CH4, as an important clean fuel and hydrogen carrier, its production from CO2 driven by renewable energy could simultaneously achieve energy supply, CO2 emission reduction, and renewable energy consumption, which is of great significance. Electrocatalytic CH4 production relies on high-valence Cu species for realizing multielectron reduction, while facing inadequate performance stability due to the reconstruction tendency of Cu. Herein, an amorphous CuOx-SiO2 catalyst (amorCuOx-SiO2) is synthesized via an electrostatic interaction strategy to construct stable Cu2+ active sites for efficient electrocatalytic CH4 production. AmorCuOx-SiO2 shows a good reconstruction resistance during electroreduction, confirmed via X-ray absorption spectroscopy studies, endowing a 63.7% CH4 faradaic efficiency at 500 mA cm- 2, which is 7.8 folds of crystalized CuOx-SiO2 (crysCuOx-SiO2). Theoretical calculations revealed that stable Cu2+ active sites enhanced *CO adsorption and were more susceptible for further hydrogenation, thus promoting the CO2-to-CH4 conversion. Our findings provide a feasible strategy for developing reconstruction-resistant electrocatalysts for advanced CH4 production performance.

CO2 electroreduction to valuable chemicals using renewable energy is a prospective strategy for realizing carbon neutrality, however, exclusive production of formate under high industry current densities (> 200 mA cm(-2)) remains challenging. Herein, we presented a lattice-dislocated hollow-fiber Bi via in situ reconstruction to make a breakthrough for such issue. A nearly perfect formate Faradaic efficiency of > 99.5 % was realized with a current density of 1 A cm(-2), completely suppressing CO and hydrogen generation. Finite element simulations showed high-concentration CO2 feeding was realized even though at ampere-level current density. And density functional theory calculations revealed that the abundant dislocated lattice acting as the active sites boosted the production of OCHO* . Thus, the synergistic combination of penetration and strain effects induced by the latticedislocated Bi hollow penetration electrode is responsible for such remarkable activities. This work represents a large step toward the application of direct conversion of CO2.

Photocatalytic conversion of methane (CH4) to value-added chemicals using H2O as the oxidant under mild conditions is a desired sustainable pathway for synthesizing commodity chemicals. However, controlling product selectivity while maintaining high product yields is greatly challenging. Herein, we develop a highly efficient strategy, based on the precise control of the types of nitrogen dopants, and the design of photocatalysts, to achieve high selectivity and productivity of oxygenates via CH4 photocatalytic conversion. The primary product (methanol) is obtained in a high yield of 159.8 mu mol & sdot;g(-1)& sdot;h(-1) and 47.7% selectivity, and the selectivity of oxygenate compounds reached 92.5%. The unique hollow porous structure and substituted nitrogen sites of nitrogen-doped TiO2 synergistically promote its photo-oxidation performance. Furthermore, in situ attenuated total reflectance Fourier transform infrared spectroscopy provides direct evidence of the key intermediates and their evolution for producing methanol and multicarbon oxygenates. This study provides insights into the mechanism of photocatalytic CH4 conversion.

Artificial photosynthesis, which utilizes sunlight to produce value-added chemicals and fuels from CO2, is a promising strategy to storage fluctuating solar energy and to realize zero carbon cycle simultaneously. While selective C2+ production via CO2 photoelectrocatalytic conversion remains a challenge due to the sluggish C -C coupling kinetics over current artificial photosynthesis catalysts. Herein, we present a carbon @ silicon carbide (C@SiC) catalyst for ambient CO2 photoelectric reduction under simulated solar irradiation, giving a CO2 conversion rate of 487 mu mol center dot gcat - 1 center dot h- 1 with an ethanol selectivity of 87.8%. The optimal sp2/sp3 carbon ratio of carbon layer not only facilitates the photo -generated electrons transfer from SiC to carbon layer, but also favors the C -C coupling kinetics of key intermediates for efficient CO2 to ethanol conversion.

