Rational Modulation of Interface Microenvironment and Design of the Flow Electrolyzer for COx Electroreduction to Alcohol.

The electrocatalytic reduction of COx (including CO2 and CO) into value-added fuels and chemicals, particularly multi-carbon (C2+) alcohols, presents a significant opportunity to close the manmade carbon cycle and support sustainable energy systems. The catalytic performance of electrochemical reduction reactions of CO2 and CO (COxRR) is strongly correlated with the local microenvironments, the flow electrolyzer, and the catalysis approaches with flow electrolyzers, which contribute to the kinetic and thermodynamic landscape of the reaction, ultimately determining the efficiency and selectivity of the COxRR toward desired reduction products. However, controllable microenvironment construction, rationally designed flow electrolyzers, and matchable flow electrolyzers derived catalysis approaches chosen for improving COxRR-to-alcohol performance still face challenges. Building upon the foundation laid by previous research, this review article will provide an in-depth summary of the regulation of the catalytic reaction interface microenvironment, the design of flow electrolyzers, and the development of derived stepwise catalysis approaches with the flow electrolyzers, which provide a comprehensive and strategic approach to enhancing the COxRR process for alcohol production, offering valuable insights and innovative solutions that can significantly impact the field of COxRR conversion to alcohol and contribute to the development of more sustainable chemical production methods.

Electrochemical C-N coupling of CO2 and nitrogenous small molecules for the electrosynthesis of organonitrogen compounds.

Electrochemical C-N coupling reactions based on abundant small molecules (such as CO2 and N2) have attracted increasing attention as a new "green synthetic strategy" for the synthesis of organonitrogen compounds, which have been widely used in organic synthesis, materials chemistry, and biochemistry. The traditional technology employed for the synthesis of organonitrogen compounds containing C-N bonds often requires the addition of metal reagents or oxidants under harsh conditions with high energy consumption and environmental concerns. By contrast, electrosynthesis avoids the use of other reducing agents or oxidants by utilizing "electrons", which are the cleanest "reagent" and can reduce the generation of by-products, consistent with the atomic economy and green chemistry. In this study, we present a comprehensive review on the electrosynthesis of high value-added organonitrogens from the abundant CO2 and nitrogenous small molecules (N2, NO, NO2-, NO3-, NH3, etc.) via the C-N coupling reaction. The associated fundamental concepts, theoretical models, emerging electrocatalysts, and value-added target products, together with the current challenges and future opportunities are discussed. This critical review will greatly increase the understanding of electrochemical C-N coupling reactions, and thus attract research interest in the fixation of carbon and nitrogen.

Disordered Au Nanoclusters for Efficient Ammonia Electrosynthesis.

The electrochemical nitrogen (N2 ) reduction reaction (N2 RR) under mild conditions is a promising and environmentally friendly alternative to the traditional Haber-Bosch process with high energy consumption and greenhouse emission for the synthesis of ammonia (NH3 ), but high-yielding production is rendered challenging by the strong nonpolar N≡N bond in N2 molecules, which hinders their dissociation or activation. In this study, disordered Au nanoclusters anchored on two-dimensional ultrathin Ti3 C2 Tx MXene nanosheets are explored as highly active and selective electrocatalysts for efficient N2 -to-NH3 conversion, exhibiting exceptional activity with an NH3 yield rate of 88.3±1.7 µg h-1 mgcat. -1 and a faradaic efficiency of 9.3±0.4 %. A combination of in situ near-ambient pressure X-ray photoelectron spectroscopy and operando X-ray absorption fine structure spectroscopy is employed to unveil the uniqueness of this catalyst for N2 RR. The disordered structure is found to serve as the active site for N2 chemisorption and activation during the N2 RR process.

Accelerated water activation and stabilized metal-organic framework via constructing triangular active-regions for ampere-level current density hydrogen production.

