Steering the Reaction Pathway of CO2 Electroreduction by Tuning the Coordination Number of Copper Catalysts.

Cu-based catalysts are optimal for the electroreduction of CO2 to generate hydrocarbon products. However, controlling product distribution remains a challenging topic. The theoretical investigations have revealed that the coordination number (CN) of Cu considerably influences the adsorption energy of *CO intermediates, thereby affecting the reaction pathway. Cu catalysts with different CNs were fabricated by reducing CuO precursors via cyclic voltammetry (Cyc-Cu), potentiostatic electrolysis (Pot-Cu), and pulsed electrolysis (Pul-Cu), respectively. High-CN Cu catalysts predominantly generate C2+ products, while low-CN Cu favors CH4 production. For instance, over the high-CN Pot-Cu, C2+ is the main product, with the Faradaic efficiency (FE) reaching 82.5% and a partial current density (j) of 514.3 mA cm-2. Conversely, the low-CN Pul(3)-Cu favors the production of CH4, achieving the highest FECH4 value of 56.7% with a jCH4 value of 234.4 mA cm-2. In situ X-ray absorption spectroscopy and Raman spectroscopy studies further confirm the different *CO adsorptions over Cu catalysts with different CN, thereby directing the reaction pathway of the CO2RR.

Urea Synthesis via Coelectrolysis of CO2 and Nitrate over Heterostructured Cu-Bi Catalysts.

Electrocatalytic coupling of CO2 and NO3- to urea is a promising way to mitigate greenhouse gas emissions, reduce waste from industrial processes, and store renewable energy. However, the poor selectivity and activity limit its application due to the multistep process involving diverse reactants and reactions. Herein, we report the first work to design heterostructured Cu-Bi bimetallic catalysts for urea electrosynthesis. A high urea Faradaic efficiency (FE) of 23.5% with a production rate of 2180.3 µg h-1 mgcat-1 was achieved in H-cells, which surpassed most reported electrocatalysts in the literature. Moreover, the catalyst had a remarkable recycling stability. Experiments and density functional theory calculations demonstrated that introduction of moderate Bi induced the formation of the Bi-Cu/O-Bi/Cu2O heterostructure with abundant phase boundaries, which are beneficial for NO3-, CO2, and H2O activation and enhance C-N coupling and promote *HONCON intermediate formation. Moreover, favorable *HNCONH2 protonation and urea desorption processes were also validated, further explaining the reason for high activity and selectivity toward urea.

Selective and Efficient CO2 Electroreduction to Formate on Copper Electrodes Modified by Cationic Gemini Surfactants.

Electroreduction of CO2 into valuable chemicals and fuels is a promising strategy to mitigate energy and environmental problems. However, it usually suffers from unsatisfactory selectivity for a single product and inadequate electrochemical stability. Herein, we report the first work to use cationic Gemini surfactants as modifiers to boost CO2 electroreduction to formate. The selectivity, activity and stability of the catalysts can be all significantly enhanced by Gemini surfactant modification. The Faradaic efficiency (FE) of formate could reach up to 96 %, and the energy efficiency (EE) could achieve 71 % over the Gemini surfactants modified Cu electrode. In addition, the Gemini surfactants modified commercial Bi2 O3 nanosheets also showed an excellent catalytic performance, and the FE of formate reached 91 % with a current density of 510 mA cm-2 using the flow cell. Detailed studies demonstrated that the double quaternary ammonium cations and alkyl chains of the Gemini surfactants played a crucial role in boosting electroreduction CO2 , which can not only stabilize the key intermediate HCOO* but also provide an easy access for CO2 . These observations could shine light on the rational design of organic modifiers for promoted CO2 electroreduction.

Polymer Modification Strategy to Modulate Reaction Microenvironment for Enhanced CO2 Electroreduction to Ethylene.

Modulation of the microenvironment on the electrode surface is one of the effective means to improve the efficiency of electrocatalytic carbon dioxide reduction (eCO2 RR). To achieve high conversion rates, the phase boundary at the electrode surface should be finely controlled to overcome the limitation of CO2 solubility in the aqueous electrolyte. Herein, we developed a simple and efficient method to structure electrocatalyst with a superhydrophobic surface microenvironment by one-step co-electrodeposition of Cu and polytetrafluoroethylene (PTFE) on carbon paper. The super-hydrophobic Cu-based electrode displayed a high ethylene (C2 H4 ) selectivity with a Faraday efficiency (FE) of 67.3 % at -1.25 V vs. reversible hydrogen electrode (RHE) in an H-type cell, which is 2.5 times higher than a regular Cu electrode without PTFE. By using PTFE as a surface modifier, the activity of eCO2 RR is enhanced and water (proton) adsorption is inhibited. This strategy has the potential to be applied to other gas-conversion electrocatalysts.

