铜基催化剂电催化高效还原CO_(2)制备C_(2+)产物的调控策略

Efficient strategies for promoting the electrochemical reduction of CO_(2)to C_(2+)products over Cu‐based catalysts

电催化CO_(2)还原,可利用太阳能、风能等可再生能源产生的清洁电能驱动CO_(2)在常温常压下绿色高效地转化为甲烷,甲醇、乙烯和乙醇等化学品.其中,多碳产物(C_(2+)产物)因能量密度大、附加值高而备受关注.Cu可以有效吸附中间体CO,促进C-C键偶联,是目前公认的可以有效催化CO_(2)转化为C_(2+)还原产物的金属,但反应涉及多电子转移、质子耦合、路径复杂,加之水相体系中析氢副反应的影响,C_(2+)产物选择性差.本文以CO_(2)还原过程中的四个关键步骤为主线,综述了Cu基催化剂表面结构的改性策略,以提高CO_(2)还原制备C_(2+)产物性能,并深入分析了催化剂表面结构与性能之间的构效关系.(1)抑制析氢:通过有机层修饰及形貌调控对催化剂表面进行疏水改性,抑制H2O传输,同时促进CO_(2)扩散.(2)促进CO_(2)吸附活化:Cu与CO_(2)捕获材料复合,可以有效促进CO_(2)吸附;卤素离子可以提供孤对电子给CO_(2),形成X-C键(X=F^(-),Cl^(-),Br^(-),I^(-)),促进CO_(2)的吸附及活化.(3)调控CO中间体的生成及吸附性能:Cu与CO高选择性催化剂复合构建双功能串联催化剂,可以有效提高催化剂表面CO浓度及覆盖度;催化剂表面增强的局部热-电场效应可促进CO中间体的吸附及耦合;线性吸附的CO和桥式吸附的CO共存,以及低频线性吸附的CO可以有效进行耦合,促进C_(2+)产物生成.(4)促进C-C耦合成键:C-C耦合是生成C_(2+)产物最关键的一步,限域形貌结构,可以有效提高中间产物在催化剂表面的浓度及保留时间,提高C-C耦合几率;氧化物衍生铜、杂原子掺杂和有机分子修饰等可以调控催化剂表面铜物种价态,Cu^(δ+)和Cu^(0)协同,可以促进CO_(2)活化,增强CO中间体吸附,降低C-C耦合能垒;空位、晶界和台阶等缺陷可以改变C1中间体在催化剂表面的吸附性能,降低C-C耦合能垒;Cu单原子催化剂较高的原子利用率以及Cu原子与配位原子协同可有效促进C-C耦合,调节单一C_(2+)产物选择性;异质界面可以改变本征电导率,提高电荷转移速率,调节催化剂表面电子结构,进一步调控对中间体的吸附,促进C-C耦合几率.催化剂表面结构重组、化学态变化、积碳、Fe/Ni等杂质沉积和微量有机杂质吸附等会影响催化反应稳定性.构建Cu-载体相互作用及限域结构,引入缺陷位点、原子掺杂、有机分子修饰和纯化电解质溶液等方法可以有效缓解催化剂失活.此外,本文指出了CO_(2)还原制C_(2+)产物领域未来潜在的研究方向:(1)开发时间及空间分辨的原位谱学技术,结合理论计算研究催化剂的动态变化及中间体的演变过程,揭示催化反应机理,为实现单一C_(2+)产物高选择性,设计高效率及高稳定性催化剂提供理论指导;(2)深入认识催化反应失活机理,设计新型催化剂及反应器,提高整个体系反应稳定性;(3)关注阳极反应,尝试新的氧化反应替代能耗较高的析氧反应;、设计高稳定的阳极反应催化剂;开发化学及机械稳定的离子交换膜,减少CO_(2)向阳极的扩散,提高整体反应能效及经济性等.

Cu‐based catalysts have been widely studied for the electrochemical CO_(2)reduction reaction(CO_(2)RR)to yield high‐value‐added products with two or more carbons(C_(2+)products).The rational design of Cu‐based catalysts is critical to improve the selectivity and energy efficiency of the CO_(2)RR‐to‐C_(2+)process.Herein,we review recent advances in Cu‐based catalysts with surface modification for four crucial factors in CO_(2)RR‐to‐C_(2+)based on briefly analyzing the reaction mechanisms:(1)surface hydrophobization to inhibit the hydrogen evolution reaction;(2)introduction of CO_(2)‐capture materials,halide‐ion doping,and Cu^(δ+)/Cu^(0)synergy to promote CO_(2)adsorption and activation;(3)bifunctional catalysts and locally enhanced electric–thermal fields for modulating CO generation and adsorption;and(4)development of confinement structures and heterostructures,addition of oxidation states or defects,and use of single‐atoms with different coordination environments to promote carbon–carbon coupling.In particular,the relationships between the surface properties of Cu‐based catalysts and improved activity and C_(2+)selectivity in CO_(2)RR are discussed,along with strategies for enhancing the stability of the catalyst.Furthermore,the current challenges and potential strategies for future CO_(2)RR‐to‐C_(2+)research are discussed in this review.