Two-dimensional metal-organic frameworks (MOFs) have been explored as effective electrocatalysts for hydrogen evolution reaction (HER). However, the sluggish water activation kinetics and structural instability under ultrahigh-current density hinder their large-scale industrial applications. Herein, we develop a universal ligand regulation strategy to build well-aligned Ni-benzenedicarboxylic acid (BDC)-based MOF nanosheet arrays with S introducing (S-NiBDC). Benefiting from the closer p-band center to the Fermi level with strong electron transferability, S-NiBDC array exhibits a low overpotential of 310 mV to attain 1.0 A cm-2 with high stability in alkaline electrolyte. We speculate the newly-constructed triangular "Ni2-S1" motif as the improved HER active region based on detailed mechanism analysis and structural characterization, and the enhanced covalency of Ni-O bonds by S introducing stabilizes S-NiBDC structure. Experimental observations and theoretical calculations elucidate that such Ni sites in "Ni2-S1" center distinctly accelerate the water activation kinetics, while the S site readily captures the H atom as the optimal HER active site, boosting the whole HER activity.

Chemically coupling SnO2 quantum dots and MXene for efficient CO2 electroreduction to formate and Zn-CO2 battery.

Electrochemical conversion of CO2 into formate is a promising strategy for mitigating the energy and environmental crisis, but simultaneously achieving high selectivity and activity of electrocatalysts remains challenging. Here, we report low-dimensional SnO2 quantum dots chemically coupled with ultrathin Ti3C2Tx MXene nanosheets (SnO2/MXene) that boost the CO2 conversion. The coupling structure is well visualized and verified by high-resolution electron tomography together with nanoscale scanning transmission X-ray microscopy and ptychography imaging. The catalyst achieves a large partial current density of -57.8 mA cm-2 and high Faradaic efficiency of 94% for formate formation. Additionally, the SnO2/MXene cathode shows excellent Zn-CO2 battery performance, with a maximum power density of 4.28 mW cm-2, an open-circuit voltage of 0.83 V, and superior rechargeability of 60 h. In situ X-ray absorption spectroscopy analysis and first-principles calculations reveal that this remarkable performance is attributed to the unique and stable structure of the SnO2/MXene, which can significantly reduce the reaction energy of CO2 hydrogenation to formate by increasing the surface coverage of adsorbed hydrogen.

Abundant (110) Facets on PdCu3 Alloy Promote Electrochemical Conversion of CO2 to CO.

Electrochemical conversion of CO2 to high-value chemical fuels offers a promising strategy for managing the global carbon balance but faces huge challenges due to the lack of effective electrocatalysts. Here, we reported PdCu3 alloy nanoparticles with abundant exposed (110) facets supported on N-doped three-dimensional interconnected carbon frameworks (PdCu3/NC) as an efficient and durable electrocatalyst for electrochemical CO2 reduction to CO. The catalyst exhibits extremely high intrinsic CO2 reduction selectivity for CO production with a Faraday efficiency of nearly 100% at a mild potential of -0.5 V. Moreover, a rechargeable high-performance Zn-CO2 battery with PdCu3/NC as a cathode is developed to deliver a record-high energy efficiency of 99.2% at 0.5 mA cm-2 and rechargeable stability of up to 133 h. Theoretical calculations elucidate that the exposed (110) facet over PdCu3/NC is the active center for CO2 activation and rapid formation of the key *COOH intermediate.

Progress in Mo/W-based electrocatalysts for nitrogen reduction to ammonia under ambient conditions.

Ammonia (NH3), possessing high hydrogen content and energy density, has been widely employed for fertilizers and value-added chemicals in green energy carriers and fuels. However, the current NH3 synthesis largely depends on the traditional Haber-Bosch process, which needs tremendous energy consumption and generates greenhouse gas, resulting in severe energy and environmental issues. The electrochemical strategy of converting N2 to NH3 under mild conditions is a potentially promising route to realize an environmentally friendly concept. Among various catalysts, molybdenum/tungsten-based electrocatalysts have been widely used in electrochemical catalytic and energy conversion. This review describes the latest progress of molybdenum/tungsten-based electrocatalysts for the electrochemical nitrogen reduction reaction. The fundamental roles of morphology, doping, defects, heterojunction, and coupling regulation in improving electrocatalytic performance are mainly discussed. Besides, some tailoring strategies for enhancing the conversion efficiency of N2 to NH3 over Mo/W-based electrocatalysts are also summarized. Finally, the existing challenges and limitations of N2 fixation are proposed, as well as possible future perspectives, which will provide a platform for further development of advanced Mo/W-based N2 reduction systems.