Electroreduction of CO2 to chemical fuels is desirable for the economically viable use of CO2 and consumption of renewable electricity. Efficient production of C2+ on Cu-based catalysts remains a challenge. Herein, a copper hollow fiber penetration electrode with a striking C-C coupling capability by virtue of modulating the electronic states through halide ion coordinated adsorption. An efficient C2+ production with a FE of 68.8 % at 2.1 A cm-2 in 3.0 M KI and remained stable during 120-h electrolysis at 2.0 A cm-2, outperforming reported catalytic performance, which is the result of combined effect of penetration effect and halide ion coordinated adsorption, which promotes the transfer of electrons to CO2, reduces the C-C coupling energy and suppresses proton adsorption, thereby reducing hydrogen evolution.

Sufficient CO 2 feeding induced by the hollow-fiber penetration configuration greatly improved CO 2 coverage on Cu active sites in strong acids, favoring CO 2 activation, *CHO and *CO formation, and their couplings to C 2+ products.

Cu-based catalysts for efficient C2+ production from CO2 electrocatalytic reduction reaction (CO2ERR) exhibit significant promise, but still suffer from ambiguous mechanisms due to the intrinsic structure instability during electroreduction. Herein, we report an oxide-derived copper nanowire bundle (OD-Cu NWB) for efficient CO2ERR to C2+ products. OD-Cu NWBs with a well-preserved nanowire bundle morphology lead to promoted multi-carbon production compared to commercial copper powders. The formation of OD-Cu NWBs shows a great dependence on the precipitation/calcination temperatures and per-reduction potentials, which further influence the ultimate CO2ERR performance correspondingly. The optimized preparation parameters for the formation of a well-ordered nanowire bundle morphology are found, leading to a preferred C2+ production ability. Besides the nanowire bundle morphology, the oxide-derived Cu essence of OD-Cu NWBs with stabilized Cu+ species from per-reduction also promotes the CO2ERR activity and facilitates the C-C coupling of key intermediates for C2+ production. This work provides a facile strategy and inspiration for CO2ERR catalyst developments targeting high-valued multi-carbon products.

Electroreduction of CO2 to CO is a promising route for greenhouse gas resource utilization, but it still suffers from impractical current density and poor durability. Here, a nanosheet shell (NS) vertically standing on the Ag hollow fiber (NS@Ag HF) surface formed by electrochemical surface reconstruction is reported. As-prepared NS@Ag HF as a gas penetration electrode exhibited a high CO faradaic efficiency of 97% at an ultra-high current density of 2.0 A cm(-2) with a sustained performance for continuous >200 h operation. The experimental and theoretical studies reveal that promoted surface electronic structures of NS@Ag HF by the nanosheets not only suppress the competitive hydrogen evolution reaction but also facilitate the CO2 reduction kinetics. This work provides a feasible strategy for fabricating robust catalysts for highly efficient and stable CO2 reduction.

Efficient C2+ production from CO2 electrocatalytic reduction exhibits significant promise but suffers from low selectivity and undesired side reactions. Stepwise electroreductions of CO2 to CO and then to C2+ products can benefit from the perfect cooperation of the first high CO production efficiency and the subsequent favorable C-C coupling kinetics of CO. Herein, by virtue of serial Ag and Cu hollow-fiber penetration electrodes, a highefficiency CO2 electroreduction to C2+ products is achieved with a partial current density of 1.8 A cm-2 and a faradaic efficiency of 90.5 %. Experimental results and density functional theory calculations demonstrate that the synergetic combination of unique penetration effect induced by hierarchical micro/nanostructured hollow fiber configurations and regulated electronic structures by chloride ion adsorption, is responsible for the superior activity. This work provides a facile tactic and encouraging headway to design applicable efficient CO2 electrocatalytic reduction systems towards high-value C2+ chemicals.