Cooperation of Different Active Sites to Promote CO2 Electroreduction to Multi-carbon Products at Ampere-Level.

Electroreduction of CO2 to C2+ products provides a promising strategy for reaching the goal of carbon neutrality. However, achieving high selectivity of C2+ products at high current density remains a challenge. In this work, we designed and prepared a multi-sites catalyst, in which Pd was atomically dispersed in Cu (Pd-Cu). It was found that the Pd-Cu catalyst had excellent performance for producing C2+ products from CO2 electroreduction. The Faradaic efficiency (FE) of C2+ products could be maintained at approximately 80.8 %, even at a high current density of 0.8 A cm-2 for at least 20 hours. In addition, the FE of C2+ products was above 70 % at 1.4 A cm-2. Experiments and density functional theory (DFT) calculations revealed that the catalyst had three distinct catalytic sites. These three active sites allowed for efficient conversion of CO2, water dissociation, and CO conversion, ultimately leading to high yields of C2+ products.

Lattice Strain Engineering Boosts CO2 Electroreduction to C2+ Products.

Regulating the binding effect between the surface of an electrode material and reaction intermediates is essential in highly efficient CO2 electro-reduction to produce high-value multicarbon (C2+) compounds. Theoretical study reveals that lattice tensile strain in single-component Cu catalysts can reduce the dipole-dipole repulsion between *CO intermediates and promotes *OH adsorption, and the high *CO and *OH coverage decreases the energy barrier for C-C coupling. In this work, Cu catalysts with varying lattice tensile strain were fabricated by electro-reducing CuO precursors with different crystallinity, without adding any extra components. The as-prepared single-component Cu catalysts were used for CO2 electro-reduction, and it is discovered that the lattice tensile strain in Cu could enhance the Faradaic efficiency (FE) of C2+ products effectively. Especially, the as-prepared CuTPA catalyst with high lattice tensile strain achieves a FEC2+ of 90.9 % at -1.25 V vs. RHE with a partial current density of 486.1 mA cm-2.

Highly Selective CO2 Electroreduction to Multi-Carbon Alcohols via Amine Modified Copper Nanoparticles at Acidic Conditions.

Electroreduction of CO2 into multi-carbon (C2+) products (e.g. C2+ alcohols) offers a promising way for CO2 utilization. Use of strong alkaline electrolytes is favorable to producing C2+ products. However, CO2 can react with hydroxide to form carbonate/bicarbonate, which results in low carbon utilization efficiency and poor stability. Using acidic electrolyte is an efficient way to solve the problems, but it is a challenge to achieve high selectivity of C2+ products. Here we report that the amine modified copper nanoparticles exhibit high selectivity of C2+ products and carbon utilization at acidic condition. The Faradaic efficiency (FE) of C2+ products reach up to 81.8 % at acidic media (pH=2) with a total current density of 410 mA cm-2 over n-butylamine modified Cu. Especially the FE of C2+ alcohols is 52.6 %, which is higher than those reported for CO2 electroreduction at acidic condition. In addition, the single-pass carbon efficiency towards C2+ production reach up to 60 %. Detailed studies demonstrate that the amine molecule on the surface of Cu cannot only enhance the formation, adsorption and coverage of *CO, but also provide a hydrophobic environment, which result in the high selectivity of C2+ alcohols at acidic condition.

Synergy of Cu/C3 N4 Interface and Cu Nanoparticles Dual Catalytic Regions in Electrolysis of CO to Acetic Acid.

Electrochemical reduction reaction of carbon monoxide (CORR) offers a promising way to manufacture acetic acid directly from gaseous CO and water at mild condition. Herein, we discovered that the graphitic carbon nitride (g-C3 N4 ) supported Cu nanoparticles (Cu-CN) with the appropriate size showed a high acetate faradaic efficiency of 62.8 % with a partial current density of 188 mA cm-2 in CORR. In situ experimental and density functional theory calculation studies revealed that the Cu/C3 N4 interface and metallic Cu surface synergistically promoted CORR into acetic acid. The generation of pivotal intermediate -*CHO is advantage around the Cu/C3 N4 interface and migrated *CHO facilitates acetic acid generation on metallic Cu surface with promoted *CHO coverage. Moreover, continuous production of acetic acid aqueous solution was achieved in a porous solid electrolyte reactor, indicating the great potential of Cu-CN catalyst in the industrial application.