Heteroatom coordination induces electric field polarization of single Pt sites to promote hydrogen evolution activity.

Herein, we reported a kind of single Pt site (Pt-SA) stabilized on an MXene support (Pt-SA/MXene) via the formation of Pt-O and Pt-Ti bonds to effectively catalyze the hydrogen evolution reaction (HER). Due to the local electric field polarization derived from its unique asymmetric coordination, Pt-SA/MXene displays remarkably higher catalytic HER activity in an alkaline electrolyte. In detail, the Pt-SA/MXene electrocatalyst only needs a low overpotential of 33 mV to reach a current density of 10 mA cm-2 and maintains the performance over 27 h. Besides, Pt-SA/MXene also has a competitive mass activity, 23.5 A mgPt-1, at an overpotential of 100 mV, which is 29.4 times greater than that of the commercial Pt/C counterpart. Density functional theory (DFT) calculations revealed that the polarized electric field could efficiently tailor the electronic structure of Pt-SA/MXene and reduce the energy barrier of adsorption/desorption of the H* intermediate step, further improving its HER catalytic activity.

Bifunctional single-atomic Mn sites for energy-efficient hydrogen production.

The electrocatalytic hydrogen evolution reaction (HER) for H2 production is essential for future renewable and clean energy technology. Screening energy-saving, low-cost, and highly active catalysts efficiently, however, is still a grand challenge due to the sluggish kinetics of the oxygen evolution reaction (OER) in electrolyzing water. Herein, we present a single atomic Mn site anchored on a boron nitrogen co-doped carbon nanotube array (Mn-SA/BNC), which is perfectly combined with the hydrazine electrooxidation reaction (HzOR) boosted water electrolysis concept. The obtained catalyst achieves 51 mV overpotential at the current density of -10 mA cm-2 for the cathodic HER and 132 mV versus the reversible hydrogen electrode for HzOR, respectively. Besides, in a two-electrode overall hydrazine splitting (OHzS) system, the Mn-SA/BNC catalyst only needs a cell voltage of only 0.41 V to output 10 mA cm-1, with strong durability and nearly 100% faradaic efficiency for H2 production. This work highlights a low-cost and high-efficiency energy-saving H2 production pathway.

Isolated copper single sites for high-performance electroreduction of carbon monoxide to multicarbon products.

Electrochemical carbon monoxide reduction is a promising strategy for the production of value-added multicarbon compounds, albeit yielding diverse products with low selectivities and Faradaic efficiencies. Here, copper single atoms anchored to Ti3C2Tx MXene nanosheets are firstly demonstrated as effective and robust catalysts for electrochemical carbon monoxide reduction, achieving an ultrahigh selectivity of 98% for the formation of multicarbon products. Particularly, it exhibits a high Faradaic efficiency of 71% towards ethylene at -0.7 V versus the reversible hydrogen electrode, superior to the previously reported copper-based catalysts. Besides, it shows a stable activity during the 68-h electrolysis. Theoretical simulations reveal that atomically dispersed Cu-O3 sites favor the C-C coupling of carbon monoxide molecules to generate the key *CO-CHO species, and then induce the decreased free energy barrier of the potential-determining step, thus accounting for the high activity and selectivity of copper single atoms for carbon monoxide reduction.

Single-atom niobium doped BCN nanotubes for highly sensitive electrochemical detection of nitrobenzene.