The urgent need for efficiency improvement in the oxide-zeolite bifunctional syngas-to-hydrocarbon catalysis necessitates in-depth mechanistic insights into this reaction, especially for the initial syn- gas conversion over the oxide component, which remains poor. Herein, we comprehensively investigated syngas conversion over a representative ZnAl2O4 spinel oxide with state-of-the-art solid- state NMR technologies. Notably, specific surface dual active sites for syngas activation with-AlIV-OH center dot center dot center dot ZnIII- structure were unam- biguously identified. More importantly, the dynamic evolution of the reaction intermediates and active sites during the reaction pro- cess was elaborated at atomic level by a series of double resonance and multi-dimensional correlation NMR experiments. In combina- tion with in situ spectroscopic characterizations, we revealed the full cycle of the formate-methoxy-based pathway for the syngas- to-methanol conversion via synergistic interplay of the dual active sites. The in-depth atomic-level understanding of the catalytic mechanism will be beneficial to further rational design of high- performance catalysts for syngas conversion.

Transition metal catalyst-based electrocatalytic CO2 reduction is a highly attractive approach to fulfill the renewable energy storage and a negative carbon cycle. However, it remains a great challenge for the earth-abundant VIII transition metal catalysts to achieve highly selective, active, and stable CO2 electroreduction. Herein, bamboo-like carbon nanotubes that anchor both Ni nanoclusters and atomically dispersed Ni-N-C sites (NiNCNT) are developed for exclusive CO2 conversion to CO at stable industry-relevant current densities. Through optimization of gas-liquid-catalyst interphases via hydrophobic modulation, NiNCNT exhibits as high as Faradaic efficiency (FE) of 99.3% for CO formation at a current density of -300 mA·cm-2 (-0.35 V vs reversible hydrogen electrode (RHE)), and even an extremely high CO partial current density (jCO) of -457 mA·cm-2 corresponding to a CO FE of 91.4% at -0.48 V vs RHE. Such superior CO2 electroreduction performance is ascribed to the enhanced electron transfer and local electron density of Ni 3d orbitals upon incorporation of Ni nanoclusters, which facilitates the formation of the COOH* intermediate.

Electrochemical conversion of carbon dioxide (CO2) to valuable fuels driven by renewable electricity exhibits significant potential for achieving carbon neutrality. Bismuth (Bi) possesses the reliable capability of electrocatalyzing CO2 to formate, and high formate faradaic efficiencies have been realized over Bi-based catalysts, but industry-level large current densities with high conversion rates at mild conditions remain challenging yet. Herein we present a bismuth hollow fiber (Bi HF) as a gas penetration electrode (GPE) that efficiently reduces CO2 with a formate faradaic efficiency of 93% and a current density of 1.13 A cm-2 at -1.26 V (vs. RHE), corresponding to a CO2 conversion rate of 37% under ambient temperature and pressure. Finite element analysis (FEA) and density functional theory (DFT) demonstrate that the synergetic combination of unlimited CO2 feeding to triphasic interface reactions and selective reduction induced by contractive Bi-Bi bond is responsible for the superior activity of Bi HF.

Using sunlight to produce valuable chemicals and fuels from carbon dioxide (CO2), i.e., artificial photosynthesis (AP) is a promising strategy to achieve solar energy storage and a negative carbon cycle. However, selective synthesis of C-2 compounds with a high CO2 conversion rate remains challenging for current AP technologies. We performed CO2 photoelectroreduction over a graphene/silicon carbide (SiC) catalyst under simulated solar irradiation with ethanol (C2H5OH) selectivity of>99 % and a CO2 conversion rate of up to 17.1 mmol g(cat)(-1) h(-1) with sustained performance. Experimental and theoretical investigations indicated an optimal interfacial layer to facilitate the transfer of photogenerated electrons from the SiC substrate to the few-layer graphene overlayer, which also favored an efficient CO2 to C2H5OH conversion pathway.