Efficient synthesis of cyclic carbonates from CO2 under ambient conditions over Zn(betaine)2Br2: experimental and theoretical studies.

It is very interesting to synthesize high value-added chemicals from CO2 under mild conditions with low energy consumption. Here, we report that a novel catalyst, Zn(betaine)2Br2, can efficiently promote the cycloaddition of CO2 with epoxides to synthesize cyclic carbonates under ambient conditions (30 °C, 1 atm). DFT calculations provide important insights into the mechanism, particularly the unusual synergistic catalytic action of Zn2+, Br- and NR4+, which is the critical factor for the outstanding performance of Zn(betaine)2Br2. The unique features of the catalyst are that it is cheap, green and very easy to prepare.

Boosting the Productivity of Electrochemical CO2 Reduction to Multi-Carbon Products by Enhancing CO2 Diffusion through a Porous Organic Cage.

Electroreduction of CO2 into valuable fuels and feedstocks offers a promising way for CO2 utilization. However, the commercialization is limited by the low productivity. Here, we report a strategy to enhance the productivity of CO2 electroreduction by improving diffusion of CO2 to the surface of catalysts using porous organic cages (POCs) as an additive. It was noted that the Faradaic efficiency (FE) of C2+ products could reach 76.1 % with a current density of 1.7 A cm-2 when Cu-nanorod(nr)/CC3 (one of the POCs) was used, which were much higher than that using Cu-nr. Detailed studies demonstrated that the hydrophobic pores of CC3 can adsorb a large amount of CO2 for the reaction, and the diffusion of CO2 in the CC3 to the nanocatalyst surface is easier than that in the liquid electrolyte. Thus, more CO2 molecules make contact with the nanocatalysts in the presence of CC3, enhancing CO2 reduction and inhibiting generation of H2 .

In Situ Periodic Regeneration of Catalyst during CO2 Electroreduction to C2+ Products.

Developing electrocatalytic reactions with high-efficiency can make important contributions to carbon neutrality. However, poor long-term stability of catalysts is a bottleneck for its practical application. Herein, an "in situ periodic regeneration of catalyst (PR-C)" strategy is proposed to give long-term high efficiency of CO2 electroreduction to generate C2+ products over Cu catalyst by applying a positive potential pulse for a short time periodically in the halide-containing electrolyte. The high Faradaic efficiency (81.2 %) and current density (22.6 mA cm-2 ) could be maintained completely at least 36 h, while the activity and selectivity decreased continuously without using the PR-C method. Control experiments and operando characterization demonstrated that the surface structure and oxidation state of Cu could be recovered periodically by the PR-C method, which was beneficial for CO2 activation and C-C coupling.

Atomic Indium Catalysts for Switching CO2 Electroreduction Products from Formate to CO.

Electrochemical reduction of CO2 to chemicals and fuels is an interesting and attractive way to mitigate greenhouse gas emissions and energy shortages. In this work, we report the use of atomic In catalysts for CO2 electroreduction to CO. The atomic In catalysts were anchored on N-doped carbon (InA/NC) through pyrolysis of In-based metal-organic frameworks (MOFs) and dicyandiamide. It was discovered that InA/NC had outstanding performance for selective CO production in the mixed electrolyte of ionic liquid/MeCN. It is different from those common In-based materials, in which formate/formic acid is formed as the main product. The faradaic efficiency (FE) of CO and total current density were 97.2% and 39.4 mA cm-2, respectively, with a turnover frequency (TOF) of ∼40 000 h-1. It is one of the highest TOF for CO production to date for all of the catalysts reported. In addition, the catalyst had remarkable stability. Detailed study indicated that InA/NC had higher double-layer capacitance, larger CO2 adsorption capacity, and lower interfacial charge transfer resistance, leading to high activity for CO2 reduction. Control experiments and theoretical calculations showed that the In-N site of InA/NC is not only beneficial for dissociation of COOH* to form CO but also hinders formate formation, leading to high selectivity toward CO instead of formate.

Understanding the Wetting and Water-Induced Dewetting Behaviors of Bitumen on Rough Aggregate Surfaces.