Herein, single-atom niobium-doped boron-carbon-nitrogen nanotubes (SANb-BCN) were synthesized and utilized to fabricate an electrochemical sensor for the detection of nitrobenzene (NB), an environmental pollutant. SANb-BCN were characterized through scanning transmission electron microscopy, scanning electron microscopy, transmission electron microscopy, X-ray diffraction analysis, and Raman spectroscopy. The Nb-BNC material modified on a glassy carbon electrode (GCE) showed an excellent electrochemical response behavior toward NB. The SANb-BCN-modified GCE (SANb-BCN/GCE) gave rise to a prominent NB reduction peak at -0.6 V, which was positively shifted by 120 mV from the NB reduction peak of the bare GCE. Furthermore, the NB peak current (55.74 µA) obtained using SANb-BCN/GCE was nearly 42-fold higher than that using the bare GCE (1.32 µA), indicating that SANb-BCN/GCE is a highly sensitive electrochemical sensor for NB. An ultralow limit of detection (0.70 µM, S/N = 3) was also achieved. Furthermore, the SANb-BCN/GCE sensor was found to possess favorable anti-interference ability during NB detection; thus, the presence of various organic and inorganic coexisting species, including Mg2+, Cr6+, Cu2+, K+, Ca2+, NH4+, Cd2+, urea, 1-bromo-4-nitrobenzene, 3-hydroxybenzoic, terephthalic acid, 1-iodo-4-nitrobenzene, and toluene, minimally affected the NB detection signal. Notably, the SANb-BNC sensor material exhibited high sensitivity and specificity toward detection of NB in environmental samples. Thus, the use of the proposed sensor will serve as an effective alternative method for the identification and treatment of pollutants.

Engineering Atomic Sites via Adjacent Dual-Metal Sub-Nanoclusters for Efficient Oxygen Reduction Reaction and Zn-Air Battery.

N-coordinated transition-metal materials are crucial alternatives to design cost-effective, efficient, and highly durable catalysts for electrocatalytic oxygen reduction reaction. Herein, the synthesis of uniformly distributed Cu-Zn clusters on porous N-doped carbon, which are accompanied by Cu/Zn-Nx single sites, is demonstrated. X-ray absorption fine structure tests reveal the co-existence of M-N (M = Cu or Zn) and M-M bonds in the catalyst. The catalyst shows excellent oxygen reduction reaction (ORR) performance in an alkaline medium with a positive half-wave potential of 0.884 V, a superior kinetic current density of 36.42 mA cm-2 at 0.85 V, and a Tafel slope of 45 mV dec-1 , all of which are among the best-reported results. Furthermore, when employed as an air cathode in Zn-Air battery, it reveals a high open-cycle potential of 1.444 V and a peak power density of 164.3 mW cm-2 . Comprehensive experiments and theoretical calculations approved that the high activity of the catalyst can be attributed to the collaboration of the Cu/Zn-N4 sites with CuZn moieties on N-doped carbons.

Trifunctional Single-Atomic Ru Sites Enable Efficient Overall Water Splitting and Oxygen Reduction in Acidic Media.

Development of cost-effective, active trifunctional catalysts for acidic oxygen reduction (ORR) as well as hydrogen and oxygen evolution reactions (HER and OER, respectively) is highly desirable, albeit challenging. Herein, single-atomic Ru sites anchored onto Ti3 C2 Tx MXene nanosheets are first reported to serve as trifunctional electrocatalysts for simultaneously catalyzing acidic HER, OER, and ORR. A half-wave potential of 0.80 V for ORR and small overpotentials of 290 and 70 mV for OER and HER, respectively, at 10 mA cm-2 are achieved. Hence, a low cell voltage of 1.56 V is required for the acidic overall water splitting. The maximum power density of an H2 -O2 fuel cell using the as-prepared catalyst can reach as high as 941 mW cm-2 . Theoretical calculations reveal that isolated Ru-O2 sites can effectively optimize the adsorption of reactants/intermediates and lower the energy barriers for the potential-determining steps, thereby accelerating the HER, ORR, and OER kinetics.

Highly Productive Electrosynthesis of Ammonia by Admolecule-Targeting Single Ag Sites.