Increasing research has shown that active sites in zeolite catalysts are structurally and spatially complex, which poses challenges to effective characterization methods, especially for the high demand in pursuing molecular-level understanding of the nature of the active sites. Herein, using trimethylphosphine (TMP) as a probe molecule, the species giving rise to 31P NMR resonance at -58 ppm, which is typically recognized as TMP physically adsorbed on unreactive species, is found to possess more catalytic meanings as the TMP bindings are proven to be strong. NMR-assisted 31P-27Al internuclear distance measurement and a comprehensive set of two-dimensional (2D) heteronuclear correlation (HETCOR) (1H -31P, 31P-27Al, and 27Al-1H) NMR experiments explicitly demonstrate that the TMP-binding site is neither a bridging acid site (BAS) nor a Lewis acid site (LAS), but special Al-OH groups, i.e., Al-OH center dot center dot center dot P(CH3)3. Further evidence including postsynthetic treatments and 31P -31P homonuclear NMR correlation experiments exclusively shows that these Al-OH groups originate from the partially bonded framework Al(IV)-2 species recently reported. By linking IR and 1H NMR spectroscopy, new insights of Al(IV)-2 (essentially Bri nsted sites) and framework-bonded Lewis sites are provided. Finally, 31P -31P homonuclear correlation experiment was capable of ruling out chemical exchange from spin diffusion and thereby exclusively demonstrates that the "BAS and Al(IV)-2" is in shorter spatial distance than that of "BAS and LAS".

Partial positive valence Cu (Cu delta+) sites on Cu-based electrocatalysts are important for C-C coupling to form C2+ products; however, maintaining the stability of Cu delta+ remains a challenge. Herein, an ultrastable Cu delta+ (0 < delta < 1) site over the copper penetration electrode was constructed using boron to tailor the *CO adsorption strength and configuration for facilitating C-C coupling, which achieves a C2+ Faradaic efficiency (FE) of 78.9% at -0.91 V (vs reversible hydrogen electrode), of which the ethanol FE reaches 52.4% with an ultrahigh partial current density of 1.25 A cm(-2), far outperforming state-of-the-art electrocatalysts, corresponding to the ethanol cathodic energy efficiency (CEE) of 27.7%. Spectroscopy and computation results show that introducing boron to optimize the coordination numbers and oxidation states of surface Cu atoms enables enrichment of locally asymmetric *COatop and *CHO intermediates to trigger asymmetric C-C coupling to form ethanol.

The reconstruction of Cu-based catalysts would greatly affect the carbon dioxide electrocatalytic reduction reaction (CO2ERR) activity and product selectivity toward C2+ production. Herein, we report phosphate-derived copper-based catalysts (PD-CuOx/C) for efficient CO2ERR toward C2+ production synthesized via in situ reconstruction. Detailed studies about the morphology and structure evolution during reconstruction procedures of PD-CuOx/C samples are conducted, revealing the formation of copper phosphate nanosheets as well as the corresponding well-dispersed Cu nanoparticles resulting from electroreduction. Such well-dispersed Cu nanoparticles in PD-CuOx/C promote the C-C coupling of key CO2ERR intermediates toward C2+ productions, resulting in an elevated FEC2+ of 45% compared to referencing non-phosphate-derived CuOx/C samples. The facilitated CO2ERR performance to form C2+ products is attributed to not only the phosphate-derived Cu essence but also the stabilized Cu+ species in PD-CuOx/C. This work provides inspiration and encourages headway to design new derived Cu electrocatalysts with efficient CO2ERR ability toward high-value C2+ chemical productions.