The interaction of bitumen colloidal (a form of heavy oil) with inorganic solids, for example, mineral aggregates, in both air and water environments is ubiquitous in nature and engineering. However, our knowledge of the underlying physical mechanism of bitumen-/solid-wetting phenomena is still very limited. The current study aims to reveal how the mineralogy and topography of aggregate surfaces affect the wetting and water-induced dewetting of bitumen on aggregate surfaces. For this, contact angle tests were performed to measure the surface energies of bitumen and aggregate surfaces varying in both mineralogy and roughness. Based on the measurements, both qualitative and quantitative analyses were conducted for the interaction of bitumen/aggregate interface in air and water environments. Complete wetting and complete dewetting hold for the air/bitumen/aggregate and water/bitumen/aggregate interfaces, respectively. The negative interfacial adhesive energy for the air/bitumen/aggregate interface and the interfacial debonding energy for the water/bitumen/aggregate interface imply that both bitumen wetting and water-induced bitumen dewetting on flat surfaces are thermodynamically favorable. The Wenzel model approximation holds up for the rough aggregate surface interface systems. The interfacial adhesive energy and interfacial debonding energy are enhanced geometrically by the roughness factor r, which indicates that the textured aggregate surface is in favor of force-induced interfacial cracking resistance but shows an adverse effect to moisture damage resistance. The findings from the current study provide guidelines for materials design in pavement engineering.

Boosting CO2 Electroreduction over a Cadmium Single-Atom Catalyst by Tuning of the Axial Coordination Structure.

Guided by first-principles calculations, it was found that Cd single-atom catalysts (SACs) have excellent performance in activating CO2 , and the introduction of axial coordination structure to Cd SACs cannot only further decrease the free energy barrier of CO2 reduction, but also suppress the hydrogen evolution reaction (HER). Based on the above discovery, we designed and synthesized a novel Cd SAC that comprises an optimized CdN4 S1 moiety incorporated in a carbon matrix. It was shown that the catalyst exhibited outstanding performance in CO2 electroreduction to CO. The faradaic efficiency (FE) of CO could reach up to 99.7 % with a current density of 182.2 mA cm-2 in a H-type electrolysis cell, and the turnover frequency (TOF) value could achieve 73000 h-1 , which was much higher than that reported to date. This work shows a successful example of how to design highly efficient catalysts guided by theoretical calculations.

Highly Efficient CO2 Electroreduction to Methanol through Atomically Dispersed Sn Coupled with Defective CuO Catalysts.

Using renewable electricity to drive CO2 electroreduction is an attractive way to achieve carbon-neutral energy cycle and produce value-added chemicals and fuels. As an important platform molecule and clean fuel, methanol requires 6-electron transfer in the process of CO2 reduction. Currently, CO2 electroreduction to methanol suffers from poor efficiency and low selectivity. Herein, we report the first work to design atomically dispersed Sn site anchored on defective CuO catalysts for CO2 electroreduction to methanol. It exhibits high methanol Faradaic efficiency (FE) of 88.6 % with a current density of 67.0 mA cm-2 and remarkable stability in a H-cell, which is the highest FE(methanol) with such high current density compared with the results reported to date. The atomic Sn site, adjacent oxygen vacancy and CuO support cooperate very well, leading to higher double-layer capacitance, larger CO2 adsorption capacity and lower interfacial charge transfer resistance. Operando experiments and density functional theory calculations demonstrate that the catalyst is beneficial for CO2 activation via decreasing the energy barrier of *COOH dissociation to form *CO. The obtained key intermediate *CO is then bound to the Cu species for further reduction, leading to high selectivity toward methanol.

Rapid Multi-Sensor Feature Fusion Based on Non-Stationary Kernel JADE for the Small-Amplitude Hunting Monitoring of High-Speed Trains.

Joint Approximate Diagonalization of Eigen-matrices (JADE) cannot deal with non-stationary data. Therefore, in this paper, a method called Non-stationary Kernel JADE (NKJADE) is proposed, which can extract non-stationary features and fuse multi-sensor features precisely and rapidly. In this method, the non-stationarity of the data is considered and the data from multi-sensor are used to fuse the features efficiently. The method is compared with EEMD-SVD-LTSA and EEMD-JADE using the bearing fault data of CWRU, and the validity of the method is verified. Considering that the vibration signals of high-speed trains are typically non-stationary, it is necessary to utilize a rapid feature fusion method to identify the evolutionary trends of hunting motions quickly before the phenomenon is fully manifested. In this paper, the proposed method is applied to identify the evolutionary trend of hunting motions quickly and accurately. Results verify that the accuracy of this method is much higher than that of the EEMD-JADE and EEMD-SVD-LTSA methods. This method can also be used to fuse multi-sensor features of non-stationary data rapidly.