The ambient electrocatalytic N2 reduction reaction (NRR) is a promising alternative to the Haber-Bosch process for producing NH3. However, a guideless search for single-atom-based and other electrocatalysts cannot promote the NH3 yield rates by NRR efficiently. Herein, our first-principles calculations reveal that the successive emergence of vertical end-on *N2 and oblique end-on *NNH admolecules on single metal sites is key to high-performance NRR. By targeting the admolecules, single Ag sites with the Ag-N4 coordination are found and synthesized massively. They exhibit a record-high NH3 yield rate (270.9 µg h-1 mgcat.-1 or 69.4 mg h-1 mgAg-1) and a desirable Faradaic efficiency (21.9%) in HCl aqueous solution under ambient conditions. The generation rate of NH3 is stable during 20 consecutive reaction cycles, and the reduction current density is almost constant for 60 h. This work provides an effective targeting-design principle to purposefully synthesize active and durable single-atom-based NRR electrocatalysts.

Nitrogen doping and titanium vacancies synergistically promote CO2 fixation in seawater.

The electrocatalytic generation of useful chemicals from CO2, H2O, and sustainable energy resources offers a promising strategy for the carbon cycle. However, the current CO2 electrolysis system is mainly operated in artificial electrolytes (e.g. ionic liquids and inorganic salt solutions), of which the high cost and impractical working conditions hinder its large-scale development. In this case, seawater represents an attractive alternative due to its abundance and good conductivity. Herein, we show that N-doping and titanium vacancies (VTi) can be introduced in Ti3C2 MXene nanosheets via a facile NH3-etching pyrolysis approach. These nanosheets demonstrate impressive CO2 reduction reaction (CO2RR) performances in seawater with a remarkable 92% faradaic efficiency and a partial current density of -16.2 mA cm-2 for CO production, being close to those of noble metal electrodes. Mechanistic studies reveal that the existence of N dopants and VTi synergistically modulates the electronic structure of the active Ti site, on which the free energy barriers for the key *COOH formation and desorption of *CO are greatly reduced, thereby leading to a notable CO2RR improvement. This study provides an opportunity for developing an active and cost-effective CO2 electrolysis system by using seawater as the electrolyte.

Single-Atom Catalysts for the Electrocatalytic Reduction of Nitrogen to Ammonia under Ambient Conditions.

Powered by renewable electricity, the electrochemical reduction of nitrogen to ammonia is proposed as a promising alternative to the energy- and capital-intensive Haber-Bosch process, and has thus attracted much attention from the scientific community. However, this process suffers from low NH3 yields and Faradaic efficiency. The development of more effective electrocatalysts is of vital importance for the practical applications of this reaction. Of the reported catalysts, single-atom catalysts (SACs) show the significant advantages of efficient atom utilization and unsaturated coordination configurations, which offer great scope for optimizing their catalytic performance. Herein, progress in state-of-the-art SACs applied in the electrocatalytic N2 reduction reaction (NRR) is discussed, and the main advantages and challenges for developing more efficient electrocatalysts are also highlighted.

AuCu Alloy Nanoparticle Embedded Cu Submicrocone Arrays for Selective Conversion of CO2 to Ethanol.

The CO2 reduction reaction (CO2 RR) driven by renewable electricity represents a promising strategy toward alleviating the energy shortage and environmental crisis facing humankind. Cu species, as one type of versatile electrocatalyst for the CO2 RR, attract tremendous research interest. However, for C2 products, ethanol formation is commonly less favored over Cu electrocatalysts. Herein, AuCu alloy nanoparticle embedded Cu submicrocone arrays (AuCu/Cu-SCA) are constructed as an active, selective, and robust electrocatalyst for the CO2 RR. Enhanced selectivity for EtOH is gained, whose Faradaic efficiency (FE) reaches 29 ± 4%, while ethylene formation is relatively inhibited (16 ± 4%) in KHCO3 aqueous solution. The ratio between partial current densities of EtOH and C2 H4 (jEtOH /jC2H4 ) can be tuned in the range from 0.15 ± 0.27 to 1.81 ± 0.55 by varying the Au content of the electrocatalysts. The combined experimental and theoretical calculation results identify the importance of Au in modifying binding energies of key intermediates, such as CH2 CHO*, CH3 CHO*, and CH3 CH2 O*, which consequently modify the activity and selectivity (jEtOH /jC2H4 ) for the CO2 RR. Moreover, AuCu/Cu-SCA also shows high durability with both the current density and FEEtOH being largely maintained for 24 h electrocatalysis.