Electrochemical reduction of carbon dioxide (CO2) to value-added chemicals is an attractive route to utilize CO2 as resources and contribute carbon neutrality. As one of common products from CO2 electroreduction, formate is an economically viable liquid fuel under current techno-economic conditions. However, the current densities of CO2 electroreduction remain insufficient yet challenging due to the limited CO2 solubility and the unclear mechanisms on electrocatalyst surface. Herein, an exquisite Cu2O surface on copper-based hollow fiber (HF) was developed as a gas penetration electrode for CO2 electroreduction that can enhance mass transfer and boost three-phase interface reactions. Moreover, the (111)-oriented Cu2O and abundant oxygen vacancies synergisti-cally promoted CO2 electrochemical reduction to formate, resulting in a high formate Faradaic efficiency of 92.3% with a partial current density of 84.4 mA center dot cm(-2) at a potential of -1.18 V vs. RHE. Operando Raman spectra suggested that carboxylate anion *CO2- was the key intermediate of CO2 reduction to formate, which was further reduced to formate via the subsequent proton-electron transfer.

Improving the scale and effectiveness of China's energy conservation and environmental protection fiscal expenditure is crucial to enhancing the capacity of ecological and environmental governance of China, considering the dual perspectives of pollution governance and public health. This article first explains the mechanism by which national energy conservation and environmental protection fiscal expenditure can improve pollution control and promote public health. Secondly, this article scrutinizes the current status and limitations of China's fiscal expenditure, highlighting the contribution of fiscal expenditure in the construction of ecological civilization from the standpoints of environmental governance and public health. Additionally, this study empirically uses DEA to measure the efficiency of the government's fiscal expenditure. Conclusions found that: First, environmental protection fiscal expenditure is mainly focused on technological transformation and pollution control, while relatively little is spent on public health protection. Second, the efficiency of environmental protection fiscal funds is relatively low. These suggestions aim to optimize the positive impact of energy conservation and environmental protection fiscal expenditure for improving pollution governance and promoting public health.

Carbon dioxide electroreduction driven by renewable electricity into high‐value chemicals enables energy storage while contributing to climate change mitigation. Herein, a CuPd bimetallic catalyst is developed by electrodeposition for efficient CO2 electroreduction, achieving a C2+ Faradaic efficiency as high as 75.6% with a current density of −200 mA cm−2 at −1.15 V versus reversible hydrogen electrode. Upon incorporation of Pd, the average d‐band center of the CuPd bimetallic catalyst downward shifts relative to the Fermi level, making the adsorbed CO intermediates active for further C–C coupling. Theoretical calculations confirm that CO generated on the Pd domain can spill over to the CuPd interface for C–C coupling with a lower energy barrier, further promoting the formation of C2+ compounds. This study provides insights into the rational design of Cu‐based bimetallic catalysts for highly efficient CO2 electroreduction to multicarbon products.

As one of the most important derivatives of propylene, the production of propylene oxide (PO) is severely restricted. The traditional chlorohydrin process is being eliminated due to environmental concerns, while processes such as Halcon and hydrogen peroxide epoxidation are limited by cost and efficiency, making it difficult to meet market demand. Therefore, achieving PO production through clean and efficient technologies has received extensive attention, and halogen-mediated electrochemical epoxidation of alkene is considered to be a desirable technology for the production of alkylene oxide. In this work, we used electrochemical methods to synthesize PO in halogen-mediated systems based on a RuO2-loaded Ti (RuO2/Ti) anode and screened out two potential mediated systems of chlorine (Cl) and bromine (Br) for the electrosynthesis of PO. At a current density of 100 mA·cm-2, both Cl- and Br-mediated systems delivered PO Faradaic efficiencies of more than 80%. In particular, the Br-mediated system obtained PO Faradaic efficiencies of more than 90% at lower potentials (≤1.5 V vs RHE) with better electrode structure durability. Furthermore, detailed product distribution investigations and DFT calculations suggested hypohalous acid molecules as key reaction intermediates in both Cl- and Br-mediated systems. This work presents a green and efficient PO production route with halogen-mediated electrochemical epoxidation of propylene driven by renewable electricity, exhibiting promising potential to replace the traditional chlorohydrin process.