Electrosynthesis of a Defective Indium Selenide with 3D†Structure on a Substrate for Tunable CO2 Electroreduction to Syngas.

Syngas (CO/H2 ) is a feedstock for the production of a variety of valuable chemicals and liquid fuels, and CO2 electrochemical reduction to syngas is very promising. However, the production of syngas with high efficiency is difficult. Herein, we show that defective indium selenide synthesized by an electrosynthesis method on carbon paper (γ-In2 Se3 /CP) is an extremely efficient electrocatalyst for this reaction. CO and H2 were the only products and the CO/H2 ratio could be tuned in a wide range by changing the applied potential or the composition of the electrolyte. In particular, using nanoflower-like γ-In2 Se3 /CP (F-γ-In2 Se3 /CP) as the electrode, the current density could be as high as 90.1 mA cm-2 at a CO/H2 ratio of 1:1. In addition, the Faradaic efficiency of CO could reach 96.5 % with a current density of 55.3 mA cm-2 at a very low overpotential of 220 mV. The outstanding electrocatalytic performance of F-γ-In2 Se3 /CP can be attributed to its defect-rich 3D structure and good contact with the CP substrate.

Hollow Metal-Organic-Framework-Mediated In†Situ Architecture of Copper Dendrites for Enhanced CO2 Electroreduction.

Electrocatalytic reduction of CO2 to a single product at high current densities and efficiencies remains a challenge. However, the conventional electrode preparation methods, such as drop-casting, usually suffer from low intrinsic activity. Herein, we report a synthesis strategy for preparing heterogeneous electrocatalyst composed of 3D hierarchical Cu dendrites that derived from an in situ electrosynthesized hollow copper metal-organic framework (MOF), for which the preparation of the Cu-MOF film took only 5 min. The synthesis strategy preferentially exposes active sites, which favor's the reduction of CO2 to formate. The current density could be as high as 102.1 mA cm-2 with a selectivity of 98.2 % in ionic-liquid-based electrolyte and a commonly used H-type cell.

Boosting CO2 Electroreduction on N,P-Co-doped Carbon Aerogels.

Electroreduction of CO2 to CO powered by renewable electricity is a possible alternative to synthesizing CO from fossil fuel. However, it is very hard to achieve high current density at high faradaic efficiency (FE). Here, the first use of N,P-co-doped carbon aerogels (NPCA) to boost CO2 reduction to CO is presented. The FE of CO could reach 99.1 % with a partial current density of -143.6 mA cm-2 , which is one of the highest current densities to date. NPCA has higher electrochemical active area and overall electronic conductivity than that of N- or P-doped carbon aerogels, which favors electron transfer from CO2 to its radical anion or other key intermediates. By control experiments and theoretical calculations, it is found that the pyridinic N was very active for CO2 reduction to CO, and co-doping of P with N hinder the hydrogen evolution reaction (HER) significantly, and thus the both current density and FE are very high.

Highly Efficient Electroreduction of CO2 to C2+ Alcohols on Heterogeneous Dual Active Sites.

Electroreduction of CO2 to liquid fuels such as ethanol and n-propanol, powered by renewable electricity, offers a promising strategy for controlling the global carbon balance and addressing the need for the storage of intermittent renewable energy. In this work, we discovered that the composite composed of nitrogen-doped graphene quantum dots (NGQ) on CuO-derived Cu nanorods (NGQ/Cu-nr) was an outstanding electrocatalyst for the reduction of CO2 to ethanol and n-propanol. The Faradaic efficiency (FE) of C2+ alcohols could reach 52.4 % with a total current density of 282.1 mA cm-2 . This is the highest FE for C2+ alcohols with a commercial current density to date. Control experiments and DFT studies show that the NGQ/Cu-nr could provide dual catalytic active sites and could stabilize the CH2 CHO intermediate to enhance the FE of alcohols significantly through further carbon protonation. The NGQ and Cu-nr had excellent synergistic effects for accelerating the reduction of CO2 to alcohols.