in Zinc Metal Anode Spontaneously Inhibiting Dendrites Growth.

Aqueous Zn-ion batteries are an attractive electrochemical energy storage solution for their budget and safe properties. However, dendrites and uncontrolled side reactions in anodes detract the cycle life and energy density of the batteries. Grain boundaries in metals are generally considered as the source of the above problems but we present a diverse result.

Electric-field-assisted proton coupling enhanced oxygen evolution reaction.

The discovery of Mn-Ca complex in photosystem II stimulates research of manganese-based catalysts for oxygen evolution reaction (OER). However, conventional chemical strategies face challenges in regulating the four electron-proton processes of OER. Herein, we investigate alpha-manganese dioxide (α-MnO) with typical Mn-O-Mn-HO motifs as a model for adjusting proton coupling.

Integrated energy storage and CO conversion using an aqueous battery with tamed asymmetric reactions.

Developing a CO-utilization and energy-storage integrated system possesses great advantages for carbon- and energy-intensive industries. Efforts have been made to developing the Zn-CO batteries, but access to long cycling life and low charging voltage remains a grand challenge. Here we unambiguously show such inefficiencies originate from the high-barrier oxygen evolution reaction on charge, and by recharging the battery via oxidation of reducing molecules, Faradaic efficiency-enhanced CO reduction and low-overpotential battery regeneration can be simultaneously achieved.

Inhibition of Vanadium Cathodes Dissolution in Aqueous Zn-Ion Batteries.

Aqueous zinc-ion batteries (AZIBs) have experienced a rapid surge in popularity, as evident from the extensive research with over 30 000 articles published in the past 5 years. Previous studies on AZIBs have showcased impressive long-cycle stability at high current densities, achieving thousands or tens of thousands of cycles. However, the practical stability of AZIBs at low current densities (<1C) is restricted to merely 50-100 cycles due to intensified cathode dissolution.

Revolutionizing Lithium Storage Capabilities in TiO by Expanding the Redox Range.

TiO is a widely recognized intercalation anode material for lithium-ion batteries (LIBs), yet its practical capacity is kinetically constrained due to sluggish lithium-ion diffusion, leading to a lithiation number of less than 1.0 Li (336 mAh g). Here, the growth of TiO crystallites is restrained by integrating Si into the TiO framework, thereby enhancing the charge transfer and creating additional active sites potentially residing at grain boundaries for Li storage.

Selective CO Reduction to Ethylene Mediated by Adaptive Small-molecule Engineering of Copper-based Electrocatalysts.

Electrochemical CO reduction reaction (CO RR) over Cu catalysts exhibits enormous potential for efficiently converting CO to ethylene (C H ). However, achieving high C H selectivity remains a considerable challenge due to the propensity of Cu catalysts to undergo structural reconstruction during CO RR. Herein, we report an in situ molecule modification strategy that involves tannic acid (TA) molecules adaptive regulating the reconstruction of a Cu-based material to a pathway that facilitates CO reduction to C H products.

The glass transition in the high-density amorphous Zn/Co-ZIF-4.

The high-density amorphous phases (HDAs) of bimetallic zeolitic imidazolate frameworks (Zn/Co-ZIF-4) were prepared. The temperature dependence of the isobaric heat capacity () of ZIF-4 HDAs was measured to determine the glass transition temperature () of HDAs. The non-linearly decreases with the molar ratio , where is Co/(Co + Zn), indicating the presence of a mixed-metal node effect.

"Mn-locking" effect by anionic coordination manipulation stabilizing Mn-rich phosphate cathodes.

High-voltage cathodes with high power and stable cyclability are needed for high-performance sodium-ion batteries. However, the low kinetics and inferior capacity retention from structural instability impede the development of Mn-rich phosphate cathodes. Here, we propose light-weight fluorine (F) doping strategy to decrease the energy gap to 0.

Surface passivation for highly active, selective, stable, and scalable CO electroreduction.

Electrochemical conversion of CO to formic acid using Bismuth catalysts is one the most promising pathways for industrialization. However, it is still difficult to achieve high formic acid production at wide voltage intervals and industrial current densities because the Bi catalysts are often poisoned by oxygenated species. Herein, we report a BiS nanowire-ascorbic acid hybrid catalyst that simultaneously improves formic acid selectivity, activity, and stability at high applied voltages.

Bio-Inspired Aerobic-Hydrophobic Janus Interface on Partially Carbonized Iron Heterostructure Promotes Bifunctional Nitrogen Fixation.

Competition from hydrogen/oxygen evolution reactions and low solubility of N in aqueous systems limited the selectivity and activity on nitrogen fixation reaction. Herein, we design an aerobic-hydrophobic Janus structure by introducing fluorinated modification on porous carbon nanofibers embedded with partially carbonized iron heterojunctions (Fe C/Fe@PCNF-F). The simulations prove that the Janus structure can keep the internal Fe C/Fe@PCNF-F away from water infiltration and endow a N molecular-concentrating effect, suppressing the competing reactions and overcoming the mass-transfer limitations to build a robust "quasi-solid-gas" state micro-domain around the catalyst surface.

Trace Amounts of Triple-Functional Additives Enable Reversible Aqueous Zinc-Ion Batteries from a Comprehensive Perspective.

Although their cost-effectiveness and intrinsic safety, aqueous zinc-ion batteries suffer from notorious side reactions including hydrogen evolution reaction, Zn corrosion and passivation, and Zn dendrite formation on the anode. Despite numerous strategies to alleviate these side reactions have been demonstrated, they can only provide limited performance improvement from a single aspect. Herein, a triple-functional additive with trace amounts, ammonium hydroxide, was demonstrated to comprehensively protect zinc anodes.

Reversible Zn Metal Anodes Enabled by Trace Amounts of Underpotential Deposition Initiators.

Routine electrolyte additives are not effective enough for uniform zinc (Zn) deposition, because they are hard to proactively guide atomic-level Zn deposition. Here, based on underpotential deposition (UPD), we propose an "escort effect" of electrolyte additives for uniform Zn deposition at the atomic level. With nickel ion (Ni ) additives, we found that metallic Ni deposits preferentially and triggers the UPD of Zn on Ni.

Charge-Separated Pd-Cu Atom Pairs Promote CO Reduction to C.

Positively charged Cu sites have been confirmed to significantly promote the production of multicarbon (C) products from an electrochemical CO reduction reaction (CORR). However, the positively charged Cu has difficulty in existing under a strong negative bias. In this work, we design a Pd-CuN catalyst containing charge-separated Pd-Cu atom pair that can stabilize the Cu sites.