Efficient Electroreduction CO2 to CO over MnO2 Nanosheets.

As a critical alternative step for the synthesis of important chemical feedstocks and complex carbon-based fuels, the electrochemical transformation of CO2 into CO holds great significance for the chemical industry. Here, MnO2 nanosheets array supported nickel foam has been synthesized and adopted as a binder-free catalyst for electrochemical CO2 reduction reaction (CO2RR). The well-distributed nanosheets of MnO2 impart a much higher density of accessible active sites for CO2RR, enabling the selective CO2 reduction to CO with a large current density (14.1 mA cm-2), excellent Faradaic efficiency (71%) and high electrochemical stability (10 h). This work first demonstrates the great potential of Mn-based oxides for electrocatalytic transformation of CO2 to valuable products.

Porous Mn-Doped FeP/Co3 (PO4 )2 Nanosheets as Efficient Electrocatalysts for Overall Water Splitting in a Wide pH Range.

Development of highly active and stable electrocatalysts for overall water splitting is important for future renewable energy systems. In this study, porous Mn-doped FeP/Co3 (PO4 )2 (PMFCP) nanosheets on carbon cloth are utilized as a highly efficient 3 D self-supported binder-free integrated electrode for the oxygen evolution and hydrogen evolution reactions (OER and HER) over a wide pH range. Specifically, overpotentials of 27, 117, 85 mV are required for the PMFCP nanosheets to attain 10 mA cm-2 for HER in 0.5 m H2 SO4 , 1.0 m phosphatebuffered saline (PBS), and 1.0 m KOH, respectively. In addition to the excellent performance for HER electrocatalysis, PMFCP nanosheets were also efficient electrocatalysts for the OER. Thus, the PMFCP nanosheets can serve as anodes and cathodes for overall water splitting (OWS). The OWS working voltages to attain 10 mA cm-2 are found to be 1.75, 1.82, and 1.61 V in acid, neutral, and alkaline electrolytes, respectively. Chronopotentiometric tests show that the PMFCP electrode can maintain its excellent pH-universal OWS activity for more than 30 000 s. This work also provides new insights into developing high-performance electrocatalysts for water splitting over a wide pH range. The improvement in electrochemical performance by introduction of Mn dopant and nano-holes offers new opportunities in the development of effective electrodes for other energy-related applications.

Facile synthesis of Al-doped NiO nanosheet arrays for high-performance supercapacitors.

Electrode material design is the key to the development of asymmetric supercapacitors with high electrochemical performances and stability. In this work, Al-doped NiO nanosheet arrays were synthesized using a facile hydrothermal method followed by a calcination process, and the synthesized arrays exhibited a superior pseudocapacitive performance, including a favourable specific capacitance of 2253 ± 105 F g-1 at a current density of 1 A g-1, larger than that of an undoped NiO electrode (1538 ± 80 F g-1). More importantly, the arrays showed a high-rate capability (75% capacitance retention at 20 A g-1) and a high cycling stability (approx. 99% maintained after 5000 cycles). The above efficient capacitive performance benefits from the large electrochemically active area and enhanced conductivity of the arrays. Furthermore, an assembled asymmetric supercapacitor based on the Al-doped NiO arrays and N-doped multiwalled carbon nanotube ones delivered a high specific capacitance of 192 ± 23 F g-1 at 0.4 A g-1 with a high-energy density of 215 ± 15 Wh kg-1 and power density of 21.6 kW kg-1. Additionally, the asymmetric device exhibited a durable cyclic stability (approx. 100% retention after 5000 cycles). This work with the proposed doping method will be beneficial to the construction of high-performance supercapacitor